diff --git a/CRNs.xlsx b/CRNs.xlsx
index fce9463821a35b4b95c969566ce0f8db10327660..1a93ebdbc67f0515cc367786e6b1dfc01e2a5d78 100644
Binary files a/CRNs.xlsx and b/CRNs.xlsx differ
diff --git a/app.py b/app.py
index f1ebeef9aa91a6f1b5d9c670262c84a2722281bb..2ea6b9064a30363bba50ab69114bd65aac4209b2 100644
--- a/app.py
+++ b/app.py
@@ -1084,6 +1084,12 @@ def _inline_math_to_unicode(text: str) -> str:
return re.sub(r'\$([^\$]+)\$', _convert, text)
+#: Tokens the formula pattern below matches but which are not chemical formulas:
+#: retrieval-channel and method names shown in the evidence list. Compared
+#: case-insensitively.
+_NON_FORMULA_TOKENS = frozenset({"BGE-M3", "BM25"})
+
+
def _normalize_report_formula_display(text: str) -> str:
if not text:
return ""
@@ -1103,6 +1109,11 @@ def _normalize_report_formula_display(text: str) -> str:
token = match.group(0)
if len(token) < 2:
return token
+ # Retrieval-channel and method names are uppercase-plus-digits, which is
+ # exactly the shape of a formula: without this guard "BGE-M3" renders as
+ # "BGE-M₃" and "BM25" as "BM₂₅" in the evidence list.
+ if token.upper() in _NON_FORMULA_TOKENS:
+ return token
prefix = ""
lowered = token.lower()
for phase_prefix, symbol in (("alpha-", "α-"), ("beta-", "β-")):
@@ -2382,7 +2393,24 @@ def _render_report_html(report_item):
if scope_note:
md_parts.append("### Evidence Scope\n\n> " + scope_note)
- retrieved_evidence_lines = []
+ # Grouped by reaction step, not by reference. Listing each reference
+ # separately repeated one conclusion once per supporting paper -- five
+ # identical "As4S4 -> p-As4S4: direct" lines in one report -- which buried
+ # the question a reader actually has: is this step supported, and by whom.
+ # Each step is stated once, with the references and channels that back it.
+ def _add_support(bucket, key, reference_index, channels):
+ entry = bucket.setdefault(
+ key, {"refs": [], "channels": []}
+ )
+ if reference_index not in entry["refs"]:
+ entry["refs"].append(reference_index)
+ for channel in channels:
+ if channel not in entry["channels"]:
+ entry["channels"].append(channel)
+
+ step_support = {}
+ endpoint_support = {}
+ unclassified_support = {}
for index, block in enumerate(evidence_blocks, 1):
if not isinstance(block, dict):
continue
@@ -2391,47 +2419,65 @@ def _render_report_html(report_item):
)
if not snippet:
continue
- status = str(block.get("evidence_status") or "unclassified").replace("_", " ")
- # Human-readable classification for researchers rather than a developer
- # log line: name the actual reaction (reactant -> product) each reference
- # supports, spell the verdict as a phrase, and list the retrieval
- # channels on their own line with display names (bge_m3 -> BGE-M3).
- edge_lines = []
- endpoint_support = False
- for match in block.get("edge_matches") or []:
- if not isinstance(match, dict):
- continue
- if match.get("evidence_scope") == "pathway_endpoint":
- endpoint_support = True
- continue
- reactant = to_unicode_subscript(str(match.get("reactant") or ""))
- product = to_unicode_subscript(str(match.get("product") or ""))
- verdict = str(match.get("verdict") or "unclassified").replace("_", " ")
- phrase = "direct literature support" if verdict == "direct" else f"{verdict} support"
- edge_lines.append(f"{reactant} → {product}: {phrase}" if reactant and product else phrase)
- # The same edge can match in several snippets of one reference; show each
- # classification once (it was being repeated).
- edge_lines = list(dict.fromkeys(edge_lines)) or [status]
- detail_lines = []
- if endpoint_support:
- detail_lines.append("Additional support: pathway endpoints")
- origins = list(dict.fromkeys(
+ channels = list(dict.fromkeys(
_RETRIEVAL_CHANNEL_LABELS.get(name, name)
for item in block.get("snippets") or []
if isinstance(item, dict) and item.get("retrieval_origin")
for name in [str(item.get("retrieval_origin") or "").replace("_", " ")]
))
- if origins:
- detail_lines.append("Retrieval channels: " + "; ".join(origins))
- # The classification stays; the quoted passage does not. It tells a reader
- # which reaction a reference supports and how it was found. The passage
- # behind it runs to 900 characters, several per report, and the exported
- # PDF already carries every one of them under "Evidence Assessment".
- block_md = f"[{index}] **{edge_lines[0]}**"
- tail = edge_lines[1:] + detail_lines
- if tail:
- block_md += " \n" + " \n".join(tail)
- retrieved_evidence_lines.append(block_md)
+ matches = [m for m in (block.get("edge_matches") or []) if isinstance(m, dict)]
+ if not matches:
+ status = str(block.get("evidence_status") or "unclassified").replace("_", " ")
+ _add_support(unclassified_support, status, index, channels)
+ continue
+ for match in matches:
+ verdict = str(match.get("verdict") or "unclassified").replace("_", " ")
+ reactant = to_unicode_subscript(str(match.get("reactant") or ""))
+ product = to_unicode_subscript(str(match.get("product") or ""))
+ if match.get("evidence_scope") == "pathway_endpoint":
+ _add_support(
+ endpoint_support, (reactant, product, verdict), index, channels
+ )
+ continue
+ try:
+ order = int(match.get("edge_index") or 0)
+ except (TypeError, ValueError):
+ order = 0
+ _add_support(
+ step_support, (order, reactant, product, verdict), index, channels
+ )
+
+ def _support_detail(entry):
+ lines = ["Sources: " + " ".join(f"[{n}]" for n in sorted(entry["refs"]))]
+ if entry["channels"]:
+ lines.append("Retrieval: " + "; ".join(entry["channels"]))
+ return lines
+
+ retrieved_evidence_lines = []
+ for (_order, reactant, product, verdict) in sorted(step_support):
+ entry = step_support[(_order, reactant, product, verdict)]
+ phrase = (
+ "direct literature support" if verdict == "direct" else f"{verdict} support"
+ )
+ heading = f"{reactant} → {product} — {phrase}" if reactant and product else phrase
+ retrieved_evidence_lines.append(
+ f"**{heading}** \n" + " \n".join(_support_detail(entry))
+ )
+ for (reactant, product, verdict) in sorted(endpoint_support):
+ entry = endpoint_support[(reactant, product, verdict)]
+ label = f"Overall {reactant} → {product}" if reactant and product else "Overall pathway"
+ phrase = (
+ "pathway-endpoint support" if verdict == "direct"
+ else f"pathway-endpoint {verdict} support"
+ )
+ retrieved_evidence_lines.append(
+ f"**{label} — {phrase}** \n" + " \n".join(_support_detail(entry))
+ )
+ for status in sorted(unclassified_support):
+ entry = unclassified_support[status]
+ retrieved_evidence_lines.append(
+ f"**{status}** \n" + " \n".join(_support_detail(entry))
+ )
if retrieved_evidence_lines:
md_parts.append(
"### Retrieved Literature Evidence\n\n"
diff --git a/chroma.sqlite3 b/chroma.sqlite3
index fe8d16defe8521104cd67a59347f0dbc9480679d..1ca9ecc7980ab71e9a6bd8c13432fef77484b2fe 100644
--- a/chroma.sqlite3
+++ b/chroma.sqlite3
@@ -1,3 +1,3 @@
version https://git-lfs.github.com/spec/v1
-oid sha256:d20c82236b019a159ad419b36c6f3e0f490437cac3c43174b64aa499c35019cf
+oid sha256:71a2ca162a767171d63c8a25878a4a4a8b36d9bf9d43cd5bb5b3d4c7c5f43327
size 26365952
diff --git a/precompute_rag_cache.py b/precompute_rag_cache.py
new file mode 100644
index 0000000000000000000000000000000000000000..a9860f36ef7a1a2f6cce52b888b5f5dc8fc699e7
--- /dev/null
+++ b/precompute_rag_cache.py
@@ -0,0 +1,93 @@
+"""Offline warm-up of the pathway report cache.
+
+Retrieval and evidence gating are deterministic in (path, corpus), but a full
+run costs minutes of CPU per path. This script computes every pathway report
+once, offline, so the running app serves them from cache instead of recomputing
+an identical answer on each request.
+
+Run it after the knowledge base changes (the cache key carries a corpus
+fingerprint, so stale entries are ignored automatically rather than served).
+
+ python precompute_rag_cache.py # all reachable targets
+ python precompute_rag_cache.py As2O3 PbO # only these targets
+
+Interrupting is safe: finished paths stay cached, so a re-run resumes.
+"""
+from __future__ import annotations
+
+import os
+import sys
+import time
+
+sys.path.insert(0, os.path.dirname(os.path.abspath(__file__)))
+
+# Some network node names carry zero-width characters, and the tracer prints the
+# target name on a miss. On a GBK console that print raises UnicodeEncodeError
+# and aborts the run, so force UTF-8 output and never fail on an odd glyph.
+for _stream in (sys.stdout, sys.stderr):
+ try:
+ _stream.reconfigure(encoding="utf-8", errors="replace")
+ except (AttributeError, ValueError):
+ pass
+
+
+def main(argv: list[str]) -> int:
+ from search_subgraph import CRNTracer, GRAPHML_PATH
+ from tracernet.crn import pathways as crn_pathways
+ from tracernet.crn.repository import CRNRepository
+ from rag_module import RAGService
+
+ project = os.path.dirname(os.path.abspath(__file__))
+ repository = CRNRepository.discover([project])
+ tracer = CRNTracer(GRAPHML_PATH, crn_repository=repository)
+ graph = tracer.G
+ service = RAGService(repository)
+ print(f"[init] graph={graph.number_of_nodes()} nodes, "
+ f"corpus signature={service._report_cache_signature()}", flush=True)
+
+ targets = argv or sorted(graph.nodes())
+ print(f"[plan] tracing {len(targets)} candidate targets ...", flush=True)
+
+ # Collect unique paths across every target. The same path is reachable from
+ # several targets, and computing it twice would cost minutes for nothing.
+ jobs: dict[str, tuple[str, object]] = {}
+ for target in targets:
+ try:
+ _resolved, _graph, _report, all_paths = crn_pathways.trace_material_pathways(
+ tracer, graph, target, max_depth=10, limit=100
+ )
+ except Exception as error: # a target with no upstream path is normal
+ print(f"[trace] {target}: skipped ({type(error).__name__})", flush=True)
+ continue
+ for info in all_paths or []:
+ path_str = info.get("path_str")
+ if path_str and path_str not in jobs:
+ jobs[path_str] = (info.get("source"), info.get("full_path"))
+ print(f"[plan] {len(jobs)} unique pathways to warm", flush=True)
+
+ started = time.time()
+ done = 0
+ for index, (path_str, (source, full_path)) in enumerate(jobs.items(), 1):
+ step = time.time()
+ try:
+ # Evidence only: the narrative is generated per request, so warming
+ # it here would be discarded work -- and with an API key configured
+ # it would spend one LLM call per path for nothing.
+ service.cached_path_evidence(source, path_str, full_path)
+ done += 1
+ status = "ok"
+ except Exception as error:
+ status = f"FAILED {type(error).__name__}: {error}"
+ elapsed = time.time() - step
+ total = time.time() - started
+ print(f"[{index}/{len(jobs)}] {elapsed:6.1f}s total {total/60:5.1f}m "
+ f"{status} {path_str[:90]}", flush=True)
+
+ print(f"[done] warmed {done}/{len(jobs)} pathways in "
+ f"{(time.time()-started)/60:.1f} minutes", flush=True)
+ print(f"[done] cache directory: {service._report_cache_dir()}", flush=True)
+ return 0
+
+
+if __name__ == "__main__":
+ raise SystemExit(main(sys.argv[1:]))
diff --git a/rag_module.py b/rag_module.py
index d91f187c22f66b9b67799360f3bcd2c0c72d5344..e8d3e2553edfb6de69ca96fe986c30ac18018089 100644
--- a/rag_module.py
+++ b/rag_module.py
@@ -2631,7 +2631,129 @@ include a "Validation note"; it is added automatically outside your paragraph.
"""
return list(candidates)[:max(0, int(output_top_k))]
+ def _report_cache_dir(self):
+ return os.getenv("RAG_REPORT_CACHE_DIR") or os.path.join(
+ os.path.dirname(os.path.abspath(__file__)), "rag_report_cache"
+ )
+
+ def _report_cache_signature(self):
+ """Corpus fingerprint, so a rebuilt knowledge base invalidates the cache.
+
+ A cached report is only valid for the corpus it was computed from. The
+ document count changes whenever papers are added or removed, which is
+ exactly when the stored evidence stops being reproducible.
+ """
+ count = self.collection_count
+ if count is None:
+ try:
+ collection = getattr(self.vector_db, "_collection", None) or self.chroma_collection
+ count = collection.count() if collection is not None else -1
+ except Exception:
+ count = -1
+ return f"docs={count}"
+
+ def _report_cache_key(self, root_material, path_str):
+ import hashlib
+
+ payload = "|".join([
+ str(root_material or ""),
+ str(path_str or ""),
+ self._report_cache_signature(),
+ ])
+ return hashlib.sha1(payload.encode("utf-8")).hexdigest()
+
def generate_report_for_path(self, root_material, path_str, full_path=None):
+ """Return the pathway report, reusing cached retrieval evidence.
+
+ Retrieval and evidence gating are deterministic in (path, corpus) yet cost
+ minutes of CPU, so recomputing them per request spends that time
+ reproducing an identical answer; they are cached on disk, keyed by path
+ and corpus fingerprint, so a changed knowledge base recomputes rather
+ than serving stale evidence. The narrative is deliberately NOT cached --
+ it is regenerated on every call so the wording is never frozen, which
+ costs seconds rather than minutes. Set RAG_REPORT_CACHE=0 to bypass.
+ """
+ cache_enabled = os.getenv("RAG_REPORT_CACHE", "1").strip().lower() not in (
+ "0", "false", "no"
+ )
+ evidence = self.cached_path_evidence(root_material, path_str, full_path)
+ return self._narrate_path_report(
+ evidence, root_material, path_str, full_path
+ )
+
+ def cached_path_evidence(self, root_material, path_str, full_path=None):
+ """Retrieval evidence for one path, computed once and cached on disk.
+
+ Exposed separately so the offline warm-up can fill the cache without
+ generating a narrative: narration is a per-request concern and, with an
+ API key configured, warming 88 paths through the full report path would
+ spend 88 LLM calls on text that is thrown away.
+ """
+ cache_enabled = os.getenv("RAG_REPORT_CACHE", "1").strip().lower() not in (
+ "0", "false", "no"
+ )
+ cache_file = None
+ evidence = None
+ if cache_enabled:
+ cache_file = os.path.join(
+ self._report_cache_dir(),
+ f"{self._report_cache_key(root_material, path_str)}.json",
+ )
+ try:
+ if os.path.isfile(cache_file):
+ with open(cache_file, "r", encoding="utf-8") as handle:
+ cached = json.load(handle)
+ stored = cached.get("evidence")
+ # Every field the narrative half reads must be present, or a
+ # cache written by an older layout would fail mid-report.
+ if isinstance(stored, dict) and all(
+ key in stored
+ for key in (
+ "context_str", "ref_list", "ref_snippets",
+ "related_context", "retrieval_trace",
+ )
+ ):
+ evidence = stored
+ logger.info(
+ "[RAG][CACHE] evidence hit path=%s", str(path_str)[:120]
+ )
+ except (OSError, ValueError):
+ logger.warning(
+ "[RAG][CACHE] unreadable entry ignored: %s", cache_file
+ )
+
+ if evidence is None:
+ evidence = self._retrieve_path_evidence(
+ root_material, path_str, full_path
+ )
+ if cache_enabled and cache_file:
+ try:
+ os.makedirs(os.path.dirname(cache_file), exist_ok=True)
+ # Write to a temporary file first so a crash mid-write cannot
+ # leave a truncated entry that later reads as valid evidence.
+ temporary = cache_file + ".tmp"
+ with open(temporary, "w", encoding="utf-8") as handle:
+ json.dump(
+ {
+ "root_material": root_material,
+ "path_str": path_str,
+ "signature": self._report_cache_signature(),
+ "evidence": evidence,
+ },
+ handle,
+ ensure_ascii=False,
+ default=str,
+ )
+ os.replace(temporary, cache_file)
+ logger.info(
+ "[RAG][CACHE] stored evidence path=%s", str(path_str)[:120]
+ )
+ except (OSError, TypeError, ValueError):
+ logger.warning("[RAG][CACHE] could not store %s", cache_file)
+
+ return evidence
+
+ def _retrieve_path_evidence(self, root_material, path_str, full_path=None):
edges = parse_path(path_str)
mini_report = {root_material: [path_str]}
generated_queries = self.query_generator.generate_queries(mini_report)
@@ -3645,6 +3767,30 @@ include a "Validation note"; it is added automatically outside your paragraph.
if not context_str:
context_str = "No relevant literature evidence was retrieved from the vector database."
+ return {
+ "context_str": context_str,
+ "ref_list": ref_list,
+ "ref_snippets": ref_snippets,
+ "related_context": related_context,
+ "retrieval_trace": retrieval_trace,
+ }
+
+ def _narrate_path_report(
+ self, evidence, root_material, path_str, full_path=None
+ ):
+ """Write the report narrative from already-retrieved evidence.
+
+ Split from retrieval so the expensive, deterministic half can be cached
+ while this half runs fresh on every request. Retrieval and evidence
+ gating depend only on (path, corpus) and cost minutes; the narrative is
+ the one part that should not be frozen in a cache, and it costs seconds.
+ """
+ context_str = evidence["context_str"]
+ ref_list = evidence["ref_list"]
+ ref_snippets = evidence["ref_snippets"]
+ related_context = evidence["related_context"]
+ retrieval_trace = evidence["retrieval_trace"]
+
safe_context = self._smart_truncate(
context_str,
max_chars=int(os.getenv("RAG_CONTEXT_MAX_CHARS", "8000")),
diff --git a/rag_report_cache/0275ae9df3f4d1cca2dfbadbf56a3d029df57b25.json b/rag_report_cache/0275ae9df3f4d1cca2dfbadbf56a3d029df57b25.json
new file mode 100644
index 0000000000000000000000000000000000000000..5b7f8e377fc1cc658d2f6277f62e2b009bb73421
--- /dev/null
+++ b/rag_report_cache/0275ae9df3f4d1cca2dfbadbf56a3d029df57b25.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[Uv]--> β-PbO2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nTherefore, XRD analysis results demonstrate that unstable minium pigment has changed into beta-PbO2 during UV aging.\n\n[1] Evidence classification: edge 1: direct\nLead (Pb) has four valence electrons distributed in 6s orbital and 6p orbitals and Pb3O4 is made of PbO2 and PbO; therefore, minium pigment contains both Pb(II) and Pb(IV) oxides, but only Pb(II) can absorb ultraviolet light energy to form an excitation state with high energy, which makes Pb(II) lose the lone pair electrons in the 6s orbital to form Pb(IV) and then oxidize to black beta-PbO2 by ozone (oxygen ionization under ultraviolet radiation) or oxygen.\n\n[1] Evidence classification: edge 1: direct\nTherefore, XRD analysis results demonstrate that unstable minium pigment has changed into beta-PbO2 during UV aging. However, for the model paint samples, because the XRD pattern of tung oil is a broad amorphous feature peak with no peak indicative of crystalline phases (Figure 2B), tung oil is proved as a noncrystalline material by aligning with the characteristics of amorphous peaks; therefore, the XRD pattern of model paint sample represents the result of minium pigment. As can been seen in Figure 2B, crystal structure of the model paint sample changes obviously during UV aging. Before aging, the crystal structure of the model paint sample agrees well with the standard crystal structure of minium, but the most noticeable peaks of minium at 26.3{}^{\\circ}, 30.7{}^{\\circ}, and 32.1{}^{\\circ} begin to diminish while the peaks at 24.8{}^{\\circ}, 27.4{}^{\\circ}, and 34.3{}^{\\circ} appear during UV aging, and the final product is identified as 2PbCO3-Pb (OH)2.[30] In addition, the intensity of XRD peak getting weaker suggests the decrease of pigment appear during UV aging, and the final product is identified as 2PbCO3-Pb (OH)2.[30] In addition, the intensity of XRD peak getting weaker suggests the decrease of pigment crystallinity under UV aging. The formation of the basic lead carbonate (lead white) gives a chalky surface.\n\n[2] Evidence classification: edge 1: direct\nIn water, the darkening of red lead is induced by light, but when NaHCO3 is added red lead transforms to plattnerite even in darkness.\n\n[2] Evidence classification: edge 1: direct\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\n\n[2] Evidence classification: edge 1: direct\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "ref_list": ["ZHAO Y, WANG J, PAN A, et al. Degradation of red lead pigment in the oil painting during UV aging [J/OL]. Color Research & Application, 2019. DOI: 10.1002/col.22386.", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001."], "ref_snippets": [{"text": "Therefore, XRD analysis results demonstrate that unstable minium pigment has changed into beta-PbO2 during UV aging.\nLead (Pb) has four valence electrons distributed in 6s orbital and 6p orbitals and Pb3O4 is made of PbO2 and PbO; therefore, minium pigment contains both Pb(II) and Pb(IV) oxides, but only Pb(II) can absorb ultraviolet light energy to form an excitation state with high energy, which makes Pb(II) lose the lone pair electrons in the 6s orbital to form Pb(IV) and then oxidize to black beta-PbO2 by ozone (oxygen ionization under ultraviolet radiation) or oxygen.\nTherefore, XRD analysis results demonstrate that unstable minium pigment has changed into beta-PbO2 during UV aging. However, for the model paint samples, because the XRD pattern of tung oil is a broad amorphous feature peak with no peak indicative of crystalline phases (Figure 2B), tung oil is proved as a noncrystalline material by aligning with the characteristics of amorphous peaks; therefore, the XRD pattern of model paint sample represents the result of minium pigment. As can been seen in Figure 2B, crystal structure of the model paint sample changes obviously during UV aging. Before aging, the crystal structure of the model paint sample agrees well with the standard crystal structure of minium, but the most noticeable peaks of minium at 26.3{}^{\\circ}, 30.7{}^{\\circ}, and 32.1{}^{\\circ} begin to diminish while the peaks at 24.8{}^{\\circ}, 27.4{}^{\\circ}, and 34.3{}^{\\circ} appear during UV aging, and the final product is identified as 2PbCO3-Pb (OH)2.[30] In addition, the intensity of XRD peak getting weaker suggests the decrease of pigment appear during UV aging, and the final product is identified as 2PbCO3-Pb (OH)2.[30] In addition, the intensity of XRD peak getting weaker suggests the decrease of pigment crystallinity under UV aging. The formation of the basic lead carbonate (lead white) gives a chalky surface.", "score": 0.45951032638549805, "snippets": [{"text": "Therefore, XRD analysis results demonstrate that unstable minium pigment has changed into beta-PbO2 during UV aging.", "score": 0.45951032638549805, "metadata": {"doi": "10.1002/col.22386", "source": "markdown_output/Degradation of red lead pigment in the oil painting during UV aging.md", "ingest_kind": "existing_chroma", "chunk_index": 24, "title": "Degradation of red lead pigment in the oil painting during UV aging", "source_file": "Degradation of red lead pigment in the oil painting during UV aging.md", "journal": "Color Research & Application", "year": "2019", "authors": [{"family": "Zhao", "given": "Yanrui"}, {"family": "Wang", "given": "Jianli"}, {"family": "Pan", "given": "Aizhao"}, {"family": "He", "given": "Ling"}, {"family": "Simon", "given": "Stefan"}], "volume": "44", "issue": "5", "pages": "790-797", "url": "https://doi.org/10.1002/col.22386"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Therefore, XRD analysis results demonstrate that unstable minium pigment has changed into beta-PbO2 during UV aging.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "minium", "product_span": "beta-PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Lead (Pb) has four valence electrons distributed in 6s orbital and 6p orbitals and Pb3O4 is made of PbO2 and PbO; therefore, minium pigment contains both Pb(II) and Pb(IV) oxides, but only Pb(II) can absorb ultraviolet light energy to form an excitation state with high energy, which makes Pb(II) lose the lone pair electrons in the 6s orbital to form Pb(IV) and then oxidize to black beta-PbO2 by ozone (oxygen ionization under ultraviolet radiation) or oxygen.", "score": 0.46735185384750366, "metadata": {"source_file": "Degradation of red lead pigment in the oil painting during UV aging.md", "title": "Degradation of red lead pigment in the oil painting during UV aging", "doi": "10.1002/col.22386", "ingest_kind": "existing_chroma", "chunk_index": 35, "journal": "Color Research & Application", "year": "2019", "source": "markdown_output/Degradation of red lead pigment in the oil painting during UV aging.md", "authors": [{"family": "Zhao", "given": "Yanrui"}, {"family": "Wang", "given": "Jianli"}, {"family": "Pan", "given": "Aizhao"}, {"family": "He", "given": "Ling"}, {"family": "Simon", "given": "Stefan"}], "volume": "44", "issue": "5", "pages": "790-797", "url": "https://doi.org/10.1002/col.22386"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "resolver", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Lead (Pb) has four valence electrons distributed in 6s orbital and 6p orbitals and Pb3O4 is made of PbO2 and PbO; therefore, minium pigment contains both Pb(II) and Pb(IV) oxides, but only Pb(II) can absorb ultraviolet light energy to form an excitation state with high energy, which makes Pb(II) lose the lone pair electrons in the 6s orbital to form Pb(IV) and then oxidize to black beta-PbO2 by ozone (oxygen ionization under ultraviolet radiation) or oxygen.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "minium", "product_span": "beta-PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Therefore, XRD analysis results demonstrate that unstable minium pigment has changed into beta-PbO2 during UV aging. However, for the model paint samples, because the XRD pattern of tung oil is a broad amorphous feature peak with no peak indicative of crystalline phases (Figure 2B), tung oil is proved as a noncrystalline material by aligning with the characteristics of amorphous peaks; therefore, the XRD pattern of model paint sample represents the result of minium pigment. As can been seen in Figure 2B, crystal structure of the model paint sample changes obviously during UV aging. Before aging, the crystal structure of the model paint sample agrees well with the standard crystal structure of minium, but the most noticeable peaks of minium at 26.3{}^{\\circ}, 30.7{}^{\\circ}, and 32.1{}^{\\circ} begin to diminish while the peaks at 24.8{}^{\\circ}, 27.4{}^{\\circ}, and 34.3{}^{\\circ} appear during UV aging, and the final product is identified as 2PbCO3-Pb (OH)2.[30] In addition, the intensity of XRD peak getting weaker suggests the decrease of pigment appear during UV aging, and the final product is identified as 2PbCO3-Pb (OH)2.[30] In addition, the intensity of XRD peak getting weaker suggests the decrease of pigment crystallinity under UV aging. The formation of the basic lead carbonate (lead white) gives a chalky surface.", "score": null, "metadata": {"year": "2019", "chunk_index": 25, "journal": "Color Research & Application", "doi": "10.1002/col.22386", "title": "Degradation of red lead pigment in the oil painting during UV aging", "source": "markdown_output/Degradation of red lead pigment in the oil painting during UV aging.md", "ingest_kind": "existing_chroma", "source_file": "Degradation of red lead pigment in the oil painting during UV aging.md", "authors": [{"family": "Zhao", "given": "Yanrui"}, {"family": "Wang", "given": "Jianli"}, {"family": "Pan", "given": "Aizhao"}, {"family": "He", "given": "Ling"}, {"family": "Simon", "given": "Stefan"}], "volume": "44", "issue": "5", "pages": "790-797", "url": "https://doi.org/10.1002/col.22386"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Therefore, XRD analysis results demonstrate that unstable minium pigment has changed into beta-PbO2 during UV aging. However, for the model paint samples, because the XRD pattern of tung oil is a broad amorphous feature peak with no peak indicative of crystalline phases (Figure 2B), tung oil is proved as a noncrystalline material by aligning with the characteristics of amorphous peaks; therefore, the XRD pattern of model paint sample represents the result of minium pigment. As can been seen in Figure 2B, crystal structure of the model paint sample changes obviously during UV aging. Before aging, the crystal structure of the model paint sample agrees well with the standard crystal structure of minium, but the most noticeable peaks of minium at 26.3{}^{\\circ}, 30.7{}^{\\circ}, and 32.1{}^{\\circ} begin to diminish while the peaks at 24.8{}^{\\circ}, 27.4{}^{\\circ}, and 34.3{}^{\\circ} appear during UV aging, and the final product is identified as 2PbCO3-Pb (OH)2.[30] In addition, the intensity of XRD peak getting weaker suggests the decrease of pigment appear during UV aging, and the final product is identified as 2PbCO3-Pb (OH)2.[30] In addition, the intensity of XRD peak getting weaker suggests the decrease of pigment crystallinity under UV aging. The formation of the basic lead carbonate (lead white) gives a chalky surface.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "minium", "product_span": "beta-PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "In water, the darkening of red lead is induced by light, but when NaHCO3 is added red lead transforms to plattnerite even in darkness.\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "score": null, "snippets": [{"text": "In water, the darkening of red lead is induced by light, but when NaHCO3 is added red lead transforms to plattnerite even in darkness.", "score": null, "metadata": {"ingest_kind": "existing_chroma", "journal": "Journal of Cultural Heritage", "chunk_index": 40, "doi": "10.1016/j.culher.2008.11.001", "source_file": "Degradation of lead-based pigments by salt solutions.md", "year": "2009", "title": "Degradation of lead-based pigments by salt solutions", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "In water, the darkening of red lead is induced by light, but when NaHCO3 is added red lead transforms to plattnerite even in darkness.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "score": null, "metadata": {"title": "Degradation of lead-based pigments by salt solutions", "year": "2009", "doi": "10.1016/j.culher.2008.11.001", "source_file": "Degradation of lead-based pigments by salt solutions.md", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "chunk_index": 42, "journal": "Journal of Cultural Heritage", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "score": null, "metadata": {"ingest_kind": "existing_chroma", "journal": "Journal of Cultural Heritage", "source_file": "Degradation of lead-based pigments by salt solutions.md", "title": "Degradation of lead-based pigments by salt solutions", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "year": "2009", "doi": "10.1016/j.culher.2008.11.001", "chunk_index": 45}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 64, "resolver_kept": 5, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 206, "lexical_kept": 6, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/05f12cb7fc2e4449922b32545909a6b0a63c42cb.json b/rag_report_cache/05f12cb7fc2e4449922b32545909a6b0a63c42cb.json
new file mode 100644
index 0000000000000000000000000000000000000000..2f21c67b7d94f7ea1fb2865b679ab87bcf4d9fab
--- /dev/null
+++ b/rag_report_cache/05f12cb7fc2e4449922b32545909a6b0a63c42cb.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Uv+Oxidant]--> HgSO4 --[Uv+Oxidant]--> Hg2SO4 --[Uv+Oxidant]--> Hg", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "ELERT K, CARDELL C. Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging [J/OL]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, 216:236-248. DOI: 10.1016/j.saa.2019.03.027.", "snippet": "An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK\\({}_{\\alpha}\\) radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\(\\times\\) 700 \\(\\upmu\\)m in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg\\({}^{0}\\) and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current). Note that it was not possible to measure the ablation depth achieved during ion-etching using scanning electron microscopy or atomic force microscopy as a result of the sample's high surface roughness (i.e., the relatively small impact of \\(<\\)1 m depth caused by ion-etching could not be distinguished from", "retrieval_origin": "bge_m3", "match": {"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current).", "reactant_match": "alias", "product_match": "exact", "reactant_span": "cinnabar", "product_span": "Hg", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "KEUNE K, BOON JJ. Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings [J/OL]. Analytical Chemistry, 2005. DOI: 10.1021/ac048158f.", "snippet": "The two components in the black product, metallic mercury and residual vermilion, react with chloride supplied by sources external to the vermilion. The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur. Corderoite (HgS\\({}_{2}\\)Cl\\({}_{2}\\)) can easily be formed in a mixture of HgS and NaCl solution kept at room temperature after a long period[3, 9] and will after light exposure degrade into a dark gray product containing (HgCl)\\({}_{2}\\).[9] The formation of corderoite could not have taken place in the first degradation steps, because of the high amount of chloride required that is suggested to accumulate after the blackening. The (HgCl\\({}_{2}\\) formed photodegrades under normal light into HgCl\\({}_{2}\\) and Hg(0).[23] The metallic mercury, derived from the photoreuction in the first step, the corderoite, and the (HgCl)\\({}_{2}\\), react with chloride", "retrieval_origin": "lexical", "match": {"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "snippet": "the intensity and type of radiation having a rate-determining influence. Besides, schuettetic has been found in cinnabar deposits exposed to natural sunlight in numerous locations, including Almaden (Spain), California and Nevada (USA), Bolivia, Moravia (Czech Republic), and Sonora (Mexico) [48]. According to Bailey et al. [19], this mineral forms through photooxidation of sunlight-exposed cinnabar in the presence of oxygen-bearing surface water. Importantly, the authors acknowledged that HgSO\\({}_{4}\\) might be an intermediate phase during schuettetic formation. In any case, sulfate formation is not limited to cinnabar deposits. Radeport et al. [2, 17] acknowledged the possible oxidation of mercury sulfide to sulfate upon cinnabar degradation in the case of a Gothic wall painting from the monastery of Pedralbes (Barcelona, Spain) and detected mercury sulfate in artificially aged cinnabar pellets.", "retrieval_origin": "crn_provenance", "match": {"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "inferred", "score": 0.87, "window": "According to Bailey et al. [19], this mineral forms through photooxidation of sunlight-exposed cinnabar in the presence of oxygen-bearing surface water. Importantly, the authors acknowledged that HgSO4 might be an intermediate phase during schuettetic formation. In any case, sulfate formation is not limited to cinnabar deposits. Radeport et al. [2, 17] acknowledged the possible oxidation of mercury sulfide to sulfate upon cinnabar degradation in the case of a Gothic wall painting from the monastery of Pedralbes (Barcelona, Spain) and detected mercury sulfate in artificially aged cinnabar pellets.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "mercury sulfide", "product_span": "mercury sulfate", "relation_basis": "author_proposal", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_author_proposal"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 29, "dense_candidates": 580, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 15, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 218, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/11a1eaafb7fdabf85c8e635c20f2938964555de4.json b/rag_report_cache/11a1eaafb7fdabf85c8e635c20f2938964555de4.json
new file mode 100644
index 0000000000000000000000000000000000000000..dd72db2a7f1729229831bacf988172803d81672a
--- /dev/null
+++ b/rag_report_cache/11a1eaafb7fdabf85c8e635c20f2938964555de4.json
@@ -0,0 +1 @@
+{"root_material": "2PbCO3·Pb(OH)2", "path_str": "2PbCO3·Pb(OH)2 --[Fresco]--> β-PbO", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nUpon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.\n\n[1] Evidence classification: edge 1: direct\nUnder a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "ref_list": ["VAGNINI M, VIVANI R, SGAMELLOTTI A, et al. Blackening of lead white: Study of model paintings [J/OL]. Journal of Raman Spectroscopy, 2020. DOI: 10.1002/jrs.5879."], "ref_snippets": [{"text": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.\nUnder a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "score": null, "snippets": [{"text": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.", "score": null, "metadata": {"year": "2020", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "title": "Blackening of lead white: Study of model paintings", "source_file": "Blackening of lead white: Study of model paintings.md", "chunk_index": 21, "ingest_kind": "existing_chroma", "doi": "10.1002/jrs.5879", "journal": "Journal of Raman Spectroscopy", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO", "condition": "Fresco", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "massicot", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "score": null, "metadata": {"journal": "Journal of Raman Spectroscopy", "doi": "10.1002/jrs.5879", "ingest_kind": "existing_chroma", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "chunk_index": 35, "source_file": "Blackening of lead white: Study of model paintings.md", "year": "2020", "title": "Blackening of lead white: Study of model paintings", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "resolver"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO", "condition": "Fresco", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 59, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 211, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/12e803bb6150e8e5f3b414e296f3989590a54392.json b/rag_report_cache/12e803bb6150e8e5f3b414e296f3989590a54392.json
new file mode 100644
index 0000000000000000000000000000000000000000..6acfd840575115639f77ec881e4688fd052f3a20
--- /dev/null
+++ b/rag_report_cache/12e803bb6150e8e5f3b414e296f3989590a54392.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Uv+Oxidant]--> HgSO4 --[Uv+Moisture]--> Hg", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nAn Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current).\n\n[1] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nGenerally, a color differences of DeltaE{}^{\\star}\\simeq3 will be perceptible to the human eye [31]. An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s.\n\n[2] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nThe residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.\n\n[3] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nAdditionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].\n\n[4] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nFinally, the photodegradation of vermillion was explained in terms of formation of metallic mercury and HgCl 2, due to the halogen impurities present in the pigment, identi - fied thanks to secondary ion mass spectrometry (SIMS) analysis [207], and to X-ray spectroscopic analysis [208].", "ref_list": ["ELERT K, CARDELL C. Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging [J/OL]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, 216:236-248. DOI: 10.1016/j.saa.2019.03.027.", "KEUNE K, BOON JJ. Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings [J/OL]. Analytical Chemistry, 2005. DOI: 10.1021/ac048158f.", "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:16. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)"], "ref_snippets": [{"text": "An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current).\nGenerally, a color differences of DeltaE{}^{\\star}\\simeq3 will be perceptible to the human eye [31]. An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s.", "score": 0.4447641968727112, "snippets": [{"text": "An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current).", "score": 0.4447641968727112, "metadata": {"doi": "10.1016/j.saa.2019.03.027", "ingest_kind": "existing_chroma", "year": "2019", "journal": "Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy", "title": "Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging", "source": "markdown_output/Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging.md", "source_file": "Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging.md", "chunk_index": 24, "authors": [{"family": "Elert", "given": "K."}, {"family": "Cardell", "given": "C."}], "volume": "216", "pages": "236-248", "url": "https://doi.org/10.1016/j.saa.2019.03.027"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current).", "reactant_match": "alias", "product_match": "exact", "reactant_span": "cinnabar", "product_span": "Hg", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Generally, a color differences of DeltaE{}^{\\star}\\simeq3 will be perceptible to the human eye [31]. An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s.", "score": null, "metadata": {"year": "2019", "source_file": "Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging.md", "title": "Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging", "chunk_index": 23, "doi": "10.1016/j.saa.2019.03.027", "ingest_kind": "existing_chroma", "journal": "Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy", "source": "markdown_output/Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging.md", "authors": [{"family": "Elert", "given": "K."}, {"family": "Cardell", "given": "C."}], "volume": "216", "pages": "236-248", "url": "https://doi.org/10.1016/j.saa.2019.03.027"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Generally, a color differences of DeltaE{}^{\\star}\\simeq3 will be perceptible to the human eye [31]. An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "cinnabar", "product_span": "Hg", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.43365007638931274, "snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.43365007638931274, "metadata": {"doi": "10.1021/ac048158f", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "journal": "Analytical Chemistry", "source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "ingest_kind": "existing_chroma", "year": "2005", "chunk_index": 46}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": null, "snippets": [{"text": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": null, "metadata": {"year": "2021", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "doi": "10.1038/s42004-021-00610-2", "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "journal": "Communications Chemistry", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "chunk_index": 3, "ingest_kind": "existing_chroma", "authors": [{"family": "Elert", "given": "Kerstin"}, {"family": "Pérez Mendoza", "given": "Manuel"}, {"family": "Cardell", "given": "Carolina"}], "volume": "4", "issue": "1", "article_number": "174", "url": "https://doi.org/10.1038/s42004-021-00610-2"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Finally, the photodegradation of vermillion was explained in terms of formation of metallic mercury and HgCl 2, due to the halogen impurities present in the pigment, identi - fied thanks to secondary ion mass spectrometry (SIMS) analysis [207], and to X-ray spectroscopic analysis [208].", "score": null, "snippets": [{"text": "Finally, the photodegradation of vermillion was explained in terms of formation of metallic mercury and HgCl 2, due to the halogen impurities present in the pigment, identi - fied thanks to secondary ion mass spectrometry (SIMS) analysis [207], and to X-ray spectroscopic analysis [208].", "score": null, "metadata": {"page": "16", "doi": "10.1186/s40494-017-0125-6", "chunk_index": "56", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "year": "2017", "journal": "Heritage Science", "source_file": "On the stability of mediaeval inorganic pigments - a review", "source": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Finally, the photodegradation of vermillion was explained in terms of formation of metallic mercury and HgCl 2, due to the halogen impurities present in the pigment, identi - fied thanks to secondary ion mass spectrometry (SIMS) analysis [207], and to X-ray spectroscopic analysis [208].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermillion", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 16, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 3, "lexical_scanned": 2314, "lexical_candidates": 214, "lexical_kept": 4, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/1527413b7dcf1856afdb156291fe59c3bd7760cf.json b/rag_report_cache/1527413b7dcf1856afdb156291fe59c3bd7760cf.json
new file mode 100644
index 0000000000000000000000000000000000000000..045fe26efef7c6f50ed82afe8e3a219bccef8659
--- /dev/null
+++ b/rag_report_cache/1527413b7dcf1856afdb156291fe59c3bd7760cf.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Biogenic+Chloride]--> Cu2Cl(OH)3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nMinerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "ref_list": ["PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1.", "DOMÉNECH‐CARBÓ MT, EDWARDS HGM, DOMÉNECH‐CARBÓ A, et al. An authentication case study: Antonio Palomino versus Vicente Guillo paintings in the vaulted ceiling of the Sant Joan del Mercat church (Valencia, Spain) [J/OL]. Journal of Raman Spectroscopy, 2012. DOI: 10.1002/jrs.3168."], "ref_snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "metadata": {"source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "year": "2024", "doi": "10.1007/s00339-024-07954-1", "journal": "Applied Physics A", "chunk_index": 23, "license": "https://creativecommons.org/licenses/by/4.0", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "page": 12, "ingest_kind": "pdf_fulltext", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Biogenic+Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 24, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 188, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/15a304fd12f686a1780fa924381f165477a13cbc.json b/rag_report_cache/15a304fd12f686a1780fa924381f165477a13cbc.json
new file mode 100644
index 0000000000000000000000000000000000000000..6bef7bb88da3fc6589128cbdd5c1b153accfa5d1
--- /dev/null
+++ b/rag_report_cache/15a304fd12f686a1780fa924381f165477a13cbc.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Uv+Moisture]--> HgSO4 --[Uv+Oxidant]--> Hg2SO4 --[Uv+Oxidant]--> Hg", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nAn Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current).\n\n[1] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nGenerally, a color differences of DeltaE{}^{\\star}\\simeq3 will be perceptible to the human eye [31]. An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s.\n\n[2] Evidence classification: edge 1: direct\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.\n\n[2] Evidence classification: edge 1: direct\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].\n\n[2] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nAdditionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].\n\n[3] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nThe residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.\n\n[4] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nFinally, the photodegradation of vermillion was explained in terms of formation of metallic mercury and HgCl 2, due to the halogen impurities present in the pigment, identi - fied thanks to secondary ion mass spectrometry (SIMS) analysis [207], and to X-ray spectroscopic analysis [208].", "ref_list": ["ELERT K, CARDELL C. Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging [J/OL]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, 216:236-248. DOI: 10.1016/j.saa.2019.03.027.", "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "KEUNE K, BOON JJ. Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings [J/OL]. Analytical Chemistry, 2005. DOI: 10.1021/ac048158f.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:16. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)"], "ref_snippets": [{"text": "An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current).\nGenerally, a color differences of DeltaE{}^{\\star}\\simeq3 will be perceptible to the human eye [31]. An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s.", "score": 0.4930061101913452, "snippets": [{"text": "An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current).", "score": 0.4930061101913452, "metadata": {"source": "markdown_output/Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging.md", "year": "2019", "source_file": "Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging.md", "chunk_index": 24, "doi": "10.1016/j.saa.2019.03.027", "journal": "Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy", "title": "Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging", "ingest_kind": "existing_chroma", "authors": [{"family": "Elert", "given": "K."}, {"family": "Cardell", "given": "C."}], "volume": "216", "pages": "236-248", "url": "https://doi.org/10.1016/j.saa.2019.03.027"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s. Ion-etching depth profiles were obtained using Argon for various periods of time (4 keV energy, 10 mA emission current).", "reactant_match": "alias", "product_match": "exact", "reactant_span": "cinnabar", "product_span": "Hg", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Generally, a color differences of DeltaE{}^{\\star}\\simeq3 will be perceptible to the human eye [31]. An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s.", "score": null, "metadata": {"year": "2019", "doi": "10.1016/j.saa.2019.03.027", "ingest_kind": "existing_chroma", "title": "Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging", "chunk_index": 23, "source_file": "Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging.md", "journal": "Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy", "source": "markdown_output/Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging.md", "authors": [{"family": "Elert", "given": "K."}, {"family": "Cardell", "given": "C."}], "volume": "216", "pages": "236-248", "url": "https://doi.org/10.1016/j.saa.2019.03.027"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Generally, a color differences of DeltaE{}^{\\star}\\simeq3 will be perceptible to the human eye [31]. An Axis Ultra-DLD (Kratos Analytical Ltd., U.K.) was used to determine the quantitative elemental composition and the oxidization state of Hg in cinnabar pigments and in the alteration layer of outdoor (city center of Granada) exposed dosimeters. Analysis was performed using monochromatic AlK{}alpha radiation with a pass energy of 160 (survey scans) and 20 eV (high resolution scans). The analyzed area was -300 \\times 700 \\upmum in size. The C1s transition at 284.6 eV was used as reference to determine binding energies of Hg{}^{0} and Hg5s.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "cinnabar", "product_span": "Hg", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].\nAdditionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": 0.40642249584198, "snippets": [{"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.", "score": 0.4948519468307495, "metadata": {"ingest_kind": "existing_chroma", "doi": "10.1038/s42004-021-00610-2", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "chunk_index": 43, "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "journal": "Communications Chemistry", "year": "2021", "authors": [{"family": "Elert", "given": "Kerstin"}, {"family": "Pérez Mendoza", "given": "Manuel"}, {"family": "Cardell", "given": "Carolina"}], "volume": "4", "issue": "1", "article_number": "174", "url": "https://doi.org/10.1038/s42004-021-00610-2"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "mercury sulfate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "score": 0.40642249584198, "metadata": {"source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "doi": "10.1038/s42004-021-00610-2", "year": "2021", "ingest_kind": "existing_chroma", "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "chunk_index": 42, "journal": "Communications Chemistry", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "authors": [{"family": "Elert", "given": "Kerstin"}, {"family": "Pérez Mendoza", "given": "Manuel"}, {"family": "Cardell", "given": "Carolina"}], "volume": "4", "issue": "1", "article_number": "174", "url": "https://doi.org/10.1038/s42004-021-00610-2"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "mercury sulfate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": null, "metadata": {"doi": "10.1038/s42004-021-00610-2", "journal": "Communications Chemistry", "chunk_index": 3, "year": "2021", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "ingest_kind": "existing_chroma", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "authors": [{"family": "Elert", "given": "Kerstin"}, {"family": "Pérez Mendoza", "given": "Manuel"}, {"family": "Cardell", "given": "Carolina"}], "volume": "4", "issue": "1", "article_number": "174", "url": "https://doi.org/10.1038/s42004-021-00610-2"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.45197176933288574, "snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.45197176933288574, "metadata": {"ingest_kind": "existing_chroma", "chunk_index": 46, "doi": "10.1021/ac048158f", "journal": "Analytical Chemistry", "source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "year": "2005", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Finally, the photodegradation of vermillion was explained in terms of formation of metallic mercury and HgCl 2, due to the halogen impurities present in the pigment, identi - fied thanks to secondary ion mass spectrometry (SIMS) analysis [207], and to X-ray spectroscopic analysis [208].", "score": null, "snippets": [{"text": "Finally, the photodegradation of vermillion was explained in terms of formation of metallic mercury and HgCl 2, due to the halogen impurities present in the pigment, identi - fied thanks to secondary ion mass spectrometry (SIMS) analysis [207], and to X-ray spectroscopic analysis [208].", "score": null, "metadata": {"page": "16", "doi": "10.1186/s40494-017-0125-6", "chunk_index": "56", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "year": "2017", "journal": "Heritage Science", "source_file": "On the stability of mediaeval inorganic pigments - a review", "source": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Finally, the photodegradation of vermillion was explained in terms of formation of metallic mercury and HgCl 2, due to the halogen impurities present in the pigment, identi - fied thanks to secondary ion mass spectrometry (SIMS) analysis [207], and to X-ray spectroscopic analysis [208].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermillion", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 29, "dense_candidates": 580, "dense_kept": 4, "resolver_scanned": 2314, "resolver_candidates": 15, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 4, "lexical_scanned": 2314, "lexical_candidates": 218, "lexical_kept": 6, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
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new file mode 100644
index 0000000000000000000000000000000000000000..d3c9f885273c6a0eb7ea01c765ccf5deb14e9a73
--- /dev/null
+++ b/rag_report_cache/161e820820e5196de774b76b895ea9dcc24b9541.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Uv]--> CuO", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThe effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124].", "ref_list": ["On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845."], "ref_snippets": [{"text": "The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124].", "score": 0.4847486615180969, "snippets": [{"text": "The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124].", "score": 0.4847486615180969, "metadata": {"ingest_kind": "pdf_fulltext", "journal": "Heritage Science", "year": "2017", "source_file": "On the stability of mediaeval inorganic pigments - a review", "doi": "10.1186/s40494-017-0125-6", "page": "13", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source": "On the stability of mediaeval inorganic pigments - a review", "chunk_index": "40"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuO", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "CuO", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 39, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 237, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/162ec05c8d8d624f9c30f8fc40c1fc205cd2d287.json b/rag_report_cache/162ec05c8d8d624f9c30f8fc40c1fc205cd2d287.json
new file mode 100644
index 0000000000000000000000000000000000000000..119bfff384a0bb60bf034bbd91b1918907283d80
--- /dev/null
+++ b/rag_report_cache/162ec05c8d8d624f9c30f8fc40c1fc205cd2d287.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[12000lux+1.5W/m2+60℃+90%RH]--> CuO", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CRN source: In-house aging experiment"], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}], "related_context": [{"source": "Blackening of copper pigments in wall paintings: impact of the fresco technique and the chemical composition of the pigments [J/OL]. Heritage Science, 2026:2. DOI: 10.1038/s40494-026-02461-3. (bibliographic metadata partially available)", "snippet": "ondary carbonates (malachite) 8,17–20.T h em o s tc o m m o n l y reported alteration, however, is blackening, generally attributed to the for- mation of tenorite (CuO) under conditions of high humidity and alkalinity in lime-based substrates2,21–27. Tenorite formation may also result from thermal damage28 or laser irradiation 29,30.I na d d i t i o n ,i n t e r a c t i o n sw i t h pollutant gases and acids can produce dark copper compounds such as copper sulphides (covellite) 31,32. Despite this extensive research, the mechanisms driving CuO formation under alkaline fresco conditions remain largely unclear. Importantly, most studies have focused on natural azurite and malachite powders, while other copper pigments—particularly silicates and acetates—have received far less attention. Furthermore, factors such as pigment origin, impurities, a nd the formation of copper species other than tenorite have rarely been explored in lime-based mural systems. Consequently, the causes and variability of blackening in fresco paintings are still not fully explained. The present study addresses this gap by examining a representative set of copper pigments applied directly onto lime-based substrates in order to clarify the mechanisms responsible for blackening.", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuO", "condition": "12000lux+1.5W/m2+60℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "ondary carbonates (malachite) 8,17–20.T h em o s tc o m m o n l y reported alteration, however, is blackening, generally attributed to the for- mation of tenorite (CuO) under conditions of high humidity and alkalinity in lime-based substrates2,21–27.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "tenorite", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "Blackening of copper pigments in wall paintings: impact of the fresco technique and the chemical composition of the pigments [J/OL]. Heritage Science, 2026:6. DOI: 10.1038/s40494-026-02461-3. (bibliographic metadata partially available)", "snippet": "bserved. Egyptian blue (EGB-F) remained chromatically stable, retaining its bluish hue and showing no reaction halos under SEM, confirming the high stability of cuprorivaite particles. Sporadic dark Cu- rich particles were occasionally detected (Fig. 6a, b), likely related to the raw materials used during pigment synthesis 8. EDS line-scan analysis of this particle (Fig. 6b) showed a similar spectrum to that observed in basic Cu-carbonates. However, these blackish particles did not affect the overall appearance of the paint layer. In contrast, chrysocolla (CHR-F) Table 2 | Mineralogical characterization by μXRD of the fresco paint mock-ups Fresco samples Assigned to the fresco technique Present in the raw pigment Alteration products Basic Cu-carbonates AZN-F Calcite, CaCO3 Azurite, Cu3(CO3)2(OH)2 Tenorite, CuO Portlandite, Ca(OH)2 Kaolinite, Al2Si2O5(OH)4 Quartz, SiO2 Phlogopite, KMg3AlSi3O10(F,OH)2 AZS-F Calcite, CaCO3 - Portlandite, Ca(OH)2 Azurite, Cu3(CO3)2(OH)2 AZP-F Calcite, CaCO3 Azurite, Cu3(CO3)2(OH)2 Tenorite, CuO Quartz, SiO2 - MAN-F Calcite, CaCO3 Malachite, CuCO3Cu(OH)2 Portlandite, Ca(OH)2 Cuprite, Cu2O Quartz, SiO2 Haematite, Fe2O3 - MAS-F Calcite, CaCO3 Malachite, CuCO3Cu(OH)2 - Portlandite, Ca(OH)2 Quartz, SiO2 Cu-silicates EGB-F Calcite, CaCO3 Cuprorivaite, CaCuSi4O10 - Portlandite, Ca(OH)2 CHR-F Calcite, CaCO3 Chrysocolla, CuSiO3 - Portlandite, Ca(OH)2 Cu-acetate VER-F Calcite, CaCO3 - Cuprite, Cu 2O Portlandite, Ca(OH)2 Quartz, SiO2 Vaterite, CaCO3 Samples were taken after 1 year left under laboratory conditions (20 ± 2 °C and 60 ± 10% RH).", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuO", "condition": "12000lux+1.5W/m2+60℃+90%RH", "evidence_scope": "edge", "verdict": "qualified", "score": 0.75, "window": "In contrast, chrysocolla (CHR-F) Table 2 | Mineralogical characterization by μXRD of the fresco paint mock-ups Fresco samples Assigned to the fresco technique Present in the raw pigment Alteration products Basic Cu-carbonates AZN-F Calcite, CaCO3 Azurite, Cu3(CO3)2(OH)2 Tenorite, CuO Portlandite, Ca(OH)2 Kaolinite, Al2Si2O5(OH)4 Quartz, SiO2 Phlogopite, KMg3AlSi3O10(F,OH)2 AZS-F Calcite, CaCO3 - Portlandite, Ca(OH)2 Azurite, Cu3(CO3)2(OH)2 AZP-F Calcite, CaCO3 Azurite, Cu3(CO3)2(OH)2 Tenorite, CuO Quartz, SiO2 - MAN-F Calcite, CaCO3 Malachite, CuCO3Cu(OH)2 Portlandite, Ca(OH)2 Cuprite, Cu2O Quartz, SiO2 Haematite, Fe2O3 - MAS-F Calcite, CaCO3 Malachite, CuCO3Cu(OH)2 - Portlandite, Ca(OH)2 Quartz, SiO2 Cu-silicates EGB-F Calcite, CaCO3 Cuprorivaite, CaCuSi4O10 - Portlandite, Ca(OH)2 CHR-F Calcite, CaCO3 Chrysocolla, CuSiO3 - Portlandite, Ca(OH)2 Cu-acetate VER-F Calcite, CaCO3 - Cuprite, Cu2O Portlandite, Ca(OH)2 Quartz, SiO2 Vaterite, CaCO3 Samples were taken after 1 year left under laboratory conditions (20 ± 2 °C and 60 ± 10% RH).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "tenorite", "relation_basis": "product_identification", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["relation_product_identification", "condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "is formed. The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124]. Malachite (CuCO3·Cu(OH)2, green) Malachite (CuCO 3·Cu(OH)2) is more stable than azurite (2CuCO 3·Cu(OH)2) and verdigris (xCu(CH3COO2)·yCu(OH)2·zH2O), therefore showing less or slower reactivity towards many factors [119, 123]. It is known to be permanent in all binding media, light - fast and alkali proof. Its deeper colour is obtained by coarse grinding, and as a consequence of having relatively low refractive index, it shows better performances in tempera than in oil [50, 126]. Due to its chemical com - position, malachite is subject to interactions with acids, bases, humidity, temperature and circulating ions. In presence of humidity, malachite stains can be observed, which are actually caused by proteinaceous binders deg - radation [64]. Moreover, ions such as Cl − present in the mortar, sand or in the bricks, can react with the basic car- bonate to form copper hydroxychlorides ((Cu 2Cl(OH)3) atacamite, clinoatacamite, paratacamite botallackite) [119, 121, 123, 126–128] and the copper chloride nan - tokite [103]. Sulphate ions are also likely to be present in wall paintings, especially from the degradation of calcite to gypsum, from gypsum preparation layers [53], or from SO 2/SO3 pollution.", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuO", "condition": "12000lux+1.5W/m2+60℃+90%RH", "evidence_scope": "edge", "verdict": "qualified", "score": 0.67, "window": "The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124]. Malachite (CuCO3·Cu(OH)2, green) Malachite (CuCO 3·Cu(OH)2) is more stable than azurite (2CuCO 3·Cu(OH)2) and verdigris (xCu(CH3COO2)·yCu(OH)2·zH2O), therefore showing less or slower reactivity towards many factors [119, 123].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "CuO", "relation_basis": "product_identification", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["relation_product_identification", "condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 28, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 163, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/1eab3d122a45a246efcacb8e92b21aa09ea0b37c.json b/rag_report_cache/1eab3d122a45a246efcacb8e92b21aa09ea0b37c.json
new file mode 100644
index 0000000000000000000000000000000000000000..1aa629e3e3fbb93f693abd9e6efb58a9e4067add
--- /dev/null
+++ b/rag_report_cache/1eab3d122a45a246efcacb8e92b21aa09ea0b37c.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Moisture]--> CuCO3·Cu(OH)2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nBlack colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "ref_list": ["POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "CARDELL C, HERRERA A, GUERRA I, et al. Pigment-size effect on the physico-chemical behavior of azurite-tempera dosimeters upon natural and accelerated photo aging [J/OL]. Dyes and Pigments, 2017. DOI: 10.1016/j.dyepig.2017.02.001."], "ref_snippets": [{"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "score": 0.422015905380249, "snippets": [{"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "score": 0.422015905380249, "metadata": {"year": "2020", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "chunk_index": 7, "journal": "Minerals", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "ingest_kind": "pdf_direct", "doi": "10.3390/min10050424", "source": "pdf_direct/min10050424_part2.pdf"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCO3·Cu(OH)2", "condition": "Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "malachite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 148, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 252, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/1fae62eed06440517bbd2f745709a92801b69c3d.json b/rag_report_cache/1fae62eed06440517bbd2f745709a92801b69c3d.json
new file mode 100644
index 0000000000000000000000000000000000000000..6cc0c0378beaa64a6e6f290a52ad17df9678a753
--- /dev/null
+++ b/rag_report_cache/1fae62eed06440517bbd2f745709a92801b69c3d.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Moisture]--> CuCO3·Cu(OH)2 --[Biogenic+Sulfate]--> Cu4SO4(OH)6", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nBlack colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "ref_list": ["POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "CARDELL C, HERRERA A, GUERRA I, et al. Pigment-size effect on the physico-chemical behavior of azurite-tempera dosimeters upon natural and accelerated photo aging [J/OL]. Dyes and Pigments, 2017. DOI: 10.1016/j.dyepig.2017.02.001."], "ref_snippets": [{"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "score": 0.422015905380249, "snippets": [{"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "score": 0.422015905380249, "metadata": {"title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "journal": "Minerals", "year": "2020", "ingest_kind": "pdf_direct", "chunk_index": 7, "source": "pdf_direct/min10050424_part2.pdf", "doi": "10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCO3·Cu(OH)2", "condition": "Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "malachite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 159, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 297, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/20e24f7154446e9fe75db49f51d62a3f5ae93bd3.json b/rag_report_cache/20e24f7154446e9fe75db49f51d62a3f5ae93bd3.json
new file mode 100644
index 0000000000000000000000000000000000000000..91ac3c517f6451f50a6ea7ac7a038aaff20c86b8
--- /dev/null
+++ b/rag_report_cache/20e24f7154446e9fe75db49f51d62a3f5ae93bd3.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[Acid]--> β-PbO2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nIn acidic solution, red lead undergoes a disproportionation reaction, resulting in the formation of plattnerite - PbO2 (reaction 1) [17]: Pb3O4+4H^{+}\\rightarrowPbO2+2 Pb^{2+}+2H2O\n\n[1] Evidence classification: edge 1: direct\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\n\n[1] Evidence classification: edge 1: direct\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite\n\n[1] Evidence classification: edge 1: direct\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite \\begin{table} \\begin{tabular}{l l l l l l} No. & Type & Area of wall painting & Sample colour & Major components & Minor components \\\\ \\hline 1 & Fragment & Southern wall, dark line between & Black and grey & Plattnerite, PbMg(CO3)2, calcite & Hydrocerussite, scrutinyite \\\\ 2 & Fragment & Southern wall, right part of & White, ochre, black & Plattnerite, cervusite, & Calcite, scrutinyite \\\\ & & Massacre of the Innocent scene & PbMg(CO3)2, hydrocerussite & \\\\ 3 & Fragment & Southern wall, right part of & Black, white, ochre & Plattnerite, cervusite, & Calcite \\\\ & & Massacre of the Innocent scene & PbMg(CO3)2, hydrocerussite & \\\\ 4 & Fragment & Southern wall, outline of the & Black, white & Plattnerite & Calcite, cervusite, scrutinyite \\\\ & & finger of Isaiah & & & \\\\ 4 & Fragment & Southern wall, outline of the & Black, white & Plattnerite & Calcite, cervusite, scrutinyite \\\\ & & finger of Isaiah & & & \\\\ 5 & Fragment & Southern wall, halo of prophet in & Black, white & Calcite, plattnerite, cervusite & Gypsum, massicot, scrutinyite \\\\ & & the Nativity scene & & & \\\\ 6 & Fragment & Southern wall, dark line between & Black, white, red & Plattnerite & Calcite, gypsum, scrutinyite \\\\ & & Measurement 1", "ref_list": ["KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001."], "ref_snippets": [{"text": "In acidic solution, red lead undergoes a disproportionation reaction, resulting in the formation of plattnerite - PbO2 (reaction 1) [17]: Pb3O4+4H^{+}\\rightarrowPbO2+2 Pb^{2+}+2H2O\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite \\begin{table} \\begin{tabular}{l l l l l l} No. & Type & Area of wall painting & Sample colour & Major components & Minor components \\\\ \\hline 1 & Fragment & Southern wall, dark line between & Black and grey & Plattnerite, PbMg(CO3)2, calcite & Hydrocerussite, scrutinyite \\\\ 2 & Fragment & Southern wall, right part of & White, ochre, black & Plattnerite, cervusite, & Calcite, scrutinyite \\\\ & & Massacre of the Innocent scene & PbMg(CO3)2, hydrocerussite & \\\\ 3 & Fragment & Southern wall, right part of & Black, white, ochre & Plattnerite, cervusite, & Calcite \\\\ & & Massacre of the Innocent scene & PbMg(CO3)2, hydrocerussite & \\\\ 4 & Fragment & Southern wall, outline of the & Black, white & Plattnerite & Calcite, cervusite, scrutinyite \\\\ & & finger of Isaiah & & & \\\\ 4 & Fragment & Southern wall, outline of the & Black, white & Plattnerite & Calcite, cervusite, scrutinyite \\\\ & & finger of Isaiah & & & \\\\ 5 & Fragment & Southern wall, halo of prophet in & Black, white & Calcite, plattnerite, cervusite & Gypsum, massicot, scrutinyite \\\\ & & the Nativity scene & & & \\\\ 6 & Fragment & Southern wall, dark line between & Black, white, red & Plattnerite & Calcite, gypsum, scrutinyite \\\\ & & Measurement 1", "score": null, "snippets": [{"text": "In acidic solution, red lead undergoes a disproportionation reaction, resulting in the formation of plattnerite - PbO2 (reaction 1) [17]: Pb3O4+4H^{+}\\rightarrowPbO2+2 Pb^{2+}+2H2O", "score": null, "metadata": {"doi": "10.1016/j.culher.2008.11.001", "title": "Degradation of lead-based pigments by salt solutions", "journal": "Journal of Cultural Heritage", "source_file": "Degradation of lead-based pigments by salt solutions.md", "year": "2009", "chunk_index": 4, "ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "authors": [{"family": "Kotulanová", "given": "Eva"}, {"family": "Bezdička", "given": "Petr"}, {"family": "Hradil", "given": "David"}, {"family": "Hradilová", "given": "Janka"}, {"family": "Švarcová", "given": "Silvie"}, {"family": "Grygar", "given": "Tomáš"}], "volume": "10", "issue": "3", "pages": "367-378", "url": "https://doi.org/10.1016/j.culher.2008.11.001"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Acid", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "In acidic solution, red lead undergoes a disproportionation reaction, resulting in the formation of plattnerite - PbO2 (reaction 1) [17]: Pb3O4+4H^{+}\\rightarrowPbO2+2 Pb^{2+}+2H2O", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "score": null, "metadata": {"year": "2009", "chunk_index": 42, "doi": "10.1016/j.culher.2008.11.001", "journal": "Journal of Cultural Heritage", "ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "source_file": "Degradation of lead-based pigments by salt solutions.md", "title": "Degradation of lead-based pigments by salt solutions", "authors": [{"family": "Kotulanová", "given": "Eva"}, {"family": "Bezdička", "given": "Petr"}, {"family": "Hradil", "given": "David"}, {"family": "Hradilová", "given": "Janka"}, {"family": "Švarcová", "given": "Silvie"}, {"family": "Grygar", "given": "Tomáš"}], "volume": "10", "issue": "3", "pages": "367-378", "url": "https://doi.org/10.1016/j.culher.2008.11.001"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Acid", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "score": null, "metadata": {"year": "2009", "journal": "Journal of Cultural Heritage", "source_file": "Degradation of lead-based pigments by salt solutions.md", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "title": "Degradation of lead-based pigments by salt solutions", "ingest_kind": "existing_chroma", "chunk_index": 45, "doi": "10.1016/j.culher.2008.11.001", "authors": [{"family": "Kotulanová", "given": "Eva"}, {"family": "Bezdička", "given": "Petr"}, {"family": "Hradil", "given": "David"}, {"family": "Hradilová", "given": "Janka"}, {"family": "Švarcová", "given": "Silvie"}, {"family": "Grygar", "given": "Tomáš"}], "volume": "10", "issue": "3", "pages": "367-378", "url": "https://doi.org/10.1016/j.culher.2008.11.001"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Acid", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite \\begin{table} \\begin{tabular}{l l l l l l} No. & Type & Area of wall painting & Sample colour & Major components & Minor components \\\\ \\hline 1 & Fragment & Southern wall, dark line between & Black and grey & Plattnerite, PbMg(CO3)2, calcite & Hydrocerussite, scrutinyite \\\\ 2 & Fragment & Southern wall, right part of & White, ochre, black & Plattnerite, cervusite, & Calcite, scrutinyite \\\\ & & Massacre of the Innocent scene & PbMg(CO3)2, hydrocerussite & \\\\ 3 & Fragment & Southern wall, right part of & Black, white, ochre & Plattnerite, cervusite, & Calcite \\\\ & & Massacre of the Innocent scene & PbMg(CO3)2, hydrocerussite & \\\\ 4 & Fragment & Southern wall, outline of the & Black, white & Plattnerite & Calcite, cervusite, scrutinyite \\\\ & & finger of Isaiah & & & \\\\ 4 & Fragment & Southern wall, outline of the & Black, white & Plattnerite & Calcite, cervusite, scrutinyite \\\\ & & finger of Isaiah & & & \\\\ 5 & Fragment & Southern wall, halo of prophet in & Black, white & Calcite, plattnerite, cervusite & Gypsum, massicot, scrutinyite \\\\ & & the Nativity scene & & & \\\\ 6 & Fragment & Southern wall, dark line between & Black, white, red & Plattnerite & Calcite, gypsum, scrutinyite \\\\ & & Measurement 1", "score": null, "metadata": {"ingest_kind": "existing_chroma", "source_file": "Degradation of lead-based pigments by salt solutions.md", "chunk_index": 46, "doi": "10.1016/j.culher.2008.11.001", "title": "Degradation of lead-based pigments by salt solutions", "journal": "Journal of Cultural Heritage", "year": "2009", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "authors": [{"family": "Kotulanová", "given": "Eva"}, {"family": "Bezdička", "given": "Petr"}, {"family": "Hradil", "given": "David"}, {"family": "Hradilová", "given": "Janka"}, {"family": "Švarcová", "given": "Silvie"}, {"family": "Grygar", "given": "Tomáš"}], "volume": "10", "issue": "3", "pages": "367-378", "url": "https://doi.org/10.1016/j.culher.2008.11.001"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Acid", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite \\begin{table} \\begin{tabular}{l l l l l l} No. & Type & Area of wall painting & Sample colour & Major components & Minor components \\\\ \\hline 1 & Fragment & Southern wall, dark line between & Black and grey & Plattnerite, PbMg(CO3)2, calcite & Hydrocerussite, scrutinyite \\\\ 2 & Fragment & Southern wall, right part of & White, ochre, black & Plattnerite, cervusite, & Calcite, scrutinyite \\\\ & & Massacre of the Innocent scene & PbMg(CO3)2, hydrocerussite & \\\\ 3 & Fragment & Southern wall, right part of & Black, white, ochre & Plattnerite, cervusite, & Calcite \\\\ & & Massacre of the Innocent scene & PbMg(CO3)2, hydrocerussite & \\\\ 4 & Fragment & Southern wall, outline of the & Black, white & Plattnerite & Calcite, cervusite, scrutinyite \\\\ & & finger of Isaiah & & & \\\\ 4 & Fragment & Southern wall, outline of the & Black, white & Plattnerite & Calcite, cervusite, scrutinyite \\\\ & & finger of Isaiah & & & \\\\ 5 & Fragment & Southern wall, halo of prophet in & Black, white & Calcite, plattnerite, cervusite & Gypsum, massicot, scrutinyite \\\\ & & the Nativity scene & & & \\\\ 6 & Fragment & Southern wall, dark line between & Black, white, red & Plattnerite & Calcite, gypsum, scrutinyite \\\\ & & Measurement 1", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 64, "resolver_kept": 3, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 201, "lexical_kept": 3, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/26e7deb714459d7fb1fafc366bc5bcdb3c847c2b.json b/rag_report_cache/26e7deb714459d7fb1fafc366bc5bcdb3c847c2b.json
new file mode 100644
index 0000000000000000000000000000000000000000..8712face23a46e5d22e0df6512b67d16095c9618
--- /dev/null
+++ b/rag_report_cache/26e7deb714459d7fb1fafc366bc5bcdb3c847c2b.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Biogenic+Sulfate]--> Cu4SO4(OH)6", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w.", "snippet": "Unfortunately no other bands could be obtained from the green area. As in the previous cases, these sculptures seem to have suffered a biological attack, as the presence of calcium oxalate suggests. Unfortunately, the raw green pigment was completely decayed (it was quantitatively transformed into moolooite) and it was not possible to identify it. Thermodynamic Modeling, Degradation Mechanisms, and Reactions. According to the experimental data obtained, it is possible to propose several degradation routes (mecha- nisms) for copper green pigments, such as malachite (Cu 2- CO3(OH)2) to moolooite (CuC 2O4·nH2O), passing through copper hydroxysulphates posnjakite (Cu 4SO4(OH)6·H2O), bro - chantite (Cu 4SO4(OH)6), antlerite (Cu 3SO4(OH)4), etc., and/ or copper hydroxychlorides atacamite (Cu 2Cl(OH) 3), parata - camite (Cu 2Cl(OH) 3), etc., depending on the chemical condi- tions. In order to assess the degradation pathways and confirm the thermodynamic stability of all the solid phases identified from the experimental data obtained, we have performed a chemical reaction simulation using the MEDUSA software. This modeling Figure 3. Chemical simulation by MEDUSA software of a micro- biological attack (continuous increasing of oxalic acid concentration) over malachite in the presence of high levels of sulfate. Malachite (Cu 2CO3(OH)2), atacamite (CuCl 2·3Cu(OH)2), brochantite (Cu 4SO4- (OH)6), and antlerite (Cu 3SO4(OH)4) are the solids appearing as predominant species. Figure 4.", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "Cu4SO4(OH)6", "condition": "Biogenic+Sulfate", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "According to the experimental data obtained, it is possible to propose several degradation routes (mecha- nisms) for copper green pigments, such as malachite (Cu 2- CO3(OH)2) to moolooite (CuC 2O4·nH2O), passing through copper hydroxysulphates posnjakite (Cu4SO4(OH)6·H2O), bro - chantite (Cu4SO4(OH)6), antlerite (Cu3SO4(OH)4), etc., and/ or copper hydroxychlorides atacamite (Cu2Cl(OH)3), parata - camite (Cu2Cl(OH)3), etc., depending on the chemical condi- tions. In order to assess the degradation pathways and confirm the thermodynamic stability of all the solid phases identified from the experimental data obtained, we have performed a chemical reaction simulation using the MEDUSA software. This modeling Figure 3. Chemical simulation by MEDUSA software of a micro- biological attack (continuous increasing of oxalic acid concentration) over malachite in the presence of high levels of sulfate. Malachite (Cu2CO3(OH)2), atacamite (CuCl 2·3Cu(OH)2), brochantite (Cu4SO4- (OH)6), and antlerite (Cu3SO4(OH)4) are the solids appearing as predominant species.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "copper green", "product_span": "brochantite", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "The Use of X-Ray Photoelectron Spectroscopy in Studying Azurite and Malachite as Minerals, Pigments and in Secondary Products on Copper Objects [J/OL]. JOJ Material Science, 2026:9. DOI: 10.19080/jojms.2026.10.555788. (bibliographic metadata partially available)", "snippet": "e changes in binding energies during the degradation process Figure 3. During the initial corrosion process, metallic copper (Cu0) is converted to Cu2O (cuprite). The Cu 2p core level spectrum is characterized by binding energies around 932.5eV [45]. The XPS analysis on copper surfaces exposed for long durations in different atmospheric conditions showed that during the initial stages, cuprite is the dominant corrosion product, where copper in Cu2O has a lower binding energy compared to Cu (II). When copper is exposed to the atmosphere for long durations, the corrosion products gradually change due to the presence of sulfur dioxide in the atmosphere. During this period, copper is converted from Cu2O to brochantite (Cu4SO4(OH)6·2H2O). The Cu (II) in brochantite is characterized by binding energies ranging from 934-935eV, showing an increase in the copper oxidation state, similar to the binding energies in the azurite and malachite minerals, as discussed in the literature by Kloprogge & Wood [40]. A particularly illustrative case of the evolution of binding energies during the process of corrosion can be exemplified by the depth profiling of multi-layered systems of patina. In the urban atmospheric environment with mixed acid rain-induced acceleration of the corrosion process, the top layer of the patina contains Cu (II)-based compounds such as sulfates, oxides, and hydroxy oxides. In the interfacial region of the corrosion product layer and the underlying Cu metal, Cu 2O is found to be favored.", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "Cu4SO4(OH)6", "condition": "Biogenic+Sulfate", "evidence_scope": "edge", "verdict": "qualified", "score": 0.75, "window": "When copper is exposed to the atmosphere for long durations, the corrosion products gradually change due to the presence of sulfur dioxide in the atmosphere. During this period, copper is converted from Cu2O to brochantite (Cu4SO4(OH)6·2H2O). The Cu (II) in brochantite is characterized by binding energies ranging from 934-935eV, showing an increase in the copper oxidation state, similar to the binding energies in the azurite and malachite minerals, as discussed in the literature by Kloprogge & Wood [40].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "brochantite", "relation_basis": "product_identification", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["relation_product_identification", "condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 18, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 181, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/2ae7d0ca8e7289a53e8dedc08130d5ab913b04e5.json b/rag_report_cache/2ae7d0ca8e7289a53e8dedc08130d5ab913b04e5.json
new file mode 100644
index 0000000000000000000000000000000000000000..4e5cd26c7539e04bea39359b1ce84772dc359a49
--- /dev/null
+++ b/rag_report_cache/2ae7d0ca8e7289a53e8dedc08130d5ab913b04e5.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Chloride]--> α-Hg3S2Cl2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThe residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "ref_list": ["KEUNE K, BOON JJ. Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings [J/OL]. Analytical Chemistry, 2005. DOI: 10.1021/ac048158f.", "CHAPPÉ M, HILDENHAGEN J, DICKMANN K, et al. Laser irradiation of medieval pigments at IR, VIS and UV wavelengths [J/OL]. Journal of Cultural Heritage, 2003. DOI: 10.1016/s1296-2074(02)01206-2.", "COTTE M, SUSINI J, METRICH N, et al. Blackening of Pompeian Cinnabar Paintings: X-ray Microspectroscopy Analysis [J/OL]. Analytical Chemistry, 2006. DOI: 10.1021/ac0612224."], "ref_snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.42070335149765015, "snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.42070335149765015, "metadata": {"doi": "10.1021/ac048158f", "year": "2005", "journal": "Analytical Chemistry", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "ingest_kind": "existing_chroma", "chunk_index": 46, "authors": [{"family": "Keune", "given": "Katrien"}, {"family": "Boon", "given": "Jaap J."}], "volume": "77", "issue": "15", "pages": "4742-4750", "url": "https://doi.org/10.1021/ac048158f"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "alpha-Hg3S2Cl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "corderoite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 11, "dense_candidates": 220, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 14, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 200, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/2bdf1cf189143389be2f028648909a518a6a36f5.json b/rag_report_cache/2bdf1cf189143389be2f028648909a518a6a36f5.json
new file mode 100644
index 0000000000000000000000000000000000000000..7966ad3c04fd8a506e9076b7092f7346d1180fc6
--- /dev/null
+++ b/rag_report_cache/2bdf1cf189143389be2f028648909a518a6a36f5.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Moisture]--> CuCO3·Cu(OH)2 --[Biogenic+Sulfate]--> Cu4SO4(OH)6 --[Biogenic+Sulfate]--> Cu3SO4(OH)4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nBlack colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "ref_list": ["POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "CARDELL C, HERRERA A, GUERRA I, et al. Pigment-size effect on the physico-chemical behavior of azurite-tempera dosimeters upon natural and accelerated photo aging [J/OL]. Dyes and Pigments, 2017. DOI: 10.1016/j.dyepig.2017.02.001."], "ref_snippets": [{"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "score": 0.422015905380249, "snippets": [{"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "score": 0.422015905380249, "metadata": {"year": "2020", "ingest_kind": "pdf_direct", "doi": "10.3390/min10050424", "journal": "Minerals", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "source": "pdf_direct/min10050424_part2.pdf", "chunk_index": 7, "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCO3·Cu(OH)2", "condition": "Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "malachite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 29, "dense_candidates": 580, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 163, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 299, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/2cbc69581f8f87272a59c929bd4f3e937839b63c.json b/rag_report_cache/2cbc69581f8f87272a59c929bd4f3e937839b63c.json
new file mode 100644
index 0000000000000000000000000000000000000000..eedb8d6e57e01dcc8539d21167fb165d1c1cf037
--- /dev/null
+++ b/rag_report_cache/2cbc69581f8f87272a59c929bd4f3e937839b63c.json
@@ -0,0 +1 @@
+{"root_material": "2PbCO3·Pb(OH)2", "path_str": "2PbCO3·Pb(OH)2 --[CO2]--> PbCO3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nPhase abbreviations: Ce: cerussite (PbCO3); H: hydrocerussite (Pb3(CO3)2(OH)2); Ma: massicot (PbO). Figure 3: X-ray pattern of reaction product of lead white pigment with solution of Na2SO4. Phase abbreviations: Ce: cerussite (PbCO3); S: Pb4(CO3)2(SO4)(OH)2; H: hydrocerussite (Pb3(CO3)2(OH)2); Ma: massicot (PbO).\n\n[2] Evidence classification: edge 1: direct\nblack compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2}\n\n[2] Evidence classification: edge 1: direct\nblack compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2} Hydrogen sulfide concentrations were measured where the drawings were stored in 2018.\n\n[3] Evidence classification: edge 1: direct\nFigure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).\n\n[3] Evidence classification: edge 1: direct\nHydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "ref_list": ["KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001.", "PASTORELLI G, MIRANDA ASO, CLERICI EA, et al. Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation [J/OL]. Microchemical Journal, 2024. DOI: 10.1016/j.microc.2024.109912.", "VAGNINI M, VIVANI R, SGAMELLOTTI A, et al. Blackening of lead white: Study of model paintings [J/OL]. Journal of Raman Spectroscopy, 2020. DOI: 10.1002/jrs.5879."], "ref_snippets": [{"text": "Phase abbreviations: Ce: cerussite (PbCO3); H: hydrocerussite (Pb3(CO3)2(OH)2); Ma: massicot (PbO). Figure 3: X-ray pattern of reaction product of lead white pigment with solution of Na2SO4. Phase abbreviations: Ce: cerussite (PbCO3); S: Pb4(CO3)2(SO4)(OH)2; H: hydrocerussite (Pb3(CO3)2(OH)2); Ma: massicot (PbO).", "score": 0.45802968740463257, "snippets": [{"text": "Phase abbreviations: Ce: cerussite (PbCO3); H: hydrocerussite (Pb3(CO3)2(OH)2); Ma: massicot (PbO). Figure 3: X-ray pattern of reaction product of lead white pigment with solution of Na2SO4. Phase abbreviations: Ce: cerussite (PbCO3); S: Pb4(CO3)2(SO4)(OH)2; H: hydrocerussite (Pb3(CO3)2(OH)2); Ma: massicot (PbO).", "score": 0.45802968740463257, "metadata": {"journal": "Journal of Cultural Heritage", "chunk_index": 31, "doi": "10.1016/j.culher.2008.11.001", "year": "2009", "title": "Degradation of lead-based pigments by salt solutions", "source_file": "Degradation of lead-based pigments by salt solutions.md", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "ingest_kind": "existing_chroma", "authors": [{"family": "Kotulanová", "given": "Eva"}, {"family": "Bezdička", "given": "Petr"}, {"family": "Hradil", "given": "David"}, {"family": "Hradilová", "given": "Janka"}, {"family": "Švarcová", "given": "Silvie"}, {"family": "Grygar", "given": "Tomáš"}], "volume": "10", "issue": "3", "pages": "367-378", "url": "https://doi.org/10.1016/j.culher.2008.11.001"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbCO3", "condition": "CO2", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Phase abbreviations: Ce: cerussite (PbCO3); H: hydrocerussite (Pb3(CO3)2(OH)2); Ma: massicot (PbO). Figure 3: X-ray pattern of reaction product of lead white pigment with solution of Na2SO4. Phase abbreviations: Ce: cerussite (PbCO3); S: Pb4(CO3)2(SO4)(OH)2; H: hydrocerussite (Pb3(CO3)2(OH)2); Ma: massicot (PbO).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "cerussite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2}\nblack compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2} Hydrogen sulfide concentrations were measured where the drawings were stored in 2018.", "score": null, "snippets": [{"text": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2}", "score": null, "metadata": {"doi": "10.1016/j.microc.2024.109912", "ingest_kind": "existing_chroma", "source_file": "Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation.md", "title": "Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation", "year": "2024", "journal": "Microchemical Journal", "chunk_index": 39, "source": "markdown_output/Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation.md"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbCO3", "condition": "CO2", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2}", "reactant_match": "exact", "product_match": "exact", "reactant_span": "2PbCO3Pb(OH)2", "product_span": "PbCO3", "relation_basis": "explicit_equation", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2} Hydrogen sulfide concentrations were measured where the drawings were stored in 2018.", "score": null, "metadata": {"year": "2024", "doi": "10.1016/j.microc.2024.109912", "title": "Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation", "source": "markdown_output/Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation.md", "journal": "Microchemical Journal", "ingest_kind": "existing_chroma", "source_file": "Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation.md", "chunk_index": 40}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbCO3", "condition": "CO2", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2} Hydrogen sulfide concentrations were measured where the drawings were stored in 2018.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "2PbCO3Pb(OH)2", "product_span": "PbCO3", "relation_basis": "explicit_equation", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Figure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).\nHydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "score": null, "snippets": [{"text": "Figure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).", "score": null, "metadata": {"doi": "10.1002/jrs.5879", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "source_file": "Blackening of lead white: Study of model paintings.md", "title": "Blackening of lead white: Study of model paintings", "chunk_index": 31, "year": "2020", "ingest_kind": "existing_chroma", "journal": "Journal of Raman Spectroscopy"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbCO3", "condition": "CO2", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Figure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "cerussite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Hydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "score": null, "metadata": {"source": "markdown_output/Blackening of lead white: Study of model paintings.md", "ingest_kind": "existing_chroma", "journal": "Journal of Raman Spectroscopy", "source_file": "Blackening of lead white: Study of model paintings.md", "doi": "10.1002/jrs.5879", "title": "Blackening of lead white: Study of model paintings", "year": "2020", "chunk_index": 33}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbCO3", "condition": "CO2", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Hydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "cerussite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 81, "resolver_kept": 3, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 217, "lexical_kept": 5, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/2fa5016f36a3a3c1d34d4975cd4edca32783a320.json b/rag_report_cache/2fa5016f36a3a3c1d34d4975cd4edca32783a320.json
new file mode 100644
index 0000000000000000000000000000000000000000..2f77b7d2e0356fd4c52d0a91dcfb525e9c606730
--- /dev/null
+++ b/rag_report_cache/2fa5016f36a3a3c1d34d4975cd4edca32783a320.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[Sulfate]--> PbSO4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nFocused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate).", "ref_list": ["AZE S, VALLET JM, BARONNET A, et al. The fading of red lead pigment in wall paintings: tracking the physico-chemical transformations by means of complementary micro-analysis techniques [J/OL]. European Journal of Mineralogy, 2006. DOI: 10.1127/0935-1221/2006/0018-0835."], "ref_snippets": [{"text": "Focused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate).", "score": null, "snippets": [{"text": "Focused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate).", "score": null, "metadata": {"page": 1, "chunk_index": 0, "year": "2006", "fulltext_url": "https://content5.schweizerbart.de//download/9Q9fZcGIB42OwmxuPRKWLBOFU34YY6", "doi": "10.1127/0935-1221/2006/0018-0835", "journal": "European Journal of Mineralogy", "source_file": "The_fading_of_red_lead_pigment_in_wall_paintings_tracking_the_physico-chemical_transformat_0761b14aeacf.pdf", "ingest_kind": "pdf_fulltext", "source": "The_fading_of_red_lead_pigment_in_wall_paintings_tracking_the_physico-chemical_transformat_0761b14aeacf.pdf", "title": "The fading of red lead pigment in wall paintings: tracking the physico-chemical transformations by means of complementary micro-analysis techniques", "authors": [{"family": "Aze", "given": "Sébastien"}, {"family": "Vallet", "given": "Jean-Marc"}, {"family": "Baronnet", "given": "Alain"}, {"family": "Grauby", "given": "Olivier"}], "volume": "18", "issue": "6", "pages": "835-843", "url": "https://doi.org/10.1127/0935-1221/2006/0018-0835"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "resolver"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "PbSO4", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Focused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "lead sulphate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 14, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 201, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/315008dc660704791be195b5abdd70c026cdab2c.json b/rag_report_cache/315008dc660704791be195b5abdd70c026cdab2c.json
new file mode 100644
index 0000000000000000000000000000000000000000..edde3a3e60d1cbca3882b7d5f8b0d95fa944dbcb
--- /dev/null
+++ b/rag_report_cache/315008dc660704791be195b5abdd70c026cdab2c.json
@@ -0,0 +1 @@
+{"root_material": "C16H10N2O2", "path_str": "C16H10N2O2 --[Uv]--> C8H5NO2 --[Uv]--> C8H5NO3 --[Uv]--> C7H7NO2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nVerification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin\n\n[1] Evidence classification: edge 1: direct\nPage 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.\n\n[2] Evidence classification: edge 1: direct\nPage 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "ref_list": ["A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions [J/OL]. Heritage Science, 2023:8. DOI: 10.1186/s40494-023-00887-7. (bibliographic metadata partially available)", "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions [J/OL]. Heritage Science, 2023:9. DOI: 10.1186/s40494-023-00887-7. (bibliographic metadata partially available)", "DELGADO MC. El índigo en la pintura de caballete novohispana: mecanismos de deterioro [J/OL]. Intervención, Revista Internacional de Conservación, Restauración y Museología, 2019. DOI: 10.30763/intervencion.2019.19.206."], "ref_snippets": [{"text": "Verification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin\nPage 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.", "score": 0.43492257595062256, "snippets": [{"text": "Verification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin", "score": 0.43492257595062256, "metadata": {"source_file": "Indigo oxidation mechanism in grottoes murals by ozone", "chunk_index": "24", "year": "2023", "doi": "10.1186/s40494-023-00887-7", "source": "Indigo oxidation mechanism in grottoes murals by ozone", "page": "8", "journal": "Heritage Science", "ingest_kind": "pdf_fulltext", "title": "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C8H5NO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Verification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "isatin", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Page 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.", "score": 0.45905983448028564, "metadata": {"source": "Indigo oxidation mechanism in grottoes murals by ozone", "chunk_index": "22", "page": "8", "title": "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions", "doi": "10.1186/s40494-023-00887-7", "year": "2023", "ingest_kind": "pdf_fulltext", "journal": "Heritage Science", "source_file": "Indigo oxidation mechanism in grottoes murals by ozone"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C8H5NO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Page 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "isatin", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Page 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "score": null, "snippets": [{"text": "Page 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "score": null, "metadata": {"ingest_kind": "pdf_fulltext", "chunk_index": "25", "year": "2023", "doi": "10.1186/s40494-023-00887-7", "page": "9", "source": "Indigo oxidation mechanism in grottoes murals by ozone", "title": "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions", "journal": "Heritage Science", "source_file": "Indigo oxidation mechanism in grottoes murals by ozone"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C8H5NO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Page 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "isatin", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 29, "dense_candidates": 580, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 46, "resolver_kept": 3, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 169, "lexical_kept": 3, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/327cc7f75d78af10323c9684d1bf63a58c2bb828.json b/rag_report_cache/327cc7f75d78af10323c9684d1bf63a58c2bb828.json
new file mode 100644
index 0000000000000000000000000000000000000000..f20f8da47c3f907ce5f3f03dd4819250b679fb05
--- /dev/null
+++ b/rag_report_cache/327cc7f75d78af10323c9684d1bf63a58c2bb828.json
@@ -0,0 +1 @@
+{"root_material": "As4S4", "path_str": "As4S4 --[5000lux+1.65W/m2+30℃+60%RH]--> p-As4S4", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization [J/OL]. Heritage Science, 2024. DOI: 10.1186/s40494-024-01350-x. (bibliographic metadata partially available)", "snippet": "elemental analysis. With these methods, it is not always possible to distinguish arsenic-bearing minerals from synthetic arsenic sulfides and secondary phases. As for the latter, the degradation of realgar into pararealgar was not described in detail until 1996. Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72]. It is important to realize that to differentiate between the three classes of arsenic compounds, additional analytical methods of high specificity such as Raman spectroscopy and X-ray powder diffraction are essential. In this article, two types of arsenic sulfide pigments discovered in Rembrandt’s oeuvre are presented: (regular) pararealgar, which is yellow, and a semi- amorphous variant that is orange to red. The historic use, complexity of identification and interpretation of arsenic sulfides is studied in relevant historical sources to explain their use by Rembrandt. The presence of arsenic sulfides in The Night Watch was first detected by non-invasive imaging when the entire surface of the painting was scanned with macroscopic X-ray fluorescence imaging spectroscopy (MA-XRF) (Fig. 1c). Subsequent examination of the paint surface with stereomicroscopy revealed small areas of bright orange paint (Fig. 1d) in several areas at the surface and in the underpainting of the embroidery of Willem van Ruytenburch’s buff coat (the figure dressed in yellow in the mi", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "5000lux+1.65W/m2+30℃+60%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "KEUNE K, MASS J, MEHTA A, et al. Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues [J/OL]. Heritage Science, 2016. DOI: 10.1186/s40494-016-0078-1.", "snippet": "tue and vice, wisdom and strength, and mars and venus united by love. In: Metropolitan museum studies in art, science, and technology; 2010. p 83–108. 5. Keune K, Mass J, Meirer F, Pottasch C, van Loon A, Hull A, Church J, Pouyet E, Cotte M, Mehta A. Tracking the transformation and transport of arsenic sulfide pigments in paints: synchrotron-based X-ray micro-analysis. J Anal At Spectrom. 2015;30:813–27. 6. Douglass DL, Shing C, Wang G. The light-induced alteration of realgar to pararealgar. American Mineralolist. 1992;77:1266–74. 7. Ballirano P , Maras A. Preliminary results on the ligh-induced alteration of realgar: kinetics of the process. Plinius. 2002;28:35–6. 8. Mass J. Personal observations; 2015. 9. Trentelman K, Stodulski L, Pavlosky M. Characterization of pararealgar and other light-induced transformation products from realgar by Raman microspectroscopy. Anal Chem. 1996;68:1755–61. 10. Rötter C, Grundmann G, Richter M, van Loon A, Keune K, Boersma A, Rapp K. The occurrence of artificial orpiment (dry process) in northern European painting and polychromy and evidence in historical sources. In: Schuller M, Emmerling E, Nerdinger W, Verlag Anton Siegl, editors. Auripigment/Orpiment: Studien zu dem Mineral und den künstlichten Produkten. Fachbuchhandlung GmbH. München; 2007. 11. van Loon A: Colour changes and chemical reactivity in seventeenth-cen- tury oil paintings. In: Ph.D. Thesis. University of Amsterdam, Molart Series (14), AMOLF: Amsterdam; 2008. 12. Sheldon L, Woodcock S, Wallert A. Orpiment overlooked-expect the", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "5000lux+1.65W/m2+30℃+60%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "J Anal At Spectrom. 2015;30:813–27. 6. Douglass DL, Shing C, Wang G. The light-induced alteration of realgar to pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9.", "snippet": "This lecture text is aimed at teaching some insight into phase transitions of minerals. It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (\\(\\alpha\\)-As\\({}_{4}\\)S\\({}_{4}\\)) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As\\({}_{4}\\)S\\({}_{5}\\)) and arsenolite (As\\({}_{2}\\)O\\({}_{3}\\)) are obtained (step 1). The process continues through a set of cyclic reactions in which the sulfur atom released by the decomposition of As\\({}_{4}\\)S\\({}_{5}\\) (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "5000lux+1.65W/m2+30℃+60%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "The process continues through a set of cyclic reactions in which the sulfur atom released by the decomposition of As4S5 (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 157, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/3549858031691aa565f37f70da789e3056a80cf3.json b/rag_report_cache/3549858031691aa565f37f70da789e3056a80cf3.json
new file mode 100644
index 0000000000000000000000000000000000000000..17381f8809f675ed75240c6891e41c105ce8c2c4
--- /dev/null
+++ b/rag_report_cache/3549858031691aa565f37f70da789e3056a80cf3.json
@@ -0,0 +1 @@
+{"root_material": "2PbCO3·Pb(OH)2", "path_str": "2PbCO3·Pb(OH)2 --[Fresco]--> β-PbO --[Fresco]--> Pb3O4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nUpon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.\n\n[1] Evidence classification: edge 1: direct, pathway endpoints 2PbCO3·Pb(OH)2 -> Pb3O4: direct\nUnder a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "ref_list": ["VAGNINI M, VIVANI R, SGAMELLOTTI A, et al. Blackening of lead white: Study of model paintings [J/OL]. Journal of Raman Spectroscopy, 2020. DOI: 10.1002/jrs.5879."], "ref_snippets": [{"text": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.\nUnder a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "score": null, "snippets": [{"text": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.", "score": null, "metadata": {"source": "markdown_output/Blackening of lead white: Study of model paintings.md", "chunk_index": 21, "title": "Blackening of lead white: Study of model paintings", "doi": "10.1002/jrs.5879", "ingest_kind": "existing_chroma", "source_file": "Blackening of lead white: Study of model paintings.md", "journal": "Journal of Raman Spectroscopy", "year": "2020", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO", "condition": "Fresco", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "massicot", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "score": null, "metadata": {"title": "Blackening of lead white: Study of model paintings", "journal": "Journal of Raman Spectroscopy", "year": "2020", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "ingest_kind": "existing_chroma", "chunk_index": 35, "source_file": "Blackening of lead white: Study of model paintings.md", "doi": "10.1002/jrs.5879", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO", "condition": "Fresco", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "2PbCO3·Pb(OH)2", "product": "Pb3O4", "condition": "Fresco", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "hydrocerussite", "product_span": "Pb3O4", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 111, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 284, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/368bc0cf6e6464b50ef710aa2729551af6a85ebb.json b/rag_report_cache/368bc0cf6e6464b50ef710aa2729551af6a85ebb.json
new file mode 100644
index 0000000000000000000000000000000000000000..426a27e1b092e4ad83469f6224b4e0cd5439927f
--- /dev/null
+++ b/rag_report_cache/368bc0cf6e6464b50ef710aa2729551af6a85ebb.json
@@ -0,0 +1 @@
+{"root_material": "As4S4", "path_str": "As4S4 --[Uv]--> As2O3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nArsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.\n\n[2] Evidence classification: edge 1: direct\nHowever, arsenic oxide is also an expected degradation product of pararealgar itself [58].\n\n[3] Evidence classification: edge 1: direct\nExposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].\n\n[4] Evidence classification: edge 1: direct\nThe highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "ref_list": ["Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization [J/OL]. Heritage Science, 2024. DOI: 10.1186/s40494-024-01350-x. (bibliographic metadata partially available)", "VERMEULEN M, SAVERWYNS S, COUDRAY A, et al. Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments [J/OL]. Dyes and Pigments, 2018. DOI: 10.1016/j.dyepig.2017.10.009.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:16. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "KEUNE K, MASS J, MEHTA A, et al. Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues [J/OL]. Heritage Science, 2016. DOI: 10.1186/s40494-016-0078-1.", "JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9."], "ref_snippets": [{"text": "Arsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.", "score": 0.49438923597335815, "snippets": [{"text": "Arsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.", "score": 0.49438923597335815, "metadata": {"year": "2024", "journal": "Heritage Science", "doi": "10.1186/s40494-024-01350-x", "source": "pdf_direct/s40494-024-01350-x", "ingest_kind": "pdf_direct", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization", "chunk_index": 22, "source_file": "s40494-024-01350-x.pdf"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Arsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "pararealgar", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "However, arsenic oxide is also an expected degradation product of pararealgar itself [58].", "score": null, "snippets": [{"text": "However, arsenic oxide is also an expected degradation product of pararealgar itself [58].", "score": null, "metadata": {"journal": "Dyes and Pigments", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "chunk_index": 24, "ingest_kind": "pdf_reextract", "year": "2018", "doi": "10.1016/j.dyepig.2017.10.009", "source": "pdf_reextract/雄黄"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "However, arsenic oxide is also an expected degradation product of pararealgar itself [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "pararealgar", "product_span": "arsenic oxide", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "score": null, "snippets": [{"text": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "score": null, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "page": "16", "ingest_kind": "pdf_fulltext", "chunk_index": "53", "source_file": "On the stability of mediaeval inorganic pigments - a review", "doi": "10.1186/s40494-017-0125-6", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "journal": "Heritage Science"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "arsenic trioxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "score": null, "snippets": [{"text": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "score": null, "metadata": {"source_file": "s40494-016-0078-1.pdf", "journal": "Heritage Science", "year": "2016", "ingest_kind": "pdf_direct", "chunk_index": 5, "title": "Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues", "source": "pdf_direct/s40494-016-0078-1", "doi": "10.1186/s40494-016-0078-1"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 30, "resolver_kept": 4, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 165, "lexical_kept": 4, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/372ea2fcc6d3322eefb7278dfa73e04a4a444831.json b/rag_report_cache/372ea2fcc6d3322eefb7278dfa73e04a4a444831.json
new file mode 100644
index 0000000000000000000000000000000000000000..495c8494d5b8cc03600570e9cb980ccec31b41c4
--- /dev/null
+++ b/rag_report_cache/372ea2fcc6d3322eefb7278dfa73e04a4a444831.json
@@ -0,0 +1 @@
+{"root_material": "CaCO3", "path_str": "CaCO3 --[Sulfate]--> CaSO4·2H2O", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nIt is formed by the transformation of calcite (CaCO3) contained in the joint mortars and renders into gypsum by dry or wet deposition (acid rain) of sulfur dioxide (SO2).", "ref_list": ["KILIAN R, BORGATTA L, WENDLER E. Investigation of the deterioration mechanisms induced by moisture and soluble salts in the necropolis of Porta Nocera, Pompeii (Italy) [J/OL]. Heritage Science, 2023. DOI: 10.1186/s40494-023-00900-z."], "ref_snippets": [{"text": "It is formed by the transformation of calcite (CaCO3) contained in the joint mortars and renders into gypsum by dry or wet deposition (acid rain) of sulfur dioxide (SO2).", "score": 0.45167970657348633, "snippets": [{"text": "It is formed by the transformation of calcite (CaCO3) contained in the joint mortars and renders into gypsum by dry or wet deposition (acid rain) of sulfur dioxide (SO2).", "score": 0.45167970657348633, "metadata": {"title": "Investigation of the deterioration mechanisms induced by moisture and soluble salts in the necropolis of Porta Nocera, Pompeii (Italy)", "doi": "10.1186/s40494-023-00900-z", "journal": "Heritage Science", "ingest_kind": "existing_chroma", "chunk_index": 54, "source_file": "Investigation of the deterioration mechanisms induced by moisture and soluble salts in the necropolis of Porta Nocera, Pompeii (Italy).md", "year": "2023", "source": "markdown_output/Investigation of the deterioration mechanisms induced by moisture and soluble salts in the necropolis of Porta Nocera, Pompeii (Italy).md", "authors": [{"family": "Kilian", "given": "Ralf"}, {"family": "Borgatta", "given": "Léo"}, {"family": "Wendler", "given": "Eberhard"}], "volume": "11", "issue": "1", "article_number": "72", "url": "https://doi.org/10.1186/s40494-023-00900-z"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CaCO3", "product": "CaSO4·2H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "It is formed by the transformation of calcite (CaCO3) contained in the joint mortars and renders into gypsum by dry or wet deposition (acid rain) of sulfur dioxide (SO2).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "calcite", "product_span": "gypsum", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 44, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 136, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/39b76ae8c17227cad4fd0036c8d6b409d2052b68.json b/rag_report_cache/39b76ae8c17227cad4fd0036c8d6b409d2052b68.json
new file mode 100644
index 0000000000000000000000000000000000000000..cb9dd7ec0e3ed4f874ffe169f6523142eb7c6fb4
--- /dev/null
+++ b/rag_report_cache/39b76ae8c17227cad4fd0036c8d6b409d2052b68.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[tung_oil+Uv]--> 2PbCO3·Pb(OH)2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nDuring UV aging, the model paint samples' surface is verified gradually from wrinkled surface into nanoscale sheet-like structure and finally a regular hexagonal plate-like crystal structure, showing hexagonal crystals of hydrocerussit 2PbCO3Pb(OH)2. This reveals the interaction between organic tung oil binder and inorganic minium to accelerate the degradation of Pb3O4 pigment. Therefore, the degradation mechanism is deduced as that CO2 and H{}^{+} formed by oxidizing ester/carboxyl groups in tung oil reacts with Pb{}^{2+} to yield the white product of 2PbCO3Pb(OH)2.", "ref_list": ["ZHAO Y, WANG J, PAN A, et al. Degradation of red lead pigment in the oil painting during UV aging [J/OL]. Color Research & Application, 2019. DOI: 10.1002/col.22386."], "ref_snippets": [{"text": "During UV aging, the model paint samples' surface is verified gradually from wrinkled surface into nanoscale sheet-like structure and finally a regular hexagonal plate-like crystal structure, showing hexagonal crystals of hydrocerussit 2PbCO3Pb(OH)2. This reveals the interaction between organic tung oil binder and inorganic minium to accelerate the degradation of Pb3O4 pigment. Therefore, the degradation mechanism is deduced as that CO2 and H{}^{+} formed by oxidizing ester/carboxyl groups in tung oil reacts with Pb{}^{2+} to yield the white product of 2PbCO3Pb(OH)2.", "score": 0.33767104148864746, "snippets": [{"text": "During UV aging, the model paint samples' surface is verified gradually from wrinkled surface into nanoscale sheet-like structure and finally a regular hexagonal plate-like crystal structure, showing hexagonal crystals of hydrocerussit 2PbCO3Pb(OH)2. This reveals the interaction between organic tung oil binder and inorganic minium to accelerate the degradation of Pb3O4 pigment. Therefore, the degradation mechanism is deduced as that CO2 and H{}^{+} formed by oxidizing ester/carboxyl groups in tung oil reacts with Pb{}^{2+} to yield the white product of 2PbCO3Pb(OH)2.", "score": 0.33767104148864746, "metadata": {"chunk_index": 3, "title": "Degradation of red lead pigment in the oil painting during UV aging", "ingest_kind": "existing_chroma", "source_file": "Degradation of red lead pigment in the oil painting during UV aging.md", "source": "markdown_output/Degradation of red lead pigment in the oil painting during UV aging.md", "year": "2019", "journal": "Color Research & Application", "doi": "10.1002/col.22386", "authors": [{"family": "Zhao", "given": "Yanrui"}, {"family": "Wang", "given": "Jianli"}, {"family": "Pan", "given": "Aizhao"}, {"family": "He", "given": "Ling"}, {"family": "Simon", "given": "Stefan"}], "volume": "44", "issue": "5", "pages": "790-797", "url": "https://doi.org/10.1002/col.22386"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "2PbCO3·Pb(OH)2", "condition": "tungoil+Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "During UV aging, the model paint samples' surface is verified gradually from wrinkled surface into nanoscale sheet-like structure and finally a regular hexagonal plate-like crystal structure, showing hexagonal crystals of hydrocerussit 2PbCO3Pb(OH)2. This reveals the interaction between organic tung oil binder and inorganic minium to accelerate the degradation of Pb3O4 pigment. Therefore, the degradation mechanism is deduced as that CO2 and H{}^{+} formed by oxidizing ester/carboxyl groups in tung oil reacts with Pb{}^{2+} to yield the white product of 2PbCO3Pb(OH)2.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "minium", "product_span": "2PbCO3Pb(OH)2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 60, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 260, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/3a0ac03db3e07ca86c7be3dfa0ed71767235cb65.json b/rag_report_cache/3a0ac03db3e07ca86c7be3dfa0ed71767235cb65.json
new file mode 100644
index 0000000000000000000000000000000000000000..50f251bd7cf256965f651ce83496efc64df5e5a8
--- /dev/null
+++ b/rag_report_cache/3a0ac03db3e07ca86c7be3dfa0ed71767235cb65.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Uv]--> β-HgS", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\n### Vermilion The colour change of the Vermilion pigment (red to black) is the result of the following reaction: \\mathrm{HgSCinnabar}\\xrightarrow{laser}\\mathrm{HgSMetacinabar} The Cinnabar-Vermilion is a red material with a hexagonal crystal structure, Metacinnabar-Vermilion is black or grey-black obtaining a metallic sheet and a cubic structure.\n\n[2] Evidence classification: edge 1: direct\nThe small relative concentration of sulfur still present in the acids.[21] Since the sulfur is lost from the particle, it is inferred that a conversion of vermilion to meta-cinnabar is unlikely. The small relative concentration of sulfur still present in the particles is ascribed to intact residual intact vermilion. XRD measurements performed on reconstructions and other paint samples elsewhere by other authors support this conclusion.[2, 47, 39] It is shown that vermilion is still present in the XRD spectra of the blackened vermilion as is deduced from the decreased intensity of the XRD patterns of vermilion. No black meta-cinnabar was shown in the XRD spectra. Chlorine plays a dominant role in the light-induced blackening phenomenon, as already suggested in the literature.[7, 9] The much more sensitive surface technique of SIMS demonstrates, in contrast to the EDX results, that chloride is present inside the vermilion particles of both MH 251/26 and HSTB 34/2.\n\n[2] Evidence classification: edge 1: direct\nacids.[21] Since the sulfur is lost from the particle, it is inferred that a conversion of vermilion to meta-cinnabar is unlikely. The small relative concentration of sulfur still present in the particles is ascribed to intact residual intact vermilion. XRD measurements performed on reconstructions and other paint samples elsewhere by other authors support this conclusion.[2, 47, 39] It is shown that vermilion is still present in the XRD spectra of the blackened vermilion as is deduced from the decreased intensity of the XRD patterns of vermilion. No black meta-cinnabar was shown in the XRD spectra. Chlorine plays a dominant role in the light-induced blackening phenomenon, as already suggested in the literature.[7, 9] The much more sensitive surface technique of SIMS demonstrates, in contrast to the EDX results, that chloride is present inside the vermilion particles of both MH 251/26 and HSTB 34/2.\n\n[3] Evidence classification: edge 1: direct\nFigure 6: **FESEM images and XPS spectra of paint mock-ups.** a UV-exposed paint mock-up showing severe binder loss; **b** unaltered paint mock-up showing drying cracks (arrows) and **c** nano- to micrometer-sized mercury droplets (ranging from <100 nm to 1.5 μm, white arrows) on the mock-up surface after UV exposure (insets show EDS spectra of Hg{}^{0} droplet (white arrows) and HgS substrate (yellow arrow)); **d**, **e** depth profiles of 5 2p1/2 and Hg 4f5/2/Hg 4f7/2 upon ion beam etching (etch time in seconds) of cinnabar paint exposed to UV radiation for 2 months. would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1}\n\n[3] Evidence classification: edge 1: direct\nFigure 6: **FESEM images and XPS spectra of paint mock-ups.** a UV-exposed paint mock-up showing severe binder loss; **b** unaltered paint mock-up showing drying cracks (arrows) and **c** nano- to micrometer-sized mercury droplets (ranging from <100 nm to 1.5 μm, white arrows) on the mock-up surface after UV exposure (insets show EDS spectra of Hg{}^{0} droplet (white arrows) and HgS substrate (yellow arrow)); **d**, **e** depth profiles of 5 2p1/2 and Hg 4f5/2/Hg 4f7/2 upon ion beam etching (etch time in seconds) of cinnabar paint exposed to UV radiation for 2 months. would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].\n\n[4] Evidence classification: edge 1: direct\nThe origins of this darkening degradation are not clearly identified yet and remain a major issue for curators. In the specific case of cinnabar (HgS)-based red pigment, a photoinduced conversion into black metacinnabar is usually suspected.", "ref_list": ["CHAPPÉ M, HILDENHAGEN J, DICKMANN K, et al. Laser irradiation of medieval pigments at IR, VIS and UV wavelengths [J/OL]. Journal of Cultural Heritage, 2003. DOI: 10.1016/s1296-2074(02)01206-2.", "KEUNE K, BOON JJ. Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings [J/OL]. Analytical Chemistry, 2005. DOI: 10.1021/ac048158f.", "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "COTTE M, SUSINI J, METRICH N, et al. Blackening of Pompeian Cinnabar Paintings: X-ray Microspectroscopy Analysis [J/OL]. Analytical Chemistry, 2006. DOI: 10.1021/ac0612224."], "ref_snippets": [{"text": "### Vermilion The colour change of the Vermilion pigment (red to black) is the result of the following reaction: \\mathrm{HgSCinnabar}\\xrightarrow{laser}\\mathrm{HgSMetacinabar} The Cinnabar-Vermilion is a red material with a hexagonal crystal structure, Metacinnabar-Vermilion is black or grey-black obtaining a metallic sheet and a cubic structure.", "score": null, "snippets": [{"text": "### Vermilion The colour change of the Vermilion pigment (red to black) is the result of the following reaction: \\mathrm{HgSCinnabar}\\xrightarrow{laser}\\mathrm{HgSMetacinabar} The Cinnabar-Vermilion is a red material with a hexagonal crystal structure, Metacinnabar-Vermilion is black or grey-black obtaining a metallic sheet and a cubic structure.", "score": null, "metadata": {"title": "Laser irradiation of medieval pigments at IR, VIS and UV wavelengths", "year": "2003", "source_file": "Laser irradiation of medieval pigments at IR, VIS and UV wavelengths.md", "doi": "10.1016/s1296-2074(02)01206-2", "journal": "Journal of Cultural Heritage", "source": "markdown_output/Laser irradiation of medieval pigments at IR, VIS and UV wavelengths.md", "chunk_index": 14, "ingest_kind": "existing_chroma", "authors": [{"family": "Chappé", "given": "M"}, {"family": "Hildenhagen", "given": "J"}, {"family": "Dickmann", "given": "K"}, {"family": "Bredol", "given": "M"}], "volume": "4", "pages": "264-270", "url": "https://doi.org/10.1016/s1296-2074(02)01206-2"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "beta-HgS", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "### Vermilion The colour change of the Vermilion pigment (red to black) is the result of the following reaction: \\mathrm{HgSCinnabar}\\xrightarrow{laser}\\mathrm{HgSMetacinabar} The Cinnabar-Vermilion is a red material with a hexagonal crystal structure, Metacinnabar-Vermilion is black or grey-black obtaining a metallic sheet and a cubic structure.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "metacinnabar", "relation_basis": "explicit_equation", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The small relative concentration of sulfur still present in the acids.[21] Since the sulfur is lost from the particle, it is inferred that a conversion of vermilion to meta-cinnabar is unlikely. The small relative concentration of sulfur still present in the particles is ascribed to intact residual intact vermilion. XRD measurements performed on reconstructions and other paint samples elsewhere by other authors support this conclusion.[2, 47, 39] It is shown that vermilion is still present in the XRD spectra of the blackened vermilion as is deduced from the decreased intensity of the XRD patterns of vermilion. No black meta-cinnabar was shown in the XRD spectra. Chlorine plays a dominant role in the light-induced blackening phenomenon, as already suggested in the literature.[7, 9] The much more sensitive surface technique of SIMS demonstrates, in contrast to the EDX results, that chloride is present inside the vermilion particles of both MH 251/26 and HSTB 34/2.\nacids.[21] Since the sulfur is lost from the particle, it is inferred that a conversion of vermilion to meta-cinnabar is unlikely. The small relative concentration of sulfur still present in the particles is ascribed to intact residual intact vermilion. XRD measurements performed on reconstructions and other paint samples elsewhere by other authors support this conclusion.[2, 47, 39] It is shown that vermilion is still present in the XRD spectra of the blackened vermilion as is deduced from the decreased intensity of the XRD patterns of vermilion. No black meta-cinnabar was shown in the XRD spectra. Chlorine plays a dominant role in the light-induced blackening phenomenon, as already suggested in the literature.[7, 9] The much more sensitive surface technique of SIMS demonstrates, in contrast to the EDX results, that chloride is present inside the vermilion particles of both MH 251/26 and HSTB 34/2.", "score": null, "snippets": [{"text": "The small relative concentration of sulfur still present in the acids.[21] Since the sulfur is lost from the particle, it is inferred that a conversion of vermilion to meta-cinnabar is unlikely. The small relative concentration of sulfur still present in the particles is ascribed to intact residual intact vermilion. XRD measurements performed on reconstructions and other paint samples elsewhere by other authors support this conclusion.[2, 47, 39] It is shown that vermilion is still present in the XRD spectra of the blackened vermilion as is deduced from the decreased intensity of the XRD patterns of vermilion. No black meta-cinnabar was shown in the XRD spectra. Chlorine plays a dominant role in the light-induced blackening phenomenon, as already suggested in the literature.[7, 9] The much more sensitive surface technique of SIMS demonstrates, in contrast to the EDX results, that chloride is present inside the vermilion particles of both MH 251/26 and HSTB 34/2.", "score": null, "metadata": {"source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "chunk_index": 39, "journal": "Analytical Chemistry", "doi": "10.1021/ac048158f", "year": "2005", "ingest_kind": "existing_chroma", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "beta-HgS", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The small relative concentration of sulfur still present in the acids.[21] Since the sulfur is lost from the particle, it is inferred that a conversion of vermilion to meta-cinnabar is unlikely. The small relative concentration of sulfur still present in the particles is ascribed to intact residual intact vermilion. XRD measurements performed on reconstructions and other paint samples elsewhere by other authors support this conclusion.[2, 47, 39] It is shown that vermilion is still present in the XRD spectra of the blackened vermilion as is deduced from the decreased intensity of the XRD patterns of vermilion. No black meta-cinnabar was shown in the XRD spectra. Chlorine plays a dominant role in the light-induced blackening phenomenon, as already suggested in the literature.[7, 9] The much more sensitive surface technique of SIMS demonstrates, in contrast to the EDX results, that chloride is present inside the vermilion particles of both MH 251/26 and HSTB 34/2.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "metacinnabar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "acids.[21] Since the sulfur is lost from the particle, it is inferred that a conversion of vermilion to meta-cinnabar is unlikely. The small relative concentration of sulfur still present in the particles is ascribed to intact residual intact vermilion. XRD measurements performed on reconstructions and other paint samples elsewhere by other authors support this conclusion.[2, 47, 39] It is shown that vermilion is still present in the XRD spectra of the blackened vermilion as is deduced from the decreased intensity of the XRD patterns of vermilion. No black meta-cinnabar was shown in the XRD spectra. Chlorine plays a dominant role in the light-induced blackening phenomenon, as already suggested in the literature.[7, 9] The much more sensitive surface technique of SIMS demonstrates, in contrast to the EDX results, that chloride is present inside the vermilion particles of both MH 251/26 and HSTB 34/2.", "score": null, "metadata": {"journal": "Analytical Chemistry", "chunk_index": 40, "year": "2005", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "doi": "10.1021/ac048158f", "source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "ingest_kind": "existing_chroma", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "beta-HgS", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "acids.[21] Since the sulfur is lost from the particle, it is inferred that a conversion of vermilion to meta-cinnabar is unlikely. The small relative concentration of sulfur still present in the particles is ascribed to intact residual intact vermilion. XRD measurements performed on reconstructions and other paint samples elsewhere by other authors support this conclusion.[2, 47, 39] It is shown that vermilion is still present in the XRD spectra of the blackened vermilion as is deduced from the decreased intensity of the XRD patterns of vermilion. No black meta-cinnabar was shown in the XRD spectra. Chlorine plays a dominant role in the light-induced blackening phenomenon, as already suggested in the literature.[7, 9] The much more sensitive surface technique of SIMS demonstrates, in contrast to the EDX results, that chloride is present inside the vermilion particles of both MH 251/26 and HSTB 34/2.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "metacinnabar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Figure 6: **FESEM images and XPS spectra of paint mock-ups.** a UV-exposed paint mock-up showing severe binder loss; **b** unaltered paint mock-up showing drying cracks (arrows) and **c** nano- to micrometer-sized mercury droplets (ranging from <100 nm to 1.5 μm, white arrows) on the mock-up surface after UV exposure (insets show EDS spectra of Hg{}^{0} droplet (white arrows) and HgS substrate (yellow arrow)); **d**, **e** depth profiles of 5 2p1/2 and Hg 4f5/2/Hg 4f7/2 upon ion beam etching (etch time in seconds) of cinnabar paint exposed to UV radiation for 2 months. would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1}\nFigure 6: **FESEM images and XPS spectra of paint mock-ups.** a UV-exposed paint mock-up showing severe binder loss; **b** unaltered paint mock-up showing drying cracks (arrows) and **c** nano- to micrometer-sized mercury droplets (ranging from <100 nm to 1.5 μm, white arrows) on the mock-up surface after UV exposure (insets show EDS spectra of Hg{}^{0} droplet (white arrows) and HgS substrate (yellow arrow)); **d**, **e** depth profiles of 5 2p1/2 and Hg 4f5/2/Hg 4f7/2 upon ion beam etching (etch time in seconds) of cinnabar paint exposed to UV radiation for 2 months. would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "score": null, "snippets": [{"text": "Figure 6: **FESEM images and XPS spectra of paint mock-ups.** a UV-exposed paint mock-up showing severe binder loss; **b** unaltered paint mock-up showing drying cracks (arrows) and **c** nano- to micrometer-sized mercury droplets (ranging from <100 nm to 1.5 μm, white arrows) on the mock-up surface after UV exposure (insets show EDS spectra of Hg{}^{0} droplet (white arrows) and HgS substrate (yellow arrow)); **d**, **e** depth profiles of 5 2p1/2 and Hg 4f5/2/Hg 4f7/2 upon ion beam etching (etch time in seconds) of cinnabar paint exposed to UV radiation for 2 months. would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1}", "score": null, "metadata": {"title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "chunk_index": 42, "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "journal": "Communications Chemistry", "year": "2021", "doi": "10.1038/s42004-021-00610-2", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "beta-HgS", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Figure 6: **FESEM images and XPS spectra of paint mock-ups.** a UV-exposed paint mock-up showing severe binder loss; **b** unaltered paint mock-up showing drying cracks (arrows) and **c** nano- to micrometer-sized mercury droplets (ranging from <100 nm to 1.5 μm, white arrows) on the mock-up surface after UV exposure (insets show EDS spectra of Hg{}^{0} droplet (white arrows) and HgS substrate (yellow arrow)); **d**, **e** depth profiles of 5 2p1/2 and Hg 4f5/2/Hg 4f7/2 upon ion beam etching (etch time in seconds) of cinnabar paint exposed to UV radiation for 2 months. would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1}", "reactant_match": "alias", "product_match": "exact", "reactant_span": "cinnabar", "product_span": "HgS", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Figure 6: **FESEM images and XPS spectra of paint mock-ups.** a UV-exposed paint mock-up showing severe binder loss; **b** unaltered paint mock-up showing drying cracks (arrows) and **c** nano- to micrometer-sized mercury droplets (ranging from <100 nm to 1.5 μm, white arrows) on the mock-up surface after UV exposure (insets show EDS spectra of Hg{}^{0} droplet (white arrows) and HgS substrate (yellow arrow)); **d**, **e** depth profiles of 5 2p1/2 and Hg 4f5/2/Hg 4f7/2 upon ion beam etching (etch time in seconds) of cinnabar paint exposed to UV radiation for 2 months. would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "score": null, "metadata": {"year": "2021", "ingest_kind": "existing_chroma", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "chunk_index": 43, "journal": "Communications Chemistry", "doi": "10.1038/s42004-021-00610-2"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "beta-HgS", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Figure 6: **FESEM images and XPS spectra of paint mock-ups.** a UV-exposed paint mock-up showing severe binder loss; **b** unaltered paint mock-up showing drying cracks (arrows) and **c** nano- to micrometer-sized mercury droplets (ranging from <100 nm to 1.5 μm, white arrows) on the mock-up surface after UV exposure (insets show EDS spectra of Hg{}^{0} droplet (white arrows) and HgS substrate (yellow arrow)); **d**, **e** depth profiles of 5 2p1/2 and Hg 4f5/2/Hg 4f7/2 upon ion beam etching (etch time in seconds) of cinnabar paint exposed to UV radiation for 2 months. would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "cinnabar", "product_span": "HgS", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The origins of this darkening degradation are not clearly identified yet and remain a major issue for curators. In the specific case of cinnabar (HgS)-based red pigment, a photoinduced conversion into black metacinnabar is usually suspected.", "score": null, "snippets": [{"text": "The origins of this darkening degradation are not clearly identified yet and remain a major issue for curators. In the specific case of cinnabar (HgS)-based red pigment, a photoinduced conversion into black metacinnabar is usually suspected.", "score": null, "metadata": {"source_file": "Blackening of Pompeian Cinnabar Paintings: X-ray Microspectroscopy Analysis.md", "source": "pdf_reextract/朱砂", "year": "2006", "ingest_kind": "pdf_reextract", "chunk_index": 0, "title": "Blackening of Pompeian Cinnabar Paintings: X-ray Microspectroscopy Analysis", "doi": "10.1021/ac0612224", "journal": "Analytical Chemistry"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "beta-HgS", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The origins of this darkening degradation are not clearly identified yet and remain a major issue for curators. In the specific case of cinnabar (HgS)-based red pigment, a photoinduced conversion into black metacinnabar is usually suspected.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "metacinnabar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 7, "dense_candidates": 140, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 217, "resolver_kept": 6, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 217, "lexical_kept": 6, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/3e838c4a5a32c0211343dc8403984e1d713e8964.json b/rag_report_cache/3e838c4a5a32c0211343dc8403984e1d713e8964.json
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index 0000000000000000000000000000000000000000..8a003add6486ebf6ccc1832a2ea28b1586654c9d
--- /dev/null
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@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[12000lux+1.5W/m2+60℃+90%RH]--> CuCO3·Cu(OH)2", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CRN source: In-house aging experiment"], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}], "related_context": [{"source": "The Use of X-Ray Photoelectron Spectroscopy in Studying Azurite and Malachite as Minerals, Pigments and in Secondary Products on Copper Objects [J/OL]. JOJ Material Science, 2026:11. DOI: 10.19080/jojms.2026.10.555788. (bibliographic metadata partially available)", "snippet": "e, reflecting changes in the coordination environment around copper, from hydroxide-rich to oxide-rich coordination [48]. At 300°C, copper oxide and copper carbonate may coexist, leading to complex XPS spectra, where multiple features may be present. The binding energies for these copper pigments at intermediate stages will be between the main features in the handbook spectra for the pure copper carbonates (934.6eV for copper in azurite and 935.1eV for copper in malachite) and the binding energies for CuO [48]. Further heating to 400°C and above leads to the complete transformation of azurite to tenorite (CuO) or malachite to a combination of tenorite and finally copper(I) oxide in a reducing environment [48]. The Cu 2p 3/2 binding energy for the pure CuO phase is centered at 933.5 to 934.0eV, which is slightly lower than the Cu 2p 3/2 binding energy for the hydroxycarbonate compounds. This is due to the absence of hydroxyl groups and the square planar coordination geometry of the Cu2+ ions in the CuO crystal. This Cu 2p binding energy for CuO at 933.5 to 934.0eV is significantly lower than the Cu2+ peak for malachite at 935.1eV and is even lower than the Cu2+ peak for azurite at 934.6eV [40]. This shows that the removal of the hydroxide ligand during the thermal decomposition leads to a decrease in the Cu 2p binding energy due to a reduction in the electrostatic potential around the Cu2+ ion.", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCO3·Cu(OH)2", "condition": "12000lux+1.5W/m2+60℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "Further heating to 400°C and above leads to the complete transformation of azurite to tenorite (CuO) or malachite to a combination of tenorite and finally copper(I) oxide in a reducing environment [48].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "malachite", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "snippet": "mpurities of other minerals such as calcite, haematite (Fe 2O3), goethite α-FeO(OH), quartz (SiO 2), cuprite (Cu 2O), rutile/anatase (TiO 2), and chrysocolle ((Cu,Al)2H2Si2O5(OH)4·nH2O, found with malachite), as well as trace elements including arsenic (As), zirconium (Zr), antimony (Sb), barium (Ba), zinc (Zn), and bismuth (Bi) [28–30]. In fact, the particular mineral composition of natural azurite and malachite varies significantly between artworks produced at different times and places, and may be related to provenance [30]. In addition to the mineralogy, the pigment grain size also influences the color and other superficial physical properties, as demonstrated for azurite in severa l scientific papers [22,31]. These studies also highlighted the importance of the binder (type and co ntent) on the physical properties of the paint. Therefore, the mineralogy, pigment grain size and the type and content of binder should be evaluated to understand the deterioration processes that ta ke place in tempera paints under different decay scenarios. Azurite is formed from cupric-ion-bearing solutions under relatively acid conditions and relatively high carbonate activity, while malachite is a more common form of copper carbonate under ambient conditions [32]. Malachite may pseudomorph after azurite; thus malachite maintains the same external form as the original azurite crystal, but the unit cells of azurite are gradually replaced by those of malachite. In aqueous systems, CO 32− and HCO3− activities (and Cu 2+ activity to a lesser extent) define the stability of bot", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCO3·Cu(OH)2", "condition": "12000lux+1.5W/m2+60℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "Azurite is formed from cupric-ion-bearing solutions under relatively acid conditions and relatively high carbonate activity, while malachite is a more common form of copper carbonate under ambient conditions [32].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "malachite", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "snippet": "azurite degrades into tenorite on ly below the critical value of 25 µm. To study the chemical alteration of azurite, the pigment has been applied on the plaster o f terracotta samples and analyzed at different pH values by micro-Raman spectroscopy. As opposed to mos t part of the analytical techniques, it can detect the presence of both azurite and tenorite molecules i n the same micro areas, and provides a valuable tool to determine azurite degradation. Copyright 2008 John Wiley & Sons, Ltd. KEYWORDS: azurite; tenorite; laser-induced degradation; pigments alteration INTRODUCTION Azurite is a natural mineral pigment whose chemical composition is basic copper carbonate (2CuCO 3ÐCu(OH)2). It was largely employed in paintings particularly around the middle Ages and the Renaissance, both in Europe and in the East. 1,2 It presents an intense blue color whose tone depends on the grain size, the smaller grains producing a paler blue color. Unfortunately, this pigment suffers from chemical and/or thermal alterations, so that the parts of the artwork containing azurite are usually less resistant than those painted with other pigments. The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite). The conversion into black compounds with formation of copper sulfide 5 (covellite: CuS) or copper oxide 6 (tenorite: CuO) occurs less frequently and is less st", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCO3·Cu(OH)2", "condition": "12000lux+1.5W/m2+60℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "malachite", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 148, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 241, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/43d381a5e376f9af2e8b85de32f8f1fa34e9c681.json b/rag_report_cache/43d381a5e376f9af2e8b85de32f8f1fa34e9c681.json
new file mode 100644
index 0000000000000000000000000000000000000000..c4aef565311d016ca5492f4c203ec2ebb776d641
--- /dev/null
+++ b/rag_report_cache/43d381a5e376f9af2e8b85de32f8f1fa34e9c681.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[tung_oil+Uv]--> 2PbCO3·Pb(OH)2 --[Fresco]--> β-PbO", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nDuring UV aging, the model paint samples' surface is verified gradually from wrinkled surface into nanoscale sheet-like structure and finally a regular hexagonal plate-like crystal structure, showing hexagonal crystals of hydrocerussit 2PbCO3Pb(OH)2. This reveals the interaction between organic tung oil binder and inorganic minium to accelerate the degradation of Pb3O4 pigment. Therefore, the degradation mechanism is deduced as that CO2 and H{}^{+} formed by oxidizing ester/carboxyl groups in tung oil reacts with Pb{}^{2+} to yield the white product of 2PbCO3Pb(OH)2.\n\n[2] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nthrough successive water and carbonate losses [25] (reactions 1.3 to 1.5). At higher temperature and in oxidizing conditions, litharge was finally converted into minium (Pb3O4, reaction 1.6). \\mathrm{Pb(s)+2CH3COOH\\to Pb(CH3COO)2+H2} \\tag{1} \\mathrm{3Pb(CH3COO)2+12O2\\to 2PbCO3\\cdot Pb(OH)2+10CO2+8H2O} \\tag{2} \\mathrm{2PbCO3\\cdot Pb(OH)2\\to 2PbCO3\\cdot PbO+H2O} \\tag{3} \\mathrm{2PbCO3\\cdot PbO\\to CO2+PbCO3\\cdot 2PbO} \\tag{4} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} According to Brown and Nees [26], litharge may be converted into minium through transitional steps, corresponding to intermediate oxidation states.\n\n[2] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nAccording to various authors, minium reduction into massicot is initiated in air over 512{}^{\\circ}C [25], 650{}^{\\circ}C [32], 535{}^{\\circ}C [33], 560{}^{\\circ}C [34].\n\n[3] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nThe parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244].\n\n[3] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nThe PbO formed by laser irra - diation can be re-oxidized to minium [142].\n\n[4] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nFormation of PbO (which can be re‐oxidised to minium, [142]) [215, 240] Formation of litharge [1, 240] Green Green earths glauconite (K,Na) (Fe 3+,Al,Mg)2 (Si,Al)4O10(OH)2) celadonite (K[(Al,Fe3+), (Fe2+,Mg)] (AlSi3,Si4) O10(OH)2 Browning [74], discolouration of oil layers [75] Green Malachite CuCO 3·Cu(OH)2 Cu acts as a biocide [124].\n\n[5] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nThe sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound.\n\n[6] Evidence classification: edge 2: direct\nUpon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.\n\n[6] Evidence classification: edge 2: direct, pathway endpoints Pb3O4 -> beta-PbO: direct\nUnder a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "ref_list": ["ZHAO Y, WANG J, PAN A, et al. Degradation of red lead pigment in the oil painting during UV aging [J/OL]. Color Research & Application, 2019. DOI: 10.1002/col.22386.", "AZE S, VALLET JM, DETALLE V, et al. Chromatic alterations of red lead pigments in artworks: a review [J/OL]. Phase Transitions, 2008. DOI: 10.1080/01411590701514326.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:19. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:8. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "SMITH GD, CLARK RJH. The role of H2S in pigment blackening [J/OL]. Journal of Cultural Heritage, 2002. DOI: 10.1016/s1296-2074(02)01173-1.", "VAGNINI M, VIVANI R, SGAMELLOTTI A, et al. Blackening of lead white: Study of model paintings [J/OL]. Journal of Raman Spectroscopy, 2020. DOI: 10.1002/jrs.5879."], "ref_snippets": [{"text": "During UV aging, the model paint samples' surface is verified gradually from wrinkled surface into nanoscale sheet-like structure and finally a regular hexagonal plate-like crystal structure, showing hexagonal crystals of hydrocerussit 2PbCO3Pb(OH)2. This reveals the interaction between organic tung oil binder and inorganic minium to accelerate the degradation of Pb3O4 pigment. Therefore, the degradation mechanism is deduced as that CO2 and H{}^{+} formed by oxidizing ester/carboxyl groups in tung oil reacts with Pb{}^{2+} to yield the white product of 2PbCO3Pb(OH)2.", "score": 0.337671160697937, "snippets": [{"text": "During UV aging, the model paint samples' surface is verified gradually from wrinkled surface into nanoscale sheet-like structure and finally a regular hexagonal plate-like crystal structure, showing hexagonal crystals of hydrocerussit 2PbCO3Pb(OH)2. This reveals the interaction between organic tung oil binder and inorganic minium to accelerate the degradation of Pb3O4 pigment. Therefore, the degradation mechanism is deduced as that CO2 and H{}^{+} formed by oxidizing ester/carboxyl groups in tung oil reacts with Pb{}^{2+} to yield the white product of 2PbCO3Pb(OH)2.", "score": 0.337671160697937, "metadata": {"chunk_index": 3, "source": "markdown_output/Degradation of red lead pigment in the oil painting during UV aging.md", "journal": "Color Research & Application", "title": "Degradation of red lead pigment in the oil painting during UV aging", "source_file": "Degradation of red lead pigment in the oil painting during UV aging.md", "year": "2019", "ingest_kind": "existing_chroma", "doi": "10.1002/col.22386", "authors": [{"family": "Zhao", "given": "Yanrui"}, {"family": "Wang", "given": "Jianli"}, {"family": "Pan", "given": "Aizhao"}, {"family": "He", "given": "Ling"}, {"family": "Simon", "given": "Stefan"}], "volume": "44", "issue": "5", "pages": "790-797", "url": "https://doi.org/10.1002/col.22386"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "2PbCO3·Pb(OH)2", "condition": "tungoil+Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "During UV aging, the model paint samples' surface is verified gradually from wrinkled surface into nanoscale sheet-like structure and finally a regular hexagonal plate-like crystal structure, showing hexagonal crystals of hydrocerussit 2PbCO3Pb(OH)2. This reveals the interaction between organic tung oil binder and inorganic minium to accelerate the degradation of Pb3O4 pigment. Therefore, the degradation mechanism is deduced as that CO2 and H{}^{+} formed by oxidizing ester/carboxyl groups in tung oil reacts with Pb{}^{2+} to yield the white product of 2PbCO3Pb(OH)2.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "minium", "product_span": "2PbCO3Pb(OH)2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "through successive water and carbonate losses [25] (reactions 1.3 to 1.5). At higher temperature and in oxidizing conditions, litharge was finally converted into minium (Pb3O4, reaction 1.6). \\mathrm{Pb(s)+2CH3COOH\\to Pb(CH3COO)2+H2} \\tag{1} \\mathrm{3Pb(CH3COO)2+12O2\\to 2PbCO3\\cdot Pb(OH)2+10CO2+8H2O} \\tag{2} \\mathrm{2PbCO3\\cdot Pb(OH)2\\to 2PbCO3\\cdot PbO+H2O} \\tag{3} \\mathrm{2PbCO3\\cdot PbO\\to CO2+PbCO3\\cdot 2PbO} \\tag{4} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} According to Brown and Nees [26], litharge may be converted into minium through transitional steps, corresponding to intermediate oxidation states.\nAccording to various authors, minium reduction into massicot is initiated in air over 512{}^{\\circ}C [25], 650{}^{\\circ}C [32], 535{}^{\\circ}C [33], 560{}^{\\circ}C [34].", "score": 0.4271876811981201, "snippets": [{"text": "through successive water and carbonate losses [25] (reactions 1.3 to 1.5). At higher temperature and in oxidizing conditions, litharge was finally converted into minium (Pb3O4, reaction 1.6). \\mathrm{Pb(s)+2CH3COOH\\to Pb(CH3COO)2+H2} \\tag{1} \\mathrm{3Pb(CH3COO)2+12O2\\to 2PbCO3\\cdot Pb(OH)2+10CO2+8H2O} \\tag{2} \\mathrm{2PbCO3\\cdot Pb(OH)2\\to 2PbCO3\\cdot PbO+H2O} \\tag{3} \\mathrm{2PbCO3\\cdot PbO\\to CO2+PbCO3\\cdot 2PbO} \\tag{4} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} According to Brown and Nees [26], litharge may be converted into minium through transitional steps, corresponding to intermediate oxidation states.", "score": 0.4271876811981201, "metadata": {"ingest_kind": "existing_chroma", "doi": "10.1080/01411590701514326", "journal": "Phase Transitions", "title": "Chromatic alterations of red lead pigments in artworks: a review", "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md", "year": "2008", "source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "chunk_index": 7}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "through successive water and carbonate losses [25] (reactions 1.3 to 1.5). At higher temperature and in oxidizing conditions, litharge was finally converted into minium (Pb3O4, reaction 1.6). \\mathrm{Pb(s)+2CH3COOH\\to Pb(CH3COO)2+H2} \\tag{1} \\mathrm{3Pb(CH3COO)2+12O2\\to 2PbCO3\\cdot Pb(OH)2+10CO2+8H2O} \\tag{2} \\mathrm{2PbCO3\\cdot Pb(OH)2\\to 2PbCO3\\cdot PbO+H2O} \\tag{3} \\mathrm{2PbCO3\\cdot PbO\\to CO2+PbCO3\\cdot 2PbO} \\tag{4} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} According to Brown and Nees [26], litharge may be converted into minium through transitional steps, corresponding to intermediate oxidation states.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "minium", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "According to various authors, minium reduction into massicot is initiated in air over 512{}^{\\circ}C [25], 650{}^{\\circ}C [32], 535{}^{\\circ}C [33], 560{}^{\\circ}C [34].", "score": 0.44352006912231445, "metadata": {"ingest_kind": "existing_chroma", "doi": "10.1080/01411590701514326", "source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "year": "2008", "journal": "Phase Transitions", "chunk_index": 8, "title": "Chromatic alterations of red lead pigments in artworks: a review", "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "According to various authors, minium reduction into massicot is initiated in air over 512{}^{\\circ}C [25], 650{}^{\\circ}C [32], 535{}^{\\circ}C [33], 560{}^{\\circ}C [34].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "minium", "product_span": "massicot", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244].\nThe PbO formed by laser irra - diation can be re-oxidized to minium [142].", "score": 0.3938230276107788, "snippets": [{"text": "The parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244].", "score": 0.3938230276107788, "metadata": {"journal": "Heritage Science", "source_file": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext", "doi": "10.1186/s40494-017-0125-6", "chunk_index": "68", "source": "On the stability of mediaeval inorganic pigments - a review", "page": "19", "year": "2017", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "red lead", "product_span": "PbO", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The PbO formed by laser irra - diation can be re-oxidized to minium [142].", "score": null, "metadata": {"doi": "10.1186/s40494-017-0125-6", "journal": "Heritage Science", "source_file": "On the stability of mediaeval inorganic pigments - a review", "chunk_index": "69", "source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "19", "ingest_kind": "pdf_fulltext"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The PbO formed by laser irra - diation can be re-oxidized to minium [142].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "minium", "product_span": "PbO", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Formation of PbO (which can be re‐oxidised to minium, [142]) [215, 240] Formation of litharge [1, 240] Green Green earths glauconite (K,Na) (Fe 3+,Al,Mg)2 (Si,Al)4O10(OH)2) celadonite (K[(Al,Fe3+), (Fe2+,Mg)] (AlSi3,Si4) O10(OH)2 Browning [74], discolouration of oil layers [75] Green Malachite CuCO 3·Cu(OH)2 Cu acts as a biocide [124].", "score": 0.43764787912368774, "snippets": [{"text": "Formation of PbO (which can be re‐oxidised to minium, [142]) [215, 240] Formation of litharge [1, 240] Green Green earths glauconite (K,Na) (Fe 3+,Al,Mg)2 (Si,Al)4O10(OH)2) celadonite (K[(Al,Fe3+), (Fe2+,Mg)] (AlSi3,Si4) O10(OH)2 Browning [74], discolouration of oil layers [75] Green Malachite CuCO 3·Cu(OH)2 Cu acts as a biocide [124].", "score": 0.43764787912368774, "metadata": {"ingest_kind": "pdf_fulltext", "year": "2017", "source_file": "On the stability of mediaeval inorganic pigments - a review", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "chunk_index": "20", "source": "On the stability of mediaeval inorganic pigments - a review", "page": "8", "doi": "10.1186/s40494-017-0125-6", "journal": "Heritage Science"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Formation of PbO (which can be re‐oxidised to minium, [142]) [215, 240] Formation of litharge [1, 240] Green Green earths glauconite (K,Na) (Fe 3+,Al,Mg)2 (Si,Al)4O10(OH)2) celadonite (K[(Al,Fe3+), (Fe2+,Mg)] (AlSi3,Si4) O10(OH)2 Browning [74], discolouration of oil layers [75] Green Malachite CuCO 3·Cu(OH)2 Cu acts as a biocide [124].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "minium", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound.", "score": null, "snippets": [{"text": "The sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound.", "score": null, "metadata": {"title": "The role of H2S in pigment blackening", "source": "markdown_output/The role of H2S in pigment blackening.md", "year": "2002", "ingest_kind": "existing_chroma", "journal": "Journal of Cultural Heritage", "doi": "10.1016/s1296-2074(02)01173-1", "source_file": "The role of H2S in pigment blackening.md", "chunk_index": 21}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "red lead", "product_span": "PbO", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.\nUnder a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "score": null, "snippets": [{"text": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.", "score": null, "metadata": {"journal": "Journal of Raman Spectroscopy", "source_file": "Blackening of lead white: Study of model paintings.md", "title": "Blackening of lead white: Study of model paintings", "ingest_kind": "existing_chroma", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "year": "2020", "doi": "10.1002/jrs.5879", "chunk_index": 21}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO", "condition": "Fresco", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "massicot", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "score": null, "metadata": {"ingest_kind": "existing_chroma", "doi": "10.1002/jrs.5879", "title": "Blackening of lead white: Study of model paintings", "chunk_index": 35, "journal": "Journal of Raman Spectroscopy", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "source_file": "Blackening of lead white: Study of model paintings.md", "year": "2020"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO", "condition": "Fresco", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "reactant_match": "exact", "product_match": "alias", "reactant_span": "Pb3O4", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 5, "resolver_scanned": 2314, "resolver_candidates": 82, "resolver_kept": 5, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 4, "lexical_scanned": 2314, "lexical_candidates": 352, "lexical_kept": 9, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/44bfe71f0a7866a1e0ec369a1ce417bec8f475a0.json b/rag_report_cache/44bfe71f0a7866a1e0ec369a1ce417bec8f475a0.json
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@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[CO2]--> PbCO3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nFocused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate). The distribution of Pb, S, O and Ca elements within the cross-section was estab - lished using electron micro-probe analysis, and correlated to micro-Raman semi-quantitative mappings of minium (Pb3O4), cerus- site (PbCO3), anglesite (PbSO 4) and calcite (CaCO 3) phases. The micro-structural characteristics of each lead-containing phase were investigated by means of scanning electron microscopy observations of the sample cross-section using backscattered elec- tron imaging. The major role of atmospheric pollutants (SO 2, CO2), together with water condensation on such a red pigment fading is emphasised.\n\n[1] Evidence classification: edge 1: direct\nFocused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate). The distribution of Pb, S, O and Ca elements within the cross-section was estab - lished using electron micro-probe analysis, and correlated to micro-Raman semi-quantitative mappings of minium (Pb3O4), cerus- site (PbCO3), anglesite (PbSO 4) and calcite (CaCO 3) phases. The micro-structural characteristics of each lead-containing phase were investigated by means of scanning electron microscopy observations of the sample cross-section using backscattered elec- tron imaging. The major role of atmospheric pollutants (SO 2, CO2), together with water condensation on such a red pigment fading is emphasised. O 3) phases.", "ref_list": ["AZE S, VALLET JM, BARONNET A, et al. The fading of red lead pigment in wall paintings: tracking the physico-chemical transformations by means of complementary micro-analysis techniques [J/OL]. European Journal of Mineralogy, 2006. DOI: 10.1127/0935-1221/2006/0018-0835."], "ref_snippets": [{"text": "Focused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate). The distribution of Pb, S, O and Ca elements within the cross-section was estab - lished using electron micro-probe analysis, and correlated to micro-Raman semi-quantitative mappings of minium (Pb3O4), cerus- site (PbCO3), anglesite (PbSO 4) and calcite (CaCO 3) phases. The micro-structural characteristics of each lead-containing phase were investigated by means of scanning electron microscopy observations of the sample cross-section using backscattered elec- tron imaging. The major role of atmospheric pollutants (SO 2, CO2), together with water condensation on such a red pigment fading is emphasised.\nFocused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate). The distribution of Pb, S, O and Ca elements within the cross-section was estab - lished using electron micro-probe analysis, and correlated to micro-Raman semi-quantitative mappings of minium (Pb3O4), cerus- site (PbCO3), anglesite (PbSO 4) and calcite (CaCO 3) phases. The micro-structural characteristics of each lead-containing phase were investigated by means of scanning electron microscopy observations of the sample cross-section using backscattered elec- tron imaging. The major role of atmospheric pollutants (SO 2, CO2), together with water condensation on such a red pigment fading is emphasised. O 3) phases.", "score": null, "snippets": [{"text": "Focused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate). The distribution of Pb, S, O and Ca elements within the cross-section was estab - lished using electron micro-probe analysis, and correlated to micro-Raman semi-quantitative mappings of minium (Pb3O4), cerus- site (PbCO3), anglesite (PbSO 4) and calcite (CaCO 3) phases. The micro-structural characteristics of each lead-containing phase were investigated by means of scanning electron microscopy observations of the sample cross-section using backscattered elec- tron imaging. The major role of atmospheric pollutants (SO 2, CO2), together with water condensation on such a red pigment fading is emphasised.", "score": null, "metadata": {"doi": "10.1127/0935-1221/2006/0018-0835", "page": 1, "journal": "European Journal of Mineralogy", "ingest_kind": "pdf_fulltext", "chunk_index": 0, "title": "The fading of red lead pigment in wall paintings: tracking the physico-chemical transformations by means of complementary micro-analysis techniques", "source": "The_fading_of_red_lead_pigment_in_wall_paintings_tracking_the_physico-chemical_transformat_0761b14aeacf.pdf", "year": "2006", "source_file": "The_fading_of_red_lead_pigment_in_wall_paintings_tracking_the_physico-chemical_transformat_0761b14aeacf.pdf", "fulltext_url": "https://content5.schweizerbart.de//download/9Q9fZcGIB42OwmxuPRKWLBOFU34YY6", "authors": [{"family": "Aze", "given": "Sébastien"}, {"family": "Vallet", "given": "Jean-Marc"}, {"family": "Baronnet", "given": "Alain"}, {"family": "Grauby", "given": "Olivier"}], "volume": "18", "issue": "6", "pages": "835-843", "url": "https://doi.org/10.1127/0935-1221/2006/0018-0835"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "PbCO3", "condition": "CO2", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Focused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate). The distribution of Pb, S, O and Ca elements within the cross-section was estab - lished using electron micro-probe analysis, and correlated to micro-Raman semi-quantitative mappings of minium (Pb3O4), cerus- site (PbCO3), anglesite (PbSO 4) and calcite (CaCO 3) phases. The micro-structural characteristics of each lead-containing phase were investigated by means of scanning electron microscopy observations of the sample cross-section using backscattered elec- tron imaging. The major role of atmospheric pollutants (SO 2, CO2), together with water condensation on such a red pigment fading is emphasised.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "cerussite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Focused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate). The distribution of Pb, S, O and Ca elements within the cross-section was estab - lished using electron micro-probe analysis, and correlated to micro-Raman semi-quantitative mappings of minium (Pb3O4), cerus- site (PbCO3), anglesite (PbSO 4) and calcite (CaCO 3) phases. The micro-structural characteristics of each lead-containing phase were investigated by means of scanning electron microscopy observations of the sample cross-section using backscattered elec- tron imaging. The major role of atmospheric pollutants (SO 2, CO2), together with water condensation on such a red pigment fading is emphasised. O 3) phases.", "score": null, "metadata": {"page": 1, "fulltext_url": "https://content5.schweizerbart.de//download/9Q9fZcGIB42OwmxuPRKWLBOFU34YY6", "ingest_kind": "pdf_fulltext", "source_file": "The_fading_of_red_lead_pigment_in_wall_paintings_tracking_the_physico-chemical_transformat_0761b14aeacf.pdf", "title": "The fading of red lead pigment in wall paintings: tracking the physico-chemical transformations by means of complementary micro-analysis techniques", "year": "2006", "journal": "European Journal of Mineralogy", "doi": "10.1127/0935-1221/2006/0018-0835", "chunk_index": 2, "source": "The_fading_of_red_lead_pigment_in_wall_paintings_tracking_the_physico-chemical_transformat_0761b14aeacf.pdf", "authors": [{"family": "Aze", "given": "Sébastien"}, {"family": "Vallet", "given": "Jean-Marc"}, {"family": "Baronnet", "given": "Alain"}, {"family": "Grauby", "given": "Olivier"}], "volume": "18", "issue": "6", "pages": "835-843", "url": "https://doi.org/10.1127/0935-1221/2006/0018-0835"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "PbCO3", "condition": "CO2", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Focused X-ray diffraction patterns of small areas were collected using a highly sensitive detector, revealing the transformation of red lead pigment into both cerussite (lead carbonate) and anglesite (lead sulphate). The distribution of Pb, S, O and Ca elements within the cross-section was estab - lished using electron micro-probe analysis, and correlated to micro-Raman semi-quantitative mappings of minium (Pb3O4), cerus- site (PbCO3), anglesite (PbSO 4) and calcite (CaCO 3) phases. The micro-structural characteristics of each lead-containing phase were investigated by means of scanning electron microscopy observations of the sample cross-section using backscattered elec- tron imaging. The major role of atmospheric pollutants (SO 2, CO2), together with water condensation on such a red pigment fading is emphasised. O 3) phases.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "cerussite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 52, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 201, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/44eeb3a4e7a3d103f8dc06f6953119be8b4cb921.json b/rag_report_cache/44eeb3a4e7a3d103f8dc06f6953119be8b4cb921.json
new file mode 100644
index 0000000000000000000000000000000000000000..5a7151c72c8b3e6545d9ee24a6f10fe2b1eb7872
--- /dev/null
+++ b/rag_report_cache/44eeb3a4e7a3d103f8dc06f6953119be8b4cb921.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Uv+Moisture]--> HgSO4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.\n\n[1] Evidence classification: edge 1: direct\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "ref_list": ["ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "CHAPPÉ M, HILDENHAGEN J, DICKMANN K, et al. Laser irradiation of medieval pigments at IR, VIS and UV wavelengths [J/OL]. Journal of Cultural Heritage, 2003. DOI: 10.1016/s1296-2074(02)01206-2.", "ELERT K, CARDELL C. Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging [J/OL]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, 216:236-248. DOI: 10.1016/j.saa.2019.03.027."], "ref_snippets": [{"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "score": 0.49485206604003906, "snippets": [{"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.", "score": 0.49485206604003906, "metadata": {"doi": "10.1038/s42004-021-00610-2", "ingest_kind": "existing_chroma", "journal": "Communications Chemistry", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "chunk_index": 43, "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "year": "2021"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "mercury sulfate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "score": null, "metadata": {"title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "chunk_index": 42, "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "journal": "Communications Chemistry", "year": "2021", "doi": "10.1038/s42004-021-00610-2", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "mercury sulfate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 11, "dense_candidates": 220, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 15, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 203, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/473d69592ad76faef4f245efcf2c9a0fa6bb39bd.json b/rag_report_cache/473d69592ad76faef4f245efcf2c9a0fa6bb39bd.json
new file mode 100644
index 0000000000000000000000000000000000000000..2d914614b2a8347cb1f330d9e52b33f1b11e7d74
--- /dev/null
+++ b/rag_report_cache/473d69592ad76faef4f245efcf2c9a0fa6bb39bd.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Moisture]--> CuCO3·Cu(OH)2 --[Chloride]--> Cu2Cl(OH)3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 2: direct, pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nThe alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).\n\n[2] Evidence classification: edge 1: direct\nBlack colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.\n\n[2] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].\n\n[4] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nSeveral authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.\n\n[5] Evidence classification: edge 2: direct, pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nMinerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\n\n[5] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nCavallo, Alteration of azurite into paratacamite at the St.\n\n[6] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nBesides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.\n\n[7] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).\n\n[7] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.\n\n[8] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nHowever, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].\n\n[9] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlteration of azurite into paratacamite at the St.", "ref_list": ["MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001.", "PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1.", "VAGNINI M, VIVANI R, VISCUSO E, et al. Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi [J/OL]. Vibrational Spectroscopy, 2018. DOI: 10.1016/j.vibspec.2018.07.006.", "LLUVERAS A, BOULARAND S, ANDREOTTI A, et al. Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR [J/OL]. Applied Physics A, 2010. DOI: 10.1007/s00339-010-5673-5.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:15. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:22. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)"], "ref_snippets": [{"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": 0.4536123275756836, "snippets": [{"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": 0.4536123275756836, "metadata": {"chunk_index": 2, "title": "Raman spectroscopic analysis of azurite blackening", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "journal": "Journal of Raman Spectroscopy", "doi": "10.1002/jrs.1845", "ingest_kind": "pdf_reextract", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "year": "2008"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "clinoatacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "clinoatacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "score": 0.422015905380249, "snippets": [{"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "score": 0.422015905380249, "metadata": {"journal": "Minerals", "ingest_kind": "pdf_direct", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "chunk_index": 7, "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "year": "2020", "doi": "10.3390/min10050424", "source": "pdf_direct/min10050424_part2.pdf"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCO3·Cu(OH)2", "condition": "Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "malachite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "score": null, "metadata": {"title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "doi": "10.3390/min10050424", "ingest_kind": "pdf_direct", "journal": "Minerals", "year": "2020", "chunk_index": 5, "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "source": "pdf_direct/min10050424_part2.pdf"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": 0.4175853729248047, "snippets": [{"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": 0.4175853729248047, "metadata": {"ingest_kind": "pdf_fulltext", "journal": "Heritage Science", "source": "On the stability of mediaeval inorganic pigments - a review", "chunk_index": "38", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "year": "2017", "source_file": "On the stability of mediaeval inorganic pigments - a review", "doi": "10.1186/s40494-017-0125-6", "page": "13"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": 0.40759676694869995, "snippets": [{"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": 0.40759676694869995, "metadata": {"source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "source_file": "Degradation of lead-based pigments by salt solutions.md", "journal": "Journal of Cultural Heritage", "ingest_kind": "existing_chroma", "doi": "10.1016/j.culher.2008.11.001", "title": "Degradation of lead-based pigments by salt solutions", "chunk_index": 1, "year": "2009"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\nCavallo, Alteration of azurite into paratacamite at the St.", "score": null, "snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "metadata": {"fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "license": "https://creativecommons.org/licenses/by/4.0", "doi": "10.1007/s00339-024-07954-1", "ingest_kind": "pdf_fulltext", "chunk_index": 22, "source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "year": "2024", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "page": 11, "journal": "Applied Physics A", "authors": [{"family": "Purdy", "given": "Ellen H."}, {"family": "Critchley", "given": "Sarah"}, {"family": "Holé", "given": "Clément"}, {"family": "Cotte", "given": "Marine"}, {"family": "Kirkham", "given": "Andrea"}, {"family": "Casford", "given": "Michael"}], "volume": "130", "issue": "11", "article_number": "817", "url": "https://doi.org/10.1007/s00339-024-07954-1"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Cavallo, Alteration of azurite into paratacamite at the St.", "score": null, "metadata": {"chunk_index": 43, "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "year": "2024", "license": "https://creativecommons.org/licenses/by/4.0", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "ingest_kind": "pdf_fulltext", "page": 19, "doi": "10.1007/s00339-024-07954-1", "journal": "Applied Physics A", "authors": [{"family": "Purdy", "given": "Ellen H."}, {"family": "Critchley", "given": "Sarah"}, {"family": "Holé", "given": "Clément"}, {"family": "Cotte", "given": "Marine"}, {"family": "Kirkham", "given": "Andrea"}, {"family": "Casford", "given": "Michael"}], "volume": "130", "issue": "11", "article_number": "817", "url": "https://doi.org/10.1007/s00339-024-07954-1"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Cavallo, Alteration of azurite into paratacamite at the St.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": null, "snippets": [{"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": null, "metadata": {"ingest_kind": "existing_chroma", "source_file": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "doi": "10.1016/j.vibspec.2018.07.006", "source": "markdown_output/Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "title": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi", "journal": "Vibrational Spectroscopy", "year": "2018", "chunk_index": 38}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "score": null, "snippets": [{"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).", "score": null, "metadata": {"source": "markdown_output/Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "year": "2010", "ingest_kind": "existing_chroma", "title": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR", "journal": "Applied Physics A", "doi": "10.1007/s00339-010-5673-5", "source_file": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "chunk_index": 4}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "score": null, "metadata": {"year": "2010", "doi": "10.1007/s00339-010-5673-5", "title": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR", "journal": "Applied Physics A", "source_file": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "chunk_index": 6}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "score": null, "snippets": [{"text": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "score": null, "metadata": {"chunk_index": "49", "year": "2017", "source_file": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "15", "ingest_kind": "pdf_fulltext", "doi": "10.1186/s40494-017-0125-6", "source": "On the stability of mediaeval inorganic pigments - a review"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Alteration of azurite into paratacamite at the St.", "score": null, "snippets": [{"text": "Alteration of azurite into paratacamite at the St.", "score": null, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "chunk_index": "91", "doi": "10.1186/s40494-017-0125-6", "year": "2017", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "22", "source_file": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Alteration of azurite into paratacamite at the St.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 4, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 6, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 7, "lexical_scanned": 2314, "lexical_candidates": 299, "lexical_kept": 12, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/47bafa4d6475ff966ed43ad8908c2a82486933a8.json b/rag_report_cache/47bafa4d6475ff966ed43ad8908c2a82486933a8.json
new file mode 100644
index 0000000000000000000000000000000000000000..bbb1698e3fb94ef939b6b278fc8bac5efb675bb4
--- /dev/null
+++ b/rag_report_cache/47bafa4d6475ff966ed43ad8908c2a82486933a8.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[Biogenic]--> β-PbO2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThe transformation of red lead into black lead dioxide (beta-PbO2, plattnerite), however, is generally stated as the main cause of red lead darkening in paintings. This compound was identified on numerous artworks, such as polychrome sculptures [8] and wall paintings [56, 57, 58]. The hypothesis of red lead oxidation into plattnerite is commonly invoked when darkened sample analyses are inefficient [59]. Besides, the use of plattnerite as a black pigment has also been proposed to explain paint micro-sample analyses [60]. ### Factors influencing red lead alteration Humidity is supposed to play a role through the activation of chemical processes [29], as well as its ability to support microbial development, which may generate alteration of lead-containing pigments [65].\n\n[1] Evidence classification: edge 1: direct\nThe darkening of red lead containing paintings from antique Chinese wall paintings has been attributed to the pigment oxidation into plattnerite by microbial activity [69].\n\n[1] Evidence classification: edge 1: direct\nIf red lead darkening on frescoes is usually attributed to the formation of plattnerite, most of the studies related to red lead alteration on manuscripts point out its transformation into lead sulfide (galena, PbS). Such a phenomenon may occur through the interaction with atmospheric hydrogen sulfide [70]. Alternatively, in the case of tempera-like paintings, lead-based pigments alteration into lead sulfide may originate from metabolic activity of certain bacterial species, which generates hydrogen sulfide [71].\n\n[2] Evidence classification: edge 1: direct\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\n\n[2] Evidence classification: edge 1: direct\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "ref_list": ["AZE S, VALLET JM, DETALLE V, et al. Chromatic alterations of red lead pigments in artworks: a review [J/OL]. Phase Transitions, 2008. DOI: 10.1080/01411590701514326.", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001.", "ROSADO T, GIL M, MIRÃO J, et al. Darkening on lead‐based pigments: Microbiological contribution [J/OL]. Color Research & Application, 2016. DOI: 10.1002/col.22014."], "ref_snippets": [{"text": "The transformation of red lead into black lead dioxide (beta-PbO2, plattnerite), however, is generally stated as the main cause of red lead darkening in paintings. This compound was identified on numerous artworks, such as polychrome sculptures [8] and wall paintings [56, 57, 58]. The hypothesis of red lead oxidation into plattnerite is commonly invoked when darkened sample analyses are inefficient [59]. Besides, the use of plattnerite as a black pigment has also been proposed to explain paint micro-sample analyses [60]. ### Factors influencing red lead alteration Humidity is supposed to play a role through the activation of chemical processes [29], as well as its ability to support microbial development, which may generate alteration of lead-containing pigments [65].\nThe darkening of red lead containing paintings from antique Chinese wall paintings has been attributed to the pigment oxidation into plattnerite by microbial activity [69].\nIf red lead darkening on frescoes is usually attributed to the formation of plattnerite, most of the studies related to red lead alteration on manuscripts point out its transformation into lead sulfide (galena, PbS). Such a phenomenon may occur through the interaction with atmospheric hydrogen sulfide [70]. Alternatively, in the case of tempera-like paintings, lead-based pigments alteration into lead sulfide may originate from metabolic activity of certain bacterial species, which generates hydrogen sulfide [71].", "score": null, "snippets": [{"text": "The transformation of red lead into black lead dioxide (beta-PbO2, plattnerite), however, is generally stated as the main cause of red lead darkening in paintings. This compound was identified on numerous artworks, such as polychrome sculptures [8] and wall paintings [56, 57, 58]. The hypothesis of red lead oxidation into plattnerite is commonly invoked when darkened sample analyses are inefficient [59]. Besides, the use of plattnerite as a black pigment has also been proposed to explain paint micro-sample analyses [60]. ### Factors influencing red lead alteration Humidity is supposed to play a role through the activation of chemical processes [29], as well as its ability to support microbial development, which may generate alteration of lead-containing pigments [65].", "score": null, "metadata": {"chunk_index": 15, "title": "Chromatic alterations of red lead pigments in artworks: a review", "journal": "Phase Transitions", "ingest_kind": "existing_chroma", "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md", "source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "year": "2008", "doi": "10.1080/01411590701514326"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The transformation of red lead into black lead dioxide (beta-PbO2, plattnerite), however, is generally stated as the main cause of red lead darkening in paintings. This compound was identified on numerous artworks, such as polychrome sculptures [8] and wall paintings [56, 57, 58]. The hypothesis of red lead oxidation into plattnerite is commonly invoked when darkened sample analyses are inefficient [59]. Besides, the use of plattnerite as a black pigment has also been proposed to explain paint micro-sample analyses [60]. ### Factors influencing red lead alteration Humidity is supposed to play a role through the activation of chemical processes [29], as well as its ability to support microbial development, which may generate alteration of lead-containing pigments [65].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "red lead", "product_span": "beta-PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The darkening of red lead containing paintings from antique Chinese wall paintings has been attributed to the pigment oxidation into plattnerite by microbial activity [69].", "score": null, "metadata": {"doi": "10.1080/01411590701514326", "journal": "Phase Transitions", "year": "2008", "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md", "title": "Chromatic alterations of red lead pigments in artworks: a review", "source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "chunk_index": 16, "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The darkening of red lead containing paintings from antique Chinese wall paintings has been attributed to the pigment oxidation into plattnerite by microbial activity [69].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "If red lead darkening on frescoes is usually attributed to the formation of plattnerite, most of the studies related to red lead alteration on manuscripts point out its transformation into lead sulfide (galena, PbS). Such a phenomenon may occur through the interaction with atmospheric hydrogen sulfide [70]. Alternatively, in the case of tempera-like paintings, lead-based pigments alteration into lead sulfide may originate from metabolic activity of certain bacterial species, which generates hydrogen sulfide [71].", "score": null, "metadata": {"source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "chunk_index": 19, "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md", "title": "Chromatic alterations of red lead pigments in artworks: a review", "year": "2008", "ingest_kind": "existing_chroma", "journal": "Phase Transitions", "doi": "10.1080/01411590701514326"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "If red lead darkening on frescoes is usually attributed to the formation of plattnerite, most of the studies related to red lead alteration on manuscripts point out its transformation into lead sulfide (galena, PbS). Such a phenomenon may occur through the interaction with atmospheric hydrogen sulfide [70]. Alternatively, in the case of tempera-like paintings, lead-based pigments alteration into lead sulfide may originate from metabolic activity of certain bacterial species, which generates hydrogen sulfide [71].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "score": null, "snippets": [{"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "score": null, "metadata": {"title": "Degradation of lead-based pigments by salt solutions", "year": "2009", "doi": "10.1016/j.culher.2008.11.001", "source_file": "Degradation of lead-based pigments by salt solutions.md", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "chunk_index": 42, "journal": "Journal of Cultural Heritage", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "score": null, "metadata": {"ingest_kind": "existing_chroma", "journal": "Journal of Cultural Heritage", "source_file": "Degradation of lead-based pigments by salt solutions.md", "title": "Degradation of lead-based pigments by salt solutions", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "year": "2009", "doi": "10.1016/j.culher.2008.11.001", "chunk_index": 45}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 64, "resolver_kept": 5, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 205, "lexical_kept": 5, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/4982a1806486aacac6f59aa62dbea49cdeb54a7f.json b/rag_report_cache/4982a1806486aacac6f59aa62dbea49cdeb54a7f.json
new file mode 100644
index 0000000000000000000000000000000000000000..03954cc986febfb50dcc31b303cdfa44c0f5ad86
--- /dev/null
+++ b/rag_report_cache/4982a1806486aacac6f59aa62dbea49cdeb54a7f.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[12000lux+1.5W/m2+60℃+90%RH]--> CuCO3·Cu(OH)2 --[Chloride]--> Cu2Cl(OH)3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nBesides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.\n\n[2] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].\n\n[3] Evidence classification: edge 2: direct, pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nMinerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nCavallo, Alteration of azurite into paratacamite at the St.\n\n[4] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nSeveral authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.\n\n[5] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).\n\n[5] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.\n\n[6] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].\n\n[6] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).\n\n[7] Evidence classification: edge 2: direct, pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nThe alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).\n\n[8] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nHowever, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].\n\n[9] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlteration of azurite into paratacamite at the St.", "ref_list": ["VAGNINI M, VIVANI R, VISCUSO E, et al. Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi [J/OL]. Vibrational Spectroscopy, 2018. DOI: 10.1016/j.vibspec.2018.07.006.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1.", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001.", "LLUVERAS A, BOULARAND S, ANDREOTTI A, et al. Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR [J/OL]. Applied Physics A, 2010. DOI: 10.1007/s00339-010-5673-5.", "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:15. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:22. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)"], "ref_snippets": [{"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": 0.4179467558860779, "snippets": [{"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": 0.4179467558860779, "metadata": {"source": "markdown_output/Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "title": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi", "year": "2018", "journal": "Vibrational Spectroscopy", "doi": "10.1016/j.vibspec.2018.07.006", "source_file": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "chunk_index": 38, "ingest_kind": "existing_chroma"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": 0.4175853729248047, "snippets": [{"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": 0.4175853729248047, "metadata": {"title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "journal": "Heritage Science", "source": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext", "doi": "10.1186/s40494-017-0125-6", "page": "13", "source_file": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "chunk_index": "38"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\nCavallo, Alteration of azurite into paratacamite at the St.", "score": null, "snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "metadata": {"ingest_kind": "pdf_fulltext", "year": "2024", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "license": "https://creativecommons.org/licenses/by/4.0", "source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "chunk_index": 22, "doi": "10.1007/s00339-024-07954-1", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "journal": "Applied Physics A", "page": 11, "authors": [{"family": "Purdy", "given": "Ellen H."}, {"family": "Critchley", "given": "Sarah"}, {"family": "Holé", "given": "Clément"}, {"family": "Cotte", "given": "Marine"}, {"family": "Kirkham", "given": "Andrea"}, {"family": "Casford", "given": "Michael"}], "volume": "130", "issue": "11", "article_number": "817", "url": "https://doi.org/10.1007/s00339-024-07954-1"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Cavallo, Alteration of azurite into paratacamite at the St.", "score": null, "metadata": {"ingest_kind": "pdf_fulltext", "doi": "10.1007/s00339-024-07954-1", "source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "chunk_index": 43, "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "year": "2024", "page": 19, "license": "https://creativecommons.org/licenses/by/4.0", "journal": "Applied Physics A", "authors": [{"family": "Purdy", "given": "Ellen H."}, {"family": "Critchley", "given": "Sarah"}, {"family": "Holé", "given": "Clément"}, {"family": "Cotte", "given": "Marine"}, {"family": "Kirkham", "given": "Andrea"}, {"family": "Casford", "given": "Michael"}], "volume": "130", "issue": "11", "article_number": "817", "url": "https://doi.org/10.1007/s00339-024-07954-1"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Cavallo, Alteration of azurite into paratacamite at the St.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": null, "snippets": [{"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": null, "metadata": {"ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "title": "Degradation of lead-based pigments by salt solutions", "journal": "Journal of Cultural Heritage", "year": "2009", "source_file": "Degradation of lead-based pigments by salt solutions.md", "doi": "10.1016/j.culher.2008.11.001", "chunk_index": 0}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "score": null, "snippets": [{"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).", "score": null, "metadata": {"source": "markdown_output/Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "year": "2010", "ingest_kind": "existing_chroma", "title": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR", "journal": "Applied Physics A", "doi": "10.1007/s00339-010-5673-5", "source_file": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "chunk_index": 4}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "score": null, "metadata": {"year": "2010", "doi": "10.1007/s00339-010-5673-5", "title": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR", "journal": "Applied Physics A", "source_file": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "chunk_index": 6}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).", "score": null, "snippets": [{"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "score": null, "metadata": {"title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "doi": "10.3390/min10050424", "ingest_kind": "pdf_direct", "journal": "Minerals", "year": "2020", "chunk_index": 5, "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "source": "pdf_direct/min10050424_part2.pdf"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).", "score": null, "metadata": {"ingest_kind": "pdf_direct", "source": "pdf_direct/min10050424_part2.pdf", "chunk_index": 7, "doi": "10.3390/min10050424", "year": "2020", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "journal": "Minerals", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "snippets": [{"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "metadata": {"ingest_kind": "pdf_reextract", "year": "2008", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "chunk_index": 0, "journal": "Journal of Raman Spectroscopy", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "doi": "10.1002/jrs.1845", "title": "Raman spectroscopic analysis of azurite blackening"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "clinoatacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "clinoatacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "score": null, "snippets": [{"text": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "score": null, "metadata": {"chunk_index": "49", "year": "2017", "source_file": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "15", "ingest_kind": "pdf_fulltext", "doi": "10.1186/s40494-017-0125-6", "source": "On the stability of mediaeval inorganic pigments - a review"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Alteration of azurite into paratacamite at the St.", "score": null, "snippets": [{"text": "Alteration of azurite into paratacamite at the St.", "score": null, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "chunk_index": "91", "doi": "10.1186/s40494-017-0125-6", "year": "2017", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "22", "source_file": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Alteration of azurite into paratacamite at the St.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 6, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 5, "lexical_scanned": 2314, "lexical_candidates": 294, "lexical_kept": 12, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/4a39a4bba9a5f29819f6abee0e69e26dd291eac0.json b/rag_report_cache/4a39a4bba9a5f29819f6abee0e69e26dd291eac0.json
new file mode 100644
index 0000000000000000000000000000000000000000..fd84ef8b41c7860057f9e855b75171e97bbeb162
--- /dev/null
+++ b/rag_report_cache/4a39a4bba9a5f29819f6abee0e69e26dd291eac0.json
@@ -0,0 +1 @@
+{"root_material": "As2S3", "path_str": "As2S3 --[Binder]--> As(III)aq --[Binder]--> As(V)aq --[Binder]--> M3(AsO4)n", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 3: direct\nAs it is improbable to encounter such very low or very high levels of humidity in a painting’s environment, this was not within the scope of our research. As(V) species can form metal arsenates with different cations, among which Pb 2+ , Fe 2+ , and Ca 2+ . All of these cations are very commonly encountered in historical oil paintings.\n\n[1] Evidence classification: edge 1: direct, edge 2: direct\nAdditionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.\n\n[1] Evidence classification: edge 2: direct\nThe relatively high concentration of As in the medium and the XANES of positions 2−4 suggest that some of the arsenolite had dissolved in the water-diluted egg yolk (since orpiment is less soluble in water than arsenolite, this phenomenon was not observed in the previous experiment 41,42 ). Literature shows that during solution of arsenolite, first hydrated arsenite species form, after which oxidation to arsenate species takes place.", "ref_list": ["BROERS FTH, JANSSENS K, WEKER JN, et al. Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings [J/OL]. Journal of the American Chemical Society, 2023. DOI: 10.1021/jacs.2c12271."], "ref_snippets": [{"text": "As it is improbable to encounter such very low or very high levels of humidity in a painting’s environment, this was not within the scope of our research. As(V) species can form metal arsenates with different cations, among which Pb 2+ , Fe 2+ , and Ca 2+ . All of these cations are very commonly encountered in historical oil paintings.\nAdditionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.\nThe relatively high concentration of As in the medium and the XANES of positions 2−4 suggest that some of the arsenolite had dissolved in the water-diluted egg yolk (since orpiment is less soluble in water than arsenolite, this phenomenon was not observed in the previous experiment 41,42 ). Literature shows that during solution of arsenolite, first hydrated arsenite species form, after which oxidation to arsenate species takes place.", "score": 0.5129972696304321, "snippets": [{"text": "As it is improbable to encounter such very low or very high levels of humidity in a painting’s environment, this was not within the scope of our research. As(V) species can form metal arsenates with different cations, among which Pb 2+ , Fe 2+ , and Ca 2+ . All of these cations are very commonly encountered in historical oil paintings.", "score": 0.5129972696304321, "metadata": {"ingest_kind": "pdf_fulltext", "chunk_index": 28, "license": "https://creativecommons.org/licenses/by/4.0/", "journal": "Journal of the American Chemical Society", "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "year": "2023", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "doi": "10.1021/jacs.2c12271", "page": 11, "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 3, "reactant": "As(V)aq", "product": "M3(AsO4)n", "condition": "Binder", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "As it is improbable to encounter such very low or very high levels of humidity in a painting’s environment, this was not within the scope of our research. As(V) species can form metal arsenates with different cations, among which Pb 2+ , Fe 2+ , and Ca 2+ . All of these cations are very commonly encountered in historical oil paintings.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "as(v)", "product_span": "metal arsenates", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "score": 0.5166073441505432, "metadata": {"license": "https://creativecommons.org/licenses/by/4.0/", "doi": "10.1021/jacs.2c12271", "ingest_kind": "pdf_fulltext", "year": "2023", "journal": "Journal of the American Chemical Society", "chunk_index": 20, "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "page": 9, "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As(III)aq", "condition": "Binder", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "as(iii)", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 2, "reactant": "As(III)aq", "product": "As(V)aq", "condition": "Binder", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "as(iii)", "product_span": "as(v)", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The relatively high concentration of As in the medium and the XANES of positions 2−4 suggest that some of the arsenolite had dissolved in the water-diluted egg yolk (since orpiment is less soluble in water than arsenolite, this phenomenon was not observed in the previous experiment 41,42 ). Literature shows that during solution of arsenolite, first hydrated arsenite species form, after which oxidation to arsenate species takes place.", "score": 0.525489330291748, "metadata": {"license": "https://creativecommons.org/licenses/by/4.0/", "chunk_index": 18, "ingest_kind": "pdf_fulltext", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "year": "2023", "doi": "10.1021/jacs.2c12271", "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "page": 8, "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "journal": "Journal of the American Chemical Society", "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "As(III)aq", "product": "As(V)aq", "condition": "Binder", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The relatively high concentration of As in the medium and the XANES of positions 2−4 suggest that some of the arsenolite had dissolved in the water-diluted egg yolk (since orpiment is less soluble in water than arsenolite, this phenomenon was not observed in the previous experiment 41,42 ). Literature shows that during solution of arsenolite, first hydrated arsenite species form, after which oxidation to arsenate species takes place.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "arsenite", "product_span": "arsenate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 25, "dense_candidates": 500, "dense_kept": 3, "resolver_scanned": 2314, "resolver_candidates": 0, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 3, "lexical_scanned": 2314, "lexical_candidates": 108, "lexical_kept": 3, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/4c096eb0ada014b5f468868a76c61cf3d0e34454.json b/rag_report_cache/4c096eb0ada014b5f468868a76c61cf3d0e34454.json
new file mode 100644
index 0000000000000000000000000000000000000000..369ebb5bb0ef14e4f71e375e6bfacbb01ba4dcf5
--- /dev/null
+++ b/rag_report_cache/4c096eb0ada014b5f468868a76c61cf3d0e34454.json
@@ -0,0 +1 @@
+{"root_material": "As2S3", "path_str": "As2S3 --[Binder]--> As(III)aq --[Binder]--> As(V)aq", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct, edge 2: direct, pathway endpoints As2S3 -> As(V)aq: direct\nAdditionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.\n\n[1] Evidence classification: edge 2: direct\nThe relatively high concentration of As in the medium and the XANES of positions 2−4 suggest that some of the arsenolite had dissolved in the water-diluted egg yolk (since orpiment is less soluble in water than arsenolite, this phenomenon was not observed in the previous experiment 41,42 ). Literature shows that during solution of arsenolite, first hydrated arsenite species form, after which oxidation to arsenate species takes place.\n\n[2] Evidence classification: pathway endpoints As2S3 -> As(V)aq: direct\nArsenates (As 5+) are formed from orpiment, realgar and emerald green degradation: these ions are water soluble and migrate throughout the whole painting, accumulat - ing at interfaces between layers, around Fe/Mn rich par - ticles, and according to the local pH conditions in the paint layer. Due to this water-based transport, appro - priate cleaning solvents must be selected, and relative humidity controlled [180, 183]. It seems that polysaccha - ridic media, or egg yolk, negatively affect the stability of the arsenic sulphide pigments [184].", "ref_list": ["BROERS FTH, JANSSENS K, WEKER JN, et al. Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings [J/OL]. Journal of the American Chemical Society, 2023. DOI: 10.1021/jacs.2c12271.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:15. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)"], "ref_snippets": [{"text": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.\nThe relatively high concentration of As in the medium and the XANES of positions 2−4 suggest that some of the arsenolite had dissolved in the water-diluted egg yolk (since orpiment is less soluble in water than arsenolite, this phenomenon was not observed in the previous experiment 41,42 ). Literature shows that during solution of arsenolite, first hydrated arsenite species form, after which oxidation to arsenate species takes place.", "score": 0.516607403755188, "snippets": [{"text": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "score": 0.516607403755188, "metadata": {"fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "journal": "Journal of the American Chemical Society", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "ingest_kind": "pdf_fulltext", "doi": "10.1021/jacs.2c12271", "year": "2023", "page": 9, "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "chunk_index": 20, "license": "https://creativecommons.org/licenses/by/4.0/", "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As(III)aq", "condition": "Binder", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "as(iii)", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 2, "reactant": "As(III)aq", "product": "As(V)aq", "condition": "Binder", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "as(iii)", "product_span": "as(v)", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "As2S3", "product": "As(V)aq", "condition": "Binder", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "as(v)", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The relatively high concentration of As in the medium and the XANES of positions 2−4 suggest that some of the arsenolite had dissolved in the water-diluted egg yolk (since orpiment is less soluble in water than arsenolite, this phenomenon was not observed in the previous experiment 41,42 ). Literature shows that during solution of arsenolite, first hydrated arsenite species form, after which oxidation to arsenate species takes place.", "score": null, "metadata": {"doi": "10.1021/jacs.2c12271", "journal": "Journal of the American Chemical Society", "page": 7, "chunk_index": 17, "ingest_kind": "pdf_fulltext", "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "license": "https://creativecommons.org/licenses/by/4.0/", "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "year": "2023", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "As(III)aq", "product": "As(V)aq", "condition": "Binder", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The relatively high concentration of As in the medium and the XANES of positions 2−4 suggest that some of the arsenolite had dissolved in the water-diluted egg yolk (since orpiment is less soluble in water than arsenolite, this phenomenon was not observed in the previous experiment 41,42 ). Literature shows that during solution of arsenolite, first hydrated arsenite species form, after which oxidation to arsenate species takes place.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "arsenite", "product_span": "arsenate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Arsenates (As 5+) are formed from orpiment, realgar and emerald green degradation: these ions are water soluble and migrate throughout the whole painting, accumulat - ing at interfaces between layers, around Fe/Mn rich par - ticles, and according to the local pH conditions in the paint layer. Due to this water-based transport, appro - priate cleaning solvents must be selected, and relative humidity controlled [180, 183]. It seems that polysaccha - ridic media, or egg yolk, negatively affect the stability of the arsenic sulphide pigments [184].", "score": null, "snippets": [{"text": "Arsenates (As 5+) are formed from orpiment, realgar and emerald green degradation: these ions are water soluble and migrate throughout the whole painting, accumulat - ing at interfaces between layers, around Fe/Mn rich par - ticles, and according to the local pH conditions in the paint layer. Due to this water-based transport, appro - priate cleaning solvents must be selected, and relative humidity controlled [180, 183]. It seems that polysaccha - ridic media, or egg yolk, negatively affect the stability of the arsenic sulphide pigments [184].", "score": null, "metadata": {"doi": "10.1186/s40494-017-0125-6", "journal": "Heritage Science", "source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "page": "15", "ingest_kind": "pdf_fulltext", "source_file": "On the stability of mediaeval inorganic pigments - a review", "chunk_index": "51", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "As2S3", "product": "As(V)aq", "condition": "Binder", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Arsenates (As 5+) are formed from orpiment, realgar and emerald green degradation: these ions are water soluble and migrate throughout the whole painting, accumulat - ing at interfaces between layers, around Fe/Mn rich par - ticles, and according to the local pH conditions in the paint layer. Due to this water-based transport, appro - priate cleaning solvents must be selected, and relative humidity controlled [180, 183]. It seems that polysaccha - ridic media, or egg yolk, negatively affect the stability of the arsenic sulphide pigments [184].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "arsenates", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 17, "dense_candidates": 340, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 0, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 108, "lexical_kept": 3, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/528d3b8d4a0cf97598cf2af6aacb5dc7310988b1.json b/rag_report_cache/528d3b8d4a0cf97598cf2af6aacb5dc7310988b1.json
new file mode 100644
index 0000000000000000000000000000000000000000..5c6da8f2732d94c8f88ba130ad482a9817fa7286
--- /dev/null
+++ b/rag_report_cache/528d3b8d4a0cf97598cf2af6aacb5dc7310988b1.json
@@ -0,0 +1 @@
+{"root_material": "As4S4", "path_str": "As4S4 --[Uv+Oxidant]--> p-As4S4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThis means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).\n\n[1] Evidence classification: edge 1: direct\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As4S5) and arsenolite (As2O3) are obtained (step 1).\n\n[1] Evidence classification: edge 1: direct\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.\n\n[1] Evidence classification: edge 1: direct\nFigure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).\n\n[1] Evidence classification: edge 1: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\n\n[1] Evidence classification: edge 1: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "ref_list": ["JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9."], "ref_snippets": [{"text": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As4S5) and arsenolite (As2O3) are obtained (step 1).\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.\nFigure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": 0.44365543127059937, "snippets": [{"text": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).", "score": 0.4943835735321045, "metadata": {"doi": "10.1007/s40828-019-0100-9", "journal": "ChemTexts", "ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 61, "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "year": "2020", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As4S5) and arsenolite (As2O3) are obtained (step 1).", "score": 0.44497865438461304, "metadata": {"source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "ingest_kind": "existing_chroma", "year": "2020", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "chunk_index": 1, "doi": "10.1007/s40828-019-0100-9", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As4S5) and arsenolite (As2O3) are obtained (step 1).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.", "score": 0.44365543127059937, "metadata": {"year": "2020", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "chunk_index": 2, "ingest_kind": "existing_chroma", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Figure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).", "score": null, "metadata": {"journal": "ChemTexts", "ingest_kind": "existing_chroma", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "doi": "10.1007/s40828-019-0100-9", "year": "2020", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 67, "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Figure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "score": null, "metadata": {"chunk_index": 73, "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "doi": "10.1007/s40828-019-0100-9", "journal": "ChemTexts", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "year": "2020", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": null, "metadata": {"source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "chunk_index": 75, "year": "2020", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "ingest_kind": "existing_chroma", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 3, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 6, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 157, "lexical_kept": 6, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/5354f72e503de256e243b44194400d6b41f9645e.json b/rag_report_cache/5354f72e503de256e243b44194400d6b41f9645e.json
new file mode 100644
index 0000000000000000000000000000000000000000..7189b10cc0cfb8af8c1eab883f6b2ef690f5e53d
--- /dev/null
+++ b/rag_report_cache/5354f72e503de256e243b44194400d6b41f9645e.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Uv+Moisture]--> HgSO4 --[Uv+Moisture]--> Hg", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.\n\n[1] Evidence classification: edge 1: direct\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "ref_list": ["ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "ELERT K, CARDELL C. Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging [J/OL]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, 216:236-248. DOI: 10.1016/j.saa.2019.03.027."], "ref_snippets": [{"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "score": 0.40421152114868164, "snippets": [{"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.", "score": 0.49485206604003906, "metadata": {"source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "ingest_kind": "existing_chroma", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "chunk_index": 43, "year": "2021", "journal": "Communications Chemistry", "doi": "10.1038/s42004-021-00610-2"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "mercury sulfate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "score": 0.40421152114868164, "metadata": {"doi": "10.1038/s42004-021-00610-2", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "year": "2021", "journal": "Communications Chemistry", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "ingest_kind": "existing_chroma", "chunk_index": 42, "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "mercury sulfate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 16, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 214, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/5496d9a92a226f46e43a5e44a401bcde6b1e8f1d.json b/rag_report_cache/5496d9a92a226f46e43a5e44a401bcde6b1e8f1d.json
new file mode 100644
index 0000000000000000000000000000000000000000..fdfea05cad4d9db89e8b0ffadef2a626ca77d57a
--- /dev/null
+++ b/rag_report_cache/5496d9a92a226f46e43a5e44a401bcde6b1e8f1d.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Chloride]--> CuCl --[Chloride]--> Cu2Cl(OH)3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].\n\n[2] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nBesides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nMinerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\n\n[4] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nSeveral authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.\n\n[5] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].\n\n[5] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).\n\n[6] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nThe alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "ref_list": ["On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "VAGNINI M, VIVANI R, VISCUSO E, et al. Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi [J/OL]. Vibrational Spectroscopy, 2018. DOI: 10.1016/j.vibspec.2018.07.006.", "PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1.", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001.", "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845."], "ref_snippets": [{"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": 0.4182766079902649, "snippets": [{"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": 0.4182766079902649, "metadata": {"title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source_file": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext", "chunk_index": "38", "journal": "Heritage Science", "doi": "10.1186/s40494-017-0125-6", "year": "2017", "page": "13", "source": "On the stability of mediaeval inorganic pigments - a review"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": 0.42595595121383667, "snippets": [{"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": 0.42595595121383667, "metadata": {"ingest_kind": "existing_chroma", "title": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi", "doi": "10.1016/j.vibspec.2018.07.006", "year": "2018", "chunk_index": 38, "journal": "Vibrational Spectroscopy", "source": "markdown_output/Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "source_file": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "metadata": {"source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "page": 11, "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "year": "2024", "chunk_index": 22, "license": "https://creativecommons.org/licenses/by/4.0", "doi": "10.1007/s00339-024-07954-1", "journal": "Applied Physics A", "ingest_kind": "pdf_fulltext", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "authors": [{"family": "Purdy", "given": "Ellen H."}, {"family": "Critchley", "given": "Sarah"}, {"family": "Holé", "given": "Clément"}, {"family": "Cotte", "given": "Marine"}, {"family": "Kirkham", "given": "Andrea"}, {"family": "Casford", "given": "Michael"}], "volume": "130", "issue": "11", "article_number": "817", "url": "https://doi.org/10.1007/s00339-024-07954-1"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": null, "snippets": [{"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": null, "metadata": {"ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "title": "Degradation of lead-based pigments by salt solutions", "journal": "Journal of Cultural Heritage", "year": "2009", "source_file": "Degradation of lead-based pigments by salt solutions.md", "doi": "10.1016/j.culher.2008.11.001", "chunk_index": 0}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).", "score": null, "snippets": [{"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "score": null, "metadata": {"title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "doi": "10.3390/min10050424", "ingest_kind": "pdf_direct", "journal": "Minerals", "year": "2020", "chunk_index": 5, "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "source": "pdf_direct/min10050424_part2.pdf"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).", "score": null, "metadata": {"ingest_kind": "pdf_direct", "source": "pdf_direct/min10050424_part2.pdf", "chunk_index": 7, "doi": "10.3390/min10050424", "year": "2020", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "journal": "Minerals", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "snippets": [{"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "metadata": {"ingest_kind": "pdf_reextract", "year": "2008", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "chunk_index": 0, "journal": "Journal of Raman Spectroscopy", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "doi": "10.1002/jrs.1845", "title": "Raman spectroscopic analysis of azurite blackening"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "clinoatacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 8, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 5, "lexical_scanned": 2314, "lexical_candidates": 229, "lexical_kept": 7, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/5bda912817ed611583b31a7acef51a21b1ff588d.json b/rag_report_cache/5bda912817ed611583b31a7acef51a21b1ff588d.json
new file mode 100644
index 0000000000000000000000000000000000000000..0e252e59d9d0c2d1c32b79efd03d1975db5ade3b
--- /dev/null
+++ b/rag_report_cache/5bda912817ed611583b31a7acef51a21b1ff588d.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Alkaline]--> Cu(OH)2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\ndesantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.\n\n[2] Evidence classification: edge 1: direct\nThe treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "ref_list": ["MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424."], "ref_snippets": [{"text": "desantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.", "score": 0.4565846920013428, "snippets": [{"text": "desantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.", "score": 0.4565846920013428, "metadata": {"title": "Raman spectroscopic analysis of azurite blackening", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "year": "2008", "chunk_index": 2, "ingest_kind": "pdf_reextract", "journal": "Journal of Raman Spectroscopy", "doi": "10.1002/jrs.1845", "authors": [{"family": "Mattei", "given": "E."}, {"family": "de Vivo", "given": "G."}, {"family": "De Santis", "given": "A."}, {"family": "Gaetani", "given": "C."}, {"family": "Pelosi", "given": "C."}, {"family": "Santamaria", "given": "U."}], "volume": "39", "issue": "2", "pages": "302-306", "url": "https://doi.org/10.1002/jrs.1845"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu(OH)2", "condition": "Alkaline", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "desantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "copper hydroxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "score": null, "snippets": [{"text": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "score": null, "metadata": {"source": "pdf_direct/min10050424_part2.pdf", "chunk_index": 6, "year": "2020", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "ingest_kind": "pdf_direct", "doi": "10.3390/min10050424", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "journal": "Minerals"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu(OH)2", "condition": "Alkaline", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "copper hydroxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 30, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 226, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/60ea96ed1016b93caf4e95daafb286edd228200c.json b/rag_report_cache/60ea96ed1016b93caf4e95daafb286edd228200c.json
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@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[12000lux+1.5W/m2+60℃+90%RH]--> CuCO3·Cu(OH)2 --[Biogenic+Chloride]--> Cu2Cl(OH)3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nBesides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.\n\n[2] Evidence classification: edge 2: direct, pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nMinerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\n\n[2] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nCavallo, Alteration of azurite into paratacamite at the St.\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nSeveral authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.\n\n[4] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).\n\n[4] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.\n\n[5] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].\n\n[5] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).\n\n[6] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nThe alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).\n\n[7] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].\n\n[8] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nHowever, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].\n\n[9] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlteration of azurite into paratacamite at the St.", "ref_list": ["VAGNINI M, VIVANI R, VISCUSO E, et al. Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi [J/OL]. Vibrational Spectroscopy, 2018. DOI: 10.1016/j.vibspec.2018.07.006.", "PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1.", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001.", "LLUVERAS A, BOULARAND S, ANDREOTTI A, et al. Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR [J/OL]. Applied Physics A, 2010. DOI: 10.1007/s00339-010-5673-5.", "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:15. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:22. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)"], "ref_snippets": [{"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": 0.4179467558860779, "snippets": [{"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": 0.4179467558860779, "metadata": {"journal": "Vibrational Spectroscopy", "source_file": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "title": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi", "chunk_index": 38, "doi": "10.1016/j.vibspec.2018.07.006", "source": "markdown_output/Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "ingest_kind": "existing_chroma", "year": "2018"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\nCavallo, Alteration of azurite into paratacamite at the St.", "score": null, "snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "metadata": {"page": 11, "source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "year": "2024", "chunk_index": 22, "journal": "Applied Physics A", "doi": "10.1007/s00339-024-07954-1", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "ingest_kind": "pdf_fulltext", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "license": "https://creativecommons.org/licenses/by/4.0", "authors": [{"family": "Purdy", "given": "Ellen H."}, {"family": "Critchley", "given": "Sarah"}, {"family": "Holé", "given": "Clément"}, {"family": "Cotte", "given": "Marine"}, {"family": "Kirkham", "given": "Andrea"}, {"family": "Casford", "given": "Michael"}], "volume": "130", "issue": "11", "article_number": "817", "url": "https://doi.org/10.1007/s00339-024-07954-1"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Biogenic+Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Cavallo, Alteration of azurite into paratacamite at the St.", "score": null, "metadata": {"license": "https://creativecommons.org/licenses/by/4.0", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "page": 19, "year": "2024", "doi": "10.1007/s00339-024-07954-1", "journal": "Applied Physics A", "chunk_index": 43, "source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "ingest_kind": "pdf_fulltext", "authors": [{"family": "Purdy", "given": "Ellen H."}, {"family": "Critchley", "given": "Sarah"}, {"family": "Holé", "given": "Clément"}, {"family": "Cotte", "given": "Marine"}, {"family": "Kirkham", "given": "Andrea"}, {"family": "Casford", "given": "Michael"}], "volume": "130", "issue": "11", "article_number": "817", "url": "https://doi.org/10.1007/s00339-024-07954-1"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Cavallo, Alteration of azurite into paratacamite at the St.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": null, "snippets": [{"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": null, "metadata": {"ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "title": "Degradation of lead-based pigments by salt solutions", "journal": "Journal of Cultural Heritage", "year": "2009", "source_file": "Degradation of lead-based pigments by salt solutions.md", "doi": "10.1016/j.culher.2008.11.001", "chunk_index": 0}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "score": null, "snippets": [{"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).", "score": null, "metadata": {"source": "markdown_output/Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "year": "2010", "ingest_kind": "existing_chroma", "title": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR", "journal": "Applied Physics A", "doi": "10.1007/s00339-010-5673-5", "source_file": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "chunk_index": 4}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "score": null, "metadata": {"year": "2010", "doi": "10.1007/s00339-010-5673-5", "title": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR", "journal": "Applied Physics A", "source_file": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "chunk_index": 6}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).", "score": null, "snippets": [{"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "score": null, "metadata": {"title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "doi": "10.3390/min10050424", "ingest_kind": "pdf_direct", "journal": "Minerals", "year": "2020", "chunk_index": 5, "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "source": "pdf_direct/min10050424_part2.pdf"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).", "score": null, "metadata": {"ingest_kind": "pdf_direct", "source": "pdf_direct/min10050424_part2.pdf", "chunk_index": 7, "doi": "10.3390/min10050424", "year": "2020", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "journal": "Minerals", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33]. The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "snippets": [{"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "metadata": {"ingest_kind": "pdf_reextract", "year": "2008", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "chunk_index": 0, "journal": "Journal of Raman Spectroscopy", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "doi": "10.1002/jrs.1845", "title": "Raman spectroscopic analysis of azurite blackening"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "clinoatacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": null, "snippets": [{"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": null, "metadata": {"journal": "Heritage Science", "year": "2017", "page": "13", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "ingest_kind": "pdf_fulltext", "source_file": "On the stability of mediaeval inorganic pigments - a review", "chunk_index": "38", "doi": "10.1186/s40494-017-0125-6", "source": "On the stability of mediaeval inorganic pigments - a review"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "score": null, "snippets": [{"text": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "score": null, "metadata": {"chunk_index": "49", "year": "2017", "source_file": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "15", "ingest_kind": "pdf_fulltext", "doi": "10.1186/s40494-017-0125-6", "source": "On the stability of mediaeval inorganic pigments - a review"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Alteration of azurite into paratacamite at the St.", "score": null, "snippets": [{"text": "Alteration of azurite into paratacamite at the St.", "score": null, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "chunk_index": "91", "doi": "10.1186/s40494-017-0125-6", "year": "2017", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "22", "source_file": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Alteration of azurite into paratacamite at the St.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 6, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 5, "lexical_scanned": 2314, "lexical_candidates": 297, "lexical_kept": 12, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
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diff --git a/rag_report_cache/62fefad4da30a7af1247f653f0139aff940e74a5.json b/rag_report_cache/62fefad4da30a7af1247f653f0139aff940e74a5.json
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index 0000000000000000000000000000000000000000..ceaac48244c8da133fcec8e061568a63e3f10e79
--- /dev/null
+++ b/rag_report_cache/62fefad4da30a7af1247f653f0139aff940e74a5.json
@@ -0,0 +1 @@
+{"root_material": "As2S3", "path_str": "As2S3 --[Binder]--> As(III)aq", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nAdditionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "ref_list": ["BROERS FTH, JANSSENS K, WEKER JN, et al. Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings [J/OL]. Journal of the American Chemical Society, 2023. DOI: 10.1021/jacs.2c12271."], "ref_snippets": [{"text": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "score": 0.516607403755188, "snippets": [{"text": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "score": 0.516607403755188, "metadata": {"fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "journal": "Journal of the American Chemical Society", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "chunk_index": 20, "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "year": "2023", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "page": 9, "license": "https://creativecommons.org/licenses/by/4.0/", "doi": "10.1021/jacs.2c12271", "ingest_kind": "pdf_fulltext", "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As(III)aq", "condition": "Binder", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Additionally, orpiment in Paraloid-72 (acrylic resin) was LA and a similar trend was observed as found in the sample with egg tempera, namely, the formation of As(III)−OH, followed by the formation and migration of As(V) species.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "as(iii)", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 0, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 108, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/658d02f04826bbf5e188a9529548b74ff6c06e50.json b/rag_report_cache/658d02f04826bbf5e188a9529548b74ff6c06e50.json
new file mode 100644
index 0000000000000000000000000000000000000000..70c2c7278a5208dde91ed342f2357364250b1c7e
--- /dev/null
+++ b/rag_report_cache/658d02f04826bbf5e188a9529548b74ff6c06e50.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Chloride]--> α-Hg3S2Cl2 --[Chloride]--> Hg2Cl2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct, edge 2: direct, pathway endpoints alpha-HgS -> Hg2Cl2: direct\nThe residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "ref_list": ["KEUNE K, BOON JJ. Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings [J/OL]. Analytical Chemistry, 2005. DOI: 10.1021/ac048158f.", "CHAPPÉ M, HILDENHAGEN J, DICKMANN K, et al. Laser irradiation of medieval pigments at IR, VIS and UV wavelengths [J/OL]. Journal of Cultural Heritage, 2003. DOI: 10.1016/s1296-2074(02)01206-2.", "COTTE M, SUSINI J, METRICH N, et al. Blackening of Pompeian Cinnabar Paintings: X-ray Microspectroscopy Analysis [J/OL]. Analytical Chemistry, 2006. DOI: 10.1021/ac0612224."], "ref_snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.5111522674560547, "snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.5111522674560547, "metadata": {"year": "2005", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "doi": "10.1021/ac048158f", "chunk_index": 46, "journal": "Analytical Chemistry", "ingest_kind": "existing_chroma", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "authors": [{"family": "Keune", "given": "Katrien"}, {"family": "Boon", "given": "Jaap J."}], "volume": "77", "issue": "15", "pages": "4742-4750", "url": "https://doi.org/10.1021/ac048158f"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "alpha-Hg3S2Cl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "corderoite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 2, "reactant": "alpha-Hg3S2Cl2", "product": "Hg2Cl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "corderoite", "product_span": "calomel", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg2Cl2", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "calomel", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 20, "dense_candidates": 400, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 16, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 200, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/6e07eeada6db2a42d40e0be0a4054d1fc453b59a.json b/rag_report_cache/6e07eeada6db2a42d40e0be0a4054d1fc453b59a.json
new file mode 100644
index 0000000000000000000000000000000000000000..83de86c8a5de997590b033dc97e68b4b0a0ee605
--- /dev/null
+++ b/rag_report_cache/6e07eeada6db2a42d40e0be0a4054d1fc453b59a.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Uv+Oxidant]--> HgSO4", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CHAPPÉ M, HILDENHAGEN J, DICKMANN K, et al. Laser irradiation of medieval pigments at IR, VIS and UV wavelengths [J/OL]. Journal of Cultural Heritage, 2003. DOI: 10.1016/s1296-2074(02)01206-2.", "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "snippet": "the intensity and type of radiation having a rate-determining influence. Besides, schuettetic has been found in cinnabar deposits exposed to natural sunlight in numerous locations, including Almaden (Spain), California and Nevada (USA), Bolivia, Moravia (Czech Republic), and Sonora (Mexico) [48]. According to Bailey et al. [19], this mineral forms through photooxidation of sunlight-exposed cinnabar in the presence of oxygen-bearing surface water. Importantly, the authors acknowledged that HgSO\\({}_{4}\\) might be an intermediate phase during schuettetic formation. In any case, sulfate formation is not limited to cinnabar deposits. Radeport et al. [2, 17] acknowledged the possible oxidation of mercury sulfide to sulfate upon cinnabar degradation in the case of a Gothic wall painting from the monastery of Pedralbes (Barcelona, Spain) and detected mercury sulfate in artificially aged cinnabar pellets.", "retrieval_origin": "crn_provenance", "match": {"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "inferred", "score": 0.87, "window": "According to Bailey et al. [19], this mineral forms through photooxidation of sunlight-exposed cinnabar in the presence of oxygen-bearing surface water. Importantly, the authors acknowledged that HgSO4 might be an intermediate phase during schuettetic formation. In any case, sulfate formation is not limited to cinnabar deposits. Radeport et al. [2, 17] acknowledged the possible oxidation of mercury sulfide to sulfate upon cinnabar degradation in the case of a Gothic wall painting from the monastery of Pedralbes (Barcelona, Spain) and detected mercury sulfate in artificially aged cinnabar pellets.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "mercury sulfide", "product_span": "mercury sulfate", "relation_basis": "author_proposal", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_author_proposal"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 11, "dense_candidates": 220, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 15, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 203, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/71b36ce9625cb4b30bb36673b5661517e134f5a6.json b/rag_report_cache/71b36ce9625cb4b30bb36673b5661517e134f5a6.json
new file mode 100644
index 0000000000000000000000000000000000000000..799ed10924f8c946635fa0795e19da1c7781d27a
--- /dev/null
+++ b/rag_report_cache/71b36ce9625cb4b30bb36673b5661517e134f5a6.json
@@ -0,0 +1 @@
+{"root_material": "As4S4", "path_str": "As4S4 --[Uv]--> p-As4S4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThis means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).\n\n[1] Evidence classification: edge 1: direct\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.\n\n[1] Evidence classification: edge 1: direct\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.\n\n[1] Evidence classification: edge 1: direct\nFigure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).\n\n[1] Evidence classification: edge 1: direct\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\n\n[1] Evidence classification: edge 1: direct\nAlthough the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.\n\n[1] Evidence classification: edge 1: direct\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\n\n[1] Evidence classification: edge 1: direct\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\n\n[1] Evidence classification: edge 1: direct\nAs it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].\n\n[1] Evidence classification: edge 1: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\n\n[1] Evidence classification: edge 1: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).\n\n[2] Evidence classification: edge 1: direct\nThe Light-Induced Alteration of Realgar to Pararealgar.\n\n[3] Evidence classification: edge 1: direct\nSmall quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.\n\n[3] Evidence classification: edge 1: direct\nAs such, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58].\n\n[3] Evidence classification: edge 1: direct\nuch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.\n\n[4] Evidence classification: edge 1: direct\nRealgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].\n\n[4] Evidence classification: edge 1: direct\nBefore this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].\n\n[4] Evidence classification: edge 1: direct\nRadiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].\n\n[5] Evidence classification: edge 1: direct\nExposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].\n\n[6] Evidence classification: edge 1: direct\nThe light‐induced alteration of realgar to pararealgar.\n\n[7] Evidence classification: edge 1: direct\nThe light-induced alteration of realgar to pararealgar.", "ref_list": ["JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9.", "BROERS FTH, JANSSENS K, WEKER JN, et al. Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings [J/OL]. Journal of the American Chemical Society, 2023. DOI: 10.1021/jacs.2c12271.", "VERMEULEN M, SAVERWYNS S, COUDRAY A, et al. Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments [J/OL]. Dyes and Pigments, 2018. DOI: 10.1016/j.dyepig.2017.10.009.", "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization [J/OL]. Heritage Science, 2024. DOI: 10.1186/s40494-024-01350-x. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:16. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:24. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "KEUNE K, MASS J, MEHTA A, et al. Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues [J/OL]. Heritage Science, 2016. DOI: 10.1186/s40494-016-0078-1."], "ref_snippets": [{"text": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.\nFigure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\nAlthough the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\nAs it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": 0.4454336166381836, "snippets": [{"text": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).", "score": 0.5155298709869385, "metadata": {"chunk_index": 61, "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "ingest_kind": "existing_chroma", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "doi": "10.1007/s40828-019-0100-9", "year": "2020", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.", "score": 0.4454336166381836, "metadata": {"title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "year": "2020", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 1, "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.", "score": 0.45685338973999023, "metadata": {"ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 2, "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "year": "2020", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Figure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).", "score": 0.4743976593017578, "metadata": {"source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 67, "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "year": "2020", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Figure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "score": 0.5056250691413879, "metadata": {"source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "doi": "10.1007/s40828-019-0100-9", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "year": "2020", "journal": "ChemTexts", "chunk_index": 42, "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Although the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.", "score": 0.5094079971313477, "metadata": {"journal": "ChemTexts", "year": "2020", "chunk_index": 35, "doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Although the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "score": null, "metadata": {"title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "ingest_kind": "existing_chroma", "doi": "10.1007/s40828-019-0100-9", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "year": "2020", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "chunk_index": 3, "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "score": null, "metadata": {"year": "2020", "chunk_index": 43, "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "doi": "10.1007/s40828-019-0100-9", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "As it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].", "score": null, "metadata": {"year": "2020", "ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 62, "doi": "10.1007/s40828-019-0100-9", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "As it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "score": null, "metadata": {"chunk_index": 73, "ingest_kind": "existing_chroma", "doi": "10.1007/s40828-019-0100-9", "year": "2020", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "journal": "ChemTexts", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": null, "metadata": {"title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "chunk_index": 75, "year": "2020", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "ingest_kind": "existing_chroma", "doi": "10.1007/s40828-019-0100-9", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The Light-Induced Alteration of Realgar to Pararealgar.", "score": 0.5079103708267212, "snippets": [{"text": "The Light-Induced Alteration of Realgar to Pararealgar.", "score": 0.5079103708267212, "metadata": {"fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "year": "2023", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "ingest_kind": "pdf_fulltext", "journal": "Journal of the American Chemical Society", "doi": "10.1021/jacs.2c12271", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "page": 13, "chunk_index": 36, "license": "https://creativecommons.org/licenses/by/4.0/"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The Light-Induced Alteration of Realgar to Pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Small quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.\nAs such, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58].\nuch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "score": null, "snippets": [{"text": "Small quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.", "score": null, "metadata": {"title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "year": "2018", "chunk_index": 3, "journal": "Dyes and Pigments", "doi": "10.1016/j.dyepig.2017.10.009", "source": "pdf_reextract/雄黄", "ingest_kind": "pdf_reextract"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Small quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "As such, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58].", "score": null, "metadata": {"journal": "Dyes and Pigments", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "chunk_index": 24, "ingest_kind": "pdf_reextract", "year": "2018", "doi": "10.1016/j.dyepig.2017.10.009", "source": "pdf_reextract/雄黄"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "As such, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "score": null, "metadata": {"journal": "Dyes and Pigments", "year": "2018", "source": "pdf_reextract/雄黄", "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "ingest_kind": "pdf_reextract", "chunk_index": 25, "doi": "10.1016/j.dyepig.2017.10.009"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Realgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].\nBefore this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].\nRadiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "score": null, "snippets": [{"text": "Realgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].", "score": null, "metadata": {"chunk_index": 7, "journal": "Heritage Science", "source_file": "s40494-024-01350-x.pdf", "ingest_kind": "pdf_direct", "doi": "10.1186/s40494-024-01350-x", "source": "pdf_direct/s40494-024-01350-x", "year": "2024", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Realgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].", "score": null, "metadata": {"source_file": "s40494-024-01350-x.pdf", "source": "pdf_direct/s40494-024-01350-x", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization", "journal": "Heritage Science", "year": "2024", "chunk_index": 9, "doi": "10.1186/s40494-024-01350-x", "ingest_kind": "pdf_direct"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Radiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "score": null, "metadata": {"source": "pdf_direct/s40494-024-01350-x", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization", "chunk_index": 19, "year": "2024", "ingest_kind": "pdf_direct", "journal": "Heritage Science", "source_file": "s40494-024-01350-x.pdf", "doi": "10.1186/s40494-024-01350-x"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Radiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "score": null, "snippets": [{"text": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "score": null, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "page": "16", "ingest_kind": "pdf_fulltext", "chunk_index": "53", "source_file": "On the stability of mediaeval inorganic pigments - a review", "doi": "10.1186/s40494-017-0125-6", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "journal": "Heritage Science"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The light‐induced alteration of realgar to pararealgar.", "score": null, "snippets": [{"text": "The light‐induced alteration of realgar to pararealgar.", "score": null, "metadata": {"source_file": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "chunk_index": "102", "journal": "Heritage Science", "page": "24", "source": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext", "doi": "10.1186/s40494-017-0125-6", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The light‐induced alteration of realgar to pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The light-induced alteration of realgar to pararealgar.", "score": null, "snippets": [{"text": "The light-induced alteration of realgar to pararealgar.", "score": null, "metadata": {"doi": "10.1186/s40494-016-0078-1", "chunk_index": 34, "ingest_kind": "pdf_direct", "source_file": "s40494-016-0078-1.pdf", "title": "Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues", "year": "2016", "source": "pdf_direct/s40494-016-0078-1", "journal": "Heritage Science"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The light-induced alteration of realgar to pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 7, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 21, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 157, "lexical_kept": 21, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
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index 0000000000000000000000000000000000000000..05262471748961273077f5ebfe51626648872941
--- /dev/null
+++ b/rag_report_cache/745b0fd0119e2843e4bc83af56a23dfeb7a12f1e.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Alkaline]--> Cu(OH)2 --[Alkaline]--> [Cu(OH)4]2- --[Alkaline]--> CuO", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 2: direct\nmetastable phases that are difficult to isolate in pure crystalline form 23,43. Consequently, at room temperature and under high pH conditions, Cu(OH)2 forms a complex anion (Cu(OH)4 2−)t h a ta c t sa sap r e c u r s o ri nt h e formation of black Cu-oxides43. Although Cu-hydroxides were not identi- fied by μXRD in our samples, their formation as an intermediate phase cannot be excluded, particularly given the strongly alkaline and humid environment of frescoes. Importantly, copper hydroxides are thermodynamically unstable under ambient conditions and tend to dehy- drate or transform into copper oxides 44. In the mock-ups here evaluated, tenorite (CuO) and cuprite (Cu2O) were identified only in some samples, suggesting that hydroxides and other intermediates may evolve towards CuO over time.\n\n[2] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> CuO: direct\nis formed. The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124]. Malachite (CuCO3·Cu(OH)2, green) Malachite (CuCO 3·Cu(OH)2) is more stable than azurite (2CuCO 3·Cu(OH)2) and verdigris (xCu(CH3COO2)·yCu(OH)2·zH2O), therefore showing less or slower reactivity towards many factors [119, 123]. It is known to be permanent in all binding media, light - fast and alkali proof.\n\n[3] Evidence classification: edge 1: direct\ndesantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> CuO: direct\nConversion of azurite into tenorite (CuO) can be due to two different causes: alkaline environment and heat.\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> CuO: direct\nThe azurite alteration in a black pigment, the copper oxide (tenor ite), has been studied by micro-Raman spectroscopy. The blackening can be due to thermal or chemical alte rations: in the second case the alterations being due to the presence of alkaline conditions.\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> CuO: direct\ne. The authors attributed the alteration to the alkaline conditions characterizing the burial site, and due to the large presence of CaO and humidity. A recent study 10 has investigated the problem of alteration of the pigment to tenorite, related both to the painting technique and to some materials traditionally employed in conservation. Other studies consider the transformation that a mural painting can undergo after exposure to heat. 11 Rickerby12 investigated the problem of the conversion of azurite into cupric oxide caused by high temperature by reproducing painted samples and heating them to different temperature ranges.\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> CuO: direct\nMicro-Raman spectroscopy turns out to be the suitable analytical technique in these cases and, as we have shown, it is possible to detect the presence of both the degraded and nondegraded forms in the same micro areas. As already known, the alkalinity conditions are responsible for the degradation of azurite into tenorite.\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> CuO: direct\nAs already known, the alkalinity conditions are responsible for the degradation of azurite into tenorite.\n\n[4] Evidence classification: edge 1: direct\nThe treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "ref_list": ["Blackening of copper pigments in wall paintings: impact of the fresco technique and the chemical composition of the pigments [J/OL]. Heritage Science, 2026:10. DOI: 10.1038/s40494-026-02461-3. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424."], "ref_snippets": [{"text": "metastable phases that are difficult to isolate in pure crystalline form 23,43. Consequently, at room temperature and under high pH conditions, Cu(OH)2 forms a complex anion (Cu(OH)4 2−)t h a ta c t sa sap r e c u r s o ri nt h e formation of black Cu-oxides43. Although Cu-hydroxides were not identi- fied by μXRD in our samples, their formation as an intermediate phase cannot be excluded, particularly given the strongly alkaline and humid environment of frescoes. Importantly, copper hydroxides are thermodynamically unstable under ambient conditions and tend to dehy- drate or transform into copper oxides 44. In the mock-ups here evaluated, tenorite (CuO) and cuprite (Cu2O) were identified only in some samples, suggesting that hydroxides and other intermediates may evolve towards CuO over time.", "score": 0.4655810594558716, "snippets": [{"text": "metastable phases that are difficult to isolate in pure crystalline form 23,43. Consequently, at room temperature and under high pH conditions, Cu(OH)2 forms a complex anion (Cu(OH)4 2−)t h a ta c t sa sap r e c u r s o ri nt h e formation of black Cu-oxides43. Although Cu-hydroxides were not identi- fied by μXRD in our samples, their formation as an intermediate phase cannot be excluded, particularly given the strongly alkaline and humid environment of frescoes. Importantly, copper hydroxides are thermodynamically unstable under ambient conditions and tend to dehy- drate or transform into copper oxides 44. In the mock-ups here evaluated, tenorite (CuO) and cuprite (Cu2O) were identified only in some samples, suggesting that hydroxides and other intermediates may evolve towards CuO over time.", "score": 0.4655810594558716, "metadata": {"source_file": "Blackening of copper pigments in wall paintings", "year": "2026", "chunk_index": "33", "page": "10", "ingest_kind": "pdf_fulltext", "source": "Blackening of copper pigments in wall paintings", "doi": "10.1038/s40494-026-02461-3", "title": "Blackening of copper pigments in wall paintings: impact of the fresco technique and the chemical composition of the pigments", "journal": "Heritage Science"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "Cu(OH)2", "product": "[Cu(OH)4]2-", "condition": "Alkaline", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "metastable phases that are difficult to isolate in pure crystalline form 23,43. Consequently, at room temperature and under high pH conditions, Cu(OH)2 forms a complex anion (Cu(OH)4 2−)t h a ta c t sa sap r e c u r s o ri nt h e formation of black Cu-oxides43. Although Cu-hydroxides were not identi- fied by μXRD in our samples, their formation as an intermediate phase cannot be excluded, particularly given the strongly alkaline and humid environment of frescoes. Importantly, copper hydroxides are thermodynamically unstable under ambient conditions and tend to dehy- drate or transform into copper oxides 44. In the mock-ups here evaluated, tenorite (CuO) and cuprite (Cu2O) were identified only in some samples, suggesting that hydroxides and other intermediates may evolve towards CuO over time.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Cu(OH)2", "product_span": "Cu(OH)4", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "is formed. The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124]. Malachite (CuCO3·Cu(OH)2, green) Malachite (CuCO 3·Cu(OH)2) is more stable than azurite (2CuCO 3·Cu(OH)2) and verdigris (xCu(CH3COO2)·yCu(OH)2·zH2O), therefore showing less or slower reactivity towards many factors [119, 123]. It is known to be permanent in all binding media, light - fast and alkali proof.", "score": 0.475486695766449, "snippets": [{"text": "is formed. The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124]. Malachite (CuCO3·Cu(OH)2, green) Malachite (CuCO 3·Cu(OH)2) is more stable than azurite (2CuCO 3·Cu(OH)2) and verdigris (xCu(CH3COO2)·yCu(OH)2·zH2O), therefore showing less or slower reactivity towards many factors [119, 123]. It is known to be permanent in all binding media, light - fast and alkali proof.", "score": 0.475486695766449, "metadata": {"year": "2017", "ingest_kind": "pdf_fulltext", "source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "chunk_index": "40", "doi": "10.1186/s40494-017-0125-6", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source_file": "On the stability of mediaeval inorganic pigments - a review", "page": "13"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "CuO", "condition": "Alkaline", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "is formed. The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124]. Malachite (CuCO3·Cu(OH)2, green) Malachite (CuCO 3·Cu(OH)2) is more stable than azurite (2CuCO 3·Cu(OH)2) and verdigris (xCu(CH3COO2)·yCu(OH)2·zH2O), therefore showing less or slower reactivity towards many factors [119, 123]. It is known to be permanent in all binding media, light - fast and alkali proof.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "CuO", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "desantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.\nConversion of azurite into tenorite (CuO) can be due to two different causes: alkaline environment and heat.\nThe azurite alteration in a black pigment, the copper oxide (tenor ite), has been studied by micro-Raman spectroscopy. The blackening can be due to thermal or chemical alte rations: in the second case the alterations being due to the presence of alkaline conditions.\ne. The authors attributed the alteration to the alkaline conditions characterizing the burial site, and due to the large presence of CaO and humidity. A recent study 10 has investigated the problem of alteration of the pigment to tenorite, related both to the painting technique and to some materials traditionally employed in conservation. Other studies consider the transformation that a mural painting can undergo after exposure to heat. 11 Rickerby12 investigated the problem of the conversion of azurite into cupric oxide caused by high temperature by reproducing painted samples and heating them to different temperature ranges.\nMicro-Raman spectroscopy turns out to be the suitable analytical technique in these cases and, as we have shown, it is possible to detect the presence of both the degraded and nondegraded forms in the same micro areas. As already known, the alkalinity conditions are responsible for the degradation of azurite into tenorite.\nAs already known, the alkalinity conditions are responsible for the degradation of azurite into tenorite.", "score": 0.4565848112106323, "snippets": [{"text": "desantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.", "score": 0.4565848112106323, "metadata": {"year": "2008", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "title": "Raman spectroscopic analysis of azurite blackening", "chunk_index": 2, "journal": "Journal of Raman Spectroscopy", "doi": "10.1002/jrs.1845", "ingest_kind": "pdf_reextract", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "authors": [{"family": "Mattei", "given": "E."}, {"family": "de Vivo", "given": "G."}, {"family": "De Santis", "given": "A."}, {"family": "Gaetani", "given": "C."}, {"family": "Pelosi", "given": "C."}, {"family": "Santamaria", "given": "U."}], "volume": "39", "issue": "2", "pages": "302-306", "url": "https://doi.org/10.1002/jrs.1845"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu(OH)2", "condition": "Alkaline", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "desantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "copper hydroxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Conversion of azurite into tenorite (CuO) can be due to two different causes: alkaline environment and heat.", "score": 0.4565848112106323, "metadata": {"year": "2008", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "title": "Raman spectroscopic analysis of azurite blackening", "chunk_index": 2, "journal": "Journal of Raman Spectroscopy", "doi": "10.1002/jrs.1845", "ingest_kind": "pdf_reextract", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "authors": [{"family": "Mattei", "given": "E."}, {"family": "de Vivo", "given": "G."}, {"family": "De Santis", "given": "A."}, {"family": "Gaetani", "given": "C."}, {"family": "Pelosi", "given": "C."}, {"family": "Santamaria", "given": "U."}], "volume": "39", "issue": "2", "pages": "302-306", "url": "https://doi.org/10.1002/jrs.1845"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "CuO", "condition": "Alkaline", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Conversion of azurite into tenorite (CuO) can be due to two different causes: alkaline environment and heat.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "tenorite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The azurite alteration in a black pigment, the copper oxide (tenor ite), has been studied by micro-Raman spectroscopy. The blackening can be due to thermal or chemical alte rations: in the second case the alterations being due to the presence of alkaline conditions.", "score": null, "metadata": {"year": "2008", "doi": "10.1002/jrs.1845", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "ingest_kind": "pdf_reextract", "chunk_index": 0, "journal": "Journal of Raman Spectroscopy", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "title": "Raman spectroscopic analysis of azurite blackening", "authors": [{"family": "Mattei", "given": "E."}, {"family": "de Vivo", "given": "G."}, {"family": "De Santis", "given": "A."}, {"family": "Gaetani", "given": "C."}, {"family": "Pelosi", "given": "C."}, {"family": "Santamaria", "given": "U."}], "volume": "39", "issue": "2", "pages": "302-306", "url": "https://doi.org/10.1002/jrs.1845"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "CuO", "condition": "Alkaline", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The azurite alteration in a black pigment, the copper oxide (tenor ite), has been studied by micro-Raman spectroscopy. The blackening can be due to thermal or chemical alte rations: in the second case the alterations being due to the presence of alkaline conditions.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "tenorite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "e. The authors attributed the alteration to the alkaline conditions characterizing the burial site, and due to the large presence of CaO and humidity. A recent study 10 has investigated the problem of alteration of the pigment to tenorite, related both to the painting technique and to some materials traditionally employed in conservation. Other studies consider the transformation that a mural painting can undergo after exposure to heat. 11 Rickerby12 investigated the problem of the conversion of azurite into cupric oxide caused by high temperature by reproducing painted samples and heating them to different temperature ranges.", "score": null, "metadata": {"title": "Raman spectroscopic analysis of azurite blackening", "journal": "Journal of Raman Spectroscopy", "chunk_index": 3, "source_file": "Raman spectroscopic analysis of azurite blackening.md", "doi": "10.1002/jrs.1845", "ingest_kind": "pdf_reextract", "year": "2008", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "authors": [{"family": "Mattei", "given": "E."}, {"family": "de Vivo", "given": "G."}, {"family": "De Santis", "given": "A."}, {"family": "Gaetani", "given": "C."}, {"family": "Pelosi", "given": "C."}, {"family": "Santamaria", "given": "U."}], "volume": "39", "issue": "2", "pages": "302-306", "url": "https://doi.org/10.1002/jrs.1845"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "CuO", "condition": "Alkaline", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "e. The authors attributed the alteration to the alkaline conditions characterizing the burial site, and due to the large presence of CaO and humidity. A recent study 10 has investigated the problem of alteration of the pigment to tenorite, related both to the painting technique and to some materials traditionally employed in conservation. Other studies consider the transformation that a mural painting can undergo after exposure to heat. 11 Rickerby12 investigated the problem of the conversion of azurite into cupric oxide caused by high temperature by reproducing painted samples and heating them to different temperature ranges.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "cupric oxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Micro-Raman spectroscopy turns out to be the suitable analytical technique in these cases and, as we have shown, it is possible to detect the presence of both the degraded and nondegraded forms in the same micro areas. As already known, the alkalinity conditions are responsible for the degradation of azurite into tenorite.", "score": null, "metadata": {"ingest_kind": "pdf_reextract", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "year": "2008", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "journal": "Journal of Raman Spectroscopy", "doi": "10.1002/jrs.1845", "title": "Raman spectroscopic analysis of azurite blackening", "chunk_index": 14, "authors": [{"family": "Mattei", "given": "E."}, {"family": "de Vivo", "given": "G."}, {"family": "De Santis", "given": "A."}, {"family": "Gaetani", "given": "C."}, {"family": "Pelosi", "given": "C."}, {"family": "Santamaria", "given": "U."}], "volume": "39", "issue": "2", "pages": "302-306", "url": "https://doi.org/10.1002/jrs.1845"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "CuO", "condition": "Alkaline", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Micro-Raman spectroscopy turns out to be the suitable analytical technique in these cases and, as we have shown, it is possible to detect the presence of both the degraded and nondegraded forms in the same micro areas. As already known, the alkalinity conditions are responsible for the degradation of azurite into tenorite.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "tenorite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "As already known, the alkalinity conditions are responsible for the degradation of azurite into tenorite.", "score": null, "metadata": {"source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "year": "2008", "journal": "Journal of Raman Spectroscopy", "doi": "10.1002/jrs.1845", "title": "Raman spectroscopic analysis of azurite blackening", "chunk_index": 16, "ingest_kind": "pdf_reextract", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "authors": [{"family": "Mattei", "given": "E."}, {"family": "de Vivo", "given": "G."}, {"family": "De Santis", "given": "A."}, {"family": "Gaetani", "given": "C."}, {"family": "Pelosi", "given": "C."}, {"family": "Santamaria", "given": "U."}], "volume": "39", "issue": "2", "pages": "302-306", "url": "https://doi.org/10.1002/jrs.1845"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "CuO", "condition": "Alkaline", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "As already known, the alkalinity conditions are responsible for the degradation of azurite into tenorite.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "tenorite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "score": 0.43921202421188354, "snippets": [{"text": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "score": 0.43921202421188354, "metadata": {"journal": "Minerals", "ingest_kind": "pdf_direct", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "chunk_index": 7, "source": "pdf_direct/min10050424_part2.pdf", "doi": "10.3390/min10050424", "year": "2020", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu(OH)2", "condition": "Alkaline", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "copper hydroxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 29, "dense_candidates": 580, "dense_kept": 4, "resolver_scanned": 2314, "resolver_candidates": 30, "resolver_kept": 4, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 6, "lexical_scanned": 2314, "lexical_candidates": 236, "lexical_kept": 9, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/75796da0d2a956763d725df3d09c24c854f3afa9.json b/rag_report_cache/75796da0d2a956763d725df3d09c24c854f3afa9.json
new file mode 100644
index 0000000000000000000000000000000000000000..b73078a71fc7c8ecbf64aa4ff2311b8fd011b079
--- /dev/null
+++ b/rag_report_cache/75796da0d2a956763d725df3d09c24c854f3afa9.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Chloride]--> CuCl", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["DOMÉNECH‐CARBÓ MT, EDWARDS HGM, DOMÉNECH‐CARBÓ A, et al. An authentication case study: Antonio Palomino versus Vicente Guillo paintings in the vaulted ceiling of the Sant Joan del Mercat church (Valencia, Spain) [J/OL]. Journal of Raman Spectroscopy, 2012. DOI: 10.1002/jrs.3168.", "PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "Page 13 of 25 Coccato et al. Herit Sci (2017) 5:12 shows good performances both in oil and tempera mediums [111, 112], although its poor hiding power in oil is reported in literature [113]. Degradation of azurite in frescoes seems related to pH and grain size [91, 114]. Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH) 2) and paratacamite/atacamite (Cu2Cl(OH) 3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu 2Cl(OH) 3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH) 2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu 2Cl(OH) 3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58]. On the other hand, oxalates attributable to the biodegrada - tion of an organic binder were found in both a gyp - sum preparation (weddellite/whewellite) and in the overlying azurite-containing paint layer [116].", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCl", "condition": "Chloride", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "nantokite", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1.", "snippet": "Characterisation of rouaite, an unusual copper‐containing pigment in early modern English... Page 15 of 18 817 suggests that formation of nantokite (CuCl) may occur as an intermediate reaction in the formation of copper hydroxychlorides (Equation 3) [80]. The reactions presented here therefore offer plausible routes for azurite as well as rouaite degradation, but further study is needed to determine whether intermediate species are indeed formed and the relative favourability. Rouaite’s metastability and propensity to react further is a possible explanation for its absence in literature. Apart from degradation or conversion to other copper minerals such as chlorides or sulfates, identification of rouaite in historical samples may be hampered by the difficulty of detecting light elements such as nitrogen, the low abundance in some samples necessitating analysis with a low detection limit, and the similarity of rouaite to synthetic malachite, copper chlorides, and verditer when examined by optical and scanning electron microscopy. 4 Conclusion Rouaite, a basic copper nitrate found to be a significant byproduct of the refiners’ synthesis of blue verditer, has been identified in historical wall painting samples for the first time to our knowledge. Table 2 presents a summary of the analytic results for both samples studied. In two samples, M9 and T1, we detected rouaite using SR-/u1D707PXRD and SR-/u1D707XANES. We show that its polymorph, gerhardtite, fits the experimental data collected more poorly; this is therefore highly suggestive of a synthetic origin for the material [27]", "retrieval_origin": "crn_provenance", "match": {"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCl", "condition": "Chloride", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "Characterisation of rouaite, an unusual copper‐containing pigment in early modern English... Page 15 of 18 817 suggests that formation of nantokite (CuCl) may occur as an intermediate reaction in the formation of copper hydroxychlorides (Equation 3) [80]. The reactions presented here therefore offer plausible routes for azurite as well as rouaite degradation, but further study is needed to determine whether intermediate species are indeed formed and the relative favourability. Rouaite’s metastability and propensity to react further is a possible explanation for its absence in literature. Apart from degradation or conversion to other copper minerals such as chlorides or sulfates, identification of rouaite in historical samples may be hampered by the difficulty of detecting light elements such as nitrogen, the low abundance in some samples necessitating analysis with a low detection limit, and the similarity of rouaite to synthetic malachite, copper chlorides, and verditer when examined by optical and scanning electron microscopy.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "nantokite", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:12. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "In glue binder, the role of humidity and airborne pollutants in accelerating glassy pigments degradation was demonstrated, where leaching of both potassium and cobalt ions occurred. No evident effect of SO 2 and NO x synergy was observed though [87]. In fresco wall paint - ings, smalt is expected to deteriorate due to the very alka- line conditions, to the presence of liquid water (including condensation, capillary rise and infiltrations), to the small particle size increasing the surface reaction, and to the possible contamination by pollutants. Again, leaching of alkali is observed, and in some strongly degraded smalt particles showing cracks, cobalt and other divalent ions are leached as well, probably due to aggressive environ - mental conditions (humidity, basic pH) [88, 91, 96]. On top of ions lixiviation and weathering of the glass, exam - ples of heat degraded smalt are reported in wall paintings affected by fire [103]. Copper (Z = 29) It was recently observed that historical copper-based pigments are not only limited to malachite, azurite, verdigris and copper resinate. In fact a variety of salts (organic acids salts such as copper citrate [104], silicates, phosphates, sulphates, chlorides, etc.) were as well used as pigments [105, 106], and should not be regarded any - more as degradation products only. Moreover, the situa - tion is complicated by inconsistent nomenclature use in artistic literature [1, 105]. It is well known that malachite and azurite are not stable in fresco, and that they tend to discolour in oil [50].", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCl", "condition": "Chloride", "evidence_scope": "edge", "verdict": "unsupported", "score": 0.62, "window": "Copper (Z = 29) It was recently observed that historical copper-based pigments are not only limited to malachite, azurite, verdigris and copper resinate. In fact a variety of salts (organic acids salts such as copper citrate [104], silicates, phosphates, sulphates, chlorides, etc.) were as well used as pigments [105, 106], and should not be regarded any - more as degradation products only.", "reactant_match": "alias", "product_match": "missing", "reactant_span": "azurite", "product_span": "", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["product_missing", "relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 3, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 218, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/77d5e3e65f308819ecaa7ffc184490c95d15105c.json b/rag_report_cache/77d5e3e65f308819ecaa7ffc184490c95d15105c.json
new file mode 100644
index 0000000000000000000000000000000000000000..ea2f94c1f7a0462914240cd16120cd856412e183
--- /dev/null
+++ b/rag_report_cache/77d5e3e65f308819ecaa7ffc184490c95d15105c.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[Oxidant]--> β-PbO2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThis energy shift provides direct evidence of the chemical transformation from Pb3O4 to PbO2 during the radical-mediated oxidation process. To quantitatively analyze this conversion, peak deconvolution was performed on the Pb 4f spectra at different reaction intervals. The spectral components were assigned to either Pb3O4 (137.7/142.7 eV) or PbO2 (137.0/142.0 eV) through Gaussian-Lorentzian curve fitting, as presented in Figure 4b-f. The progressive enhancement of PbO2-associated peak intensities (137.0 eV and 142.0 eV) relative to the diminishing Pb3O4 components demonstrates a time-dependent increase in PbO2 formation. This observation aligns with the hypothesis that superoxide radicals facilitate the oxidation of Pb (II) in Pb3O4 to Pb (IV) in PbO2 through electron transfer processes.\n\n[1] Evidence classification: edge 1: direct\nThe quantitative correlation between reaction duration and PbO2/Pb3O4 ratio, as revealed by peak area analysis, further confirms the gradual conversion mechanism. The systematic transition in Pb oxidation states provides spectroscopic evidence for the formation of PbO2 as the primary product in the superoxide-mediated oxidation of Pb3O4.\n\n[1] Evidence classification: edge 1: direct\nThese trends are consistent with the stoichiometric transformation from Pb3O4 to PbO2, related to the oxidation of Pb3O4.\n\n[1] Evidence classification: edge 1: direct\nThese ratios indicate a progressive decrease in both atomic and mass ratios of Pb to O during the conversion from Pb3O4 to PbO2. Furthermore, the mixed oxidation states of Pb in Pb3O4 comprise Pb (II) and Pb (IV) in a 2:1 ratio, while PbO2 exclusively contains Pb (IV) species.\n\n[1] Evidence classification: edge 1: direct\nThe temporal evolution of these spectral characteristics provides compelling evidence of the gradual chemical transformation from Pb3O4 to PbO2 with prolonged reaction duration. This experimental observation aligns well with the proposed reaction mechanism that Pb3O4 serves as the precursor material undergoing oxidative conversion to PbO2.\n\n[1] Evidence classification: edge 1: direct\n## 4 Conclusions It has been demonstrated that the reaction of Pb3O4 with superoxide radicals over varying durations produces the mixtures of partially oxidized Pb3O4 and PbO2 in distinct ratios. The singlet oxygen and superoxide radical made the main contribution to Pb3O4 oxidation under the experimental conditions.\n\n[1] Evidence classification: edge 1: direct\nOver extended temporal scales, these radicals continuously react with the red lead pigments through oxidation mechanisms, ultimately resulting in the observed blackened lead dioxide formations seen in historical artifacts.\n\n[2] Evidence classification: edge 1: direct\nLead (Pb) has four valence electrons distributed in 6s orbital and 6p orbitals and Pb3O4 is made of PbO2 and PbO; therefore, minium pigment contains both Pb(II) and Pb(IV) oxides, but only Pb(II) can absorb ultraviolet light energy to form an excitation state with high energy, which makes Pb(II) lose the lone pair electrons in the 6s orbital to form Pb(IV) and then oxidize to black beta-PbO2 by ozone (oxygen ionization under ultraviolet radiation) or oxygen.\n\n[3] Evidence classification: edge 1: direct\nThe darkening of red lead containing paintings from antique Chinese wall paintings has been attributed to the pigment oxidation into plattnerite by microbial activity [69].\n\n[3] Evidence classification: edge 1: direct\nThe transformation of red lead into black lead dioxide (beta-PbO2, plattnerite), however, is generally stated as the main cause of red lead darkening in paintings. This compound was identified on numerous artworks, such as polychrome sculptures [8] and wall paintings [56, 57, 58]. The hypothesis of red lead oxidation into plattnerite is commonly invoked when darkened sample analyses are inefficient [59].\n\n[4] Evidence classification: edge 1: direct\nNo oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2.\n\n[5] Evidence classification: edge 1: direct\nThe sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound. As an oxidising agent, PbO2 should be highly susceptible to the reducing power of H2S, but in red lead, the structure consists of chains of PbIVO6 edge-sharing octahedra linked pyramidally to each other by Pb(II) atoms [11, 12].\n\n[6] Evidence classification: edge 1: direct\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\n\n[6] Evidence classification: edge 1: direct\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34]. Scrutinyite was also not used as a pigment. The presence of hydrocerussite and creussite in the wall paintings in Saint George church could indicate that the lead white pigment originally used had converted to plattnerite, the evidence for this being that no red lead was found. But, as we found earlier, strong oxidizing agents, are necessary to enable this conversion. On the other hand, red lead darkening was found as the most common reaction of red lead in our laboratory experiments and it is possible and probable that during hundreds of years its conversion to plattnerite and creussite was total.\n\n[6] Evidence classification: edge 1: direct\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite\n\n[6] Evidence classification: edge 1: direct\nPhase abbreviations: Ca: calcite (CaCO3); Ce: cervasite (PbCO3); H: hydrocervasite (Pb9(CO3)2(OH)2); L: PbMg(CO3)2; P: plattrerite (PbO2). Figure 7: X-ray pattern of reaction product of red lead pigment with solution of MgSO4 and (NH4)2CO3. The reaction mixture reacted for six months. Phase abbreviations: Ce: cervasite (PbCO3); L: PbMg(CO3)2; M: minimum (Pb3O4); P: plattrerite (PbO2). Lead white (hydrocerussite) darkened immediately when in contact with a solution of NaClO due to its oxidation to brown-black plattrerite (PbO2).", "ref_list": ["ZHANG Z, HUANG Q, SUN J, et al. Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions [J/OL]. Molecules, 2025. DOI: 10.3390/molecules30102136.", "ZHAO Y, WANG J, PAN A, et al. Degradation of red lead pigment in the oil painting during UV aging [J/OL]. Color Research & Application, 2019. DOI: 10.1002/col.22386.", "AZE S, VALLET JM, DETALLE V, et al. Chromatic alterations of red lead pigments in artworks: a review [J/OL]. Phase Transitions, 2008. DOI: 10.1080/01411590701514326.", "VAGNINI M, VIVANI R, SGAMELLOTTI A, et al. Blackening of lead white: Study of model paintings [J/OL]. Journal of Raman Spectroscopy, 2020. DOI: 10.1002/jrs.5879.", "SMITH GD, CLARK RJH. The role of H2S in pigment blackening [J/OL]. Journal of Cultural Heritage, 2002. DOI: 10.1016/s1296-2074(02)01173-1.", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001."], "ref_snippets": [{"text": "This energy shift provides direct evidence of the chemical transformation from Pb3O4 to PbO2 during the radical-mediated oxidation process. To quantitatively analyze this conversion, peak deconvolution was performed on the Pb 4f spectra at different reaction intervals. The spectral components were assigned to either Pb3O4 (137.7/142.7 eV) or PbO2 (137.0/142.0 eV) through Gaussian-Lorentzian curve fitting, as presented in Figure 4b-f. The progressive enhancement of PbO2-associated peak intensities (137.0 eV and 142.0 eV) relative to the diminishing Pb3O4 components demonstrates a time-dependent increase in PbO2 formation. This observation aligns with the hypothesis that superoxide radicals facilitate the oxidation of Pb (II) in Pb3O4 to Pb (IV) in PbO2 through electron transfer processes.\nThe quantitative correlation between reaction duration and PbO2/Pb3O4 ratio, as revealed by peak area analysis, further confirms the gradual conversion mechanism. The systematic transition in Pb oxidation states provides spectroscopic evidence for the formation of PbO2 as the primary product in the superoxide-mediated oxidation of Pb3O4.\nThese trends are consistent with the stoichiometric transformation from Pb3O4 to PbO2, related to the oxidation of Pb3O4.\nThese ratios indicate a progressive decrease in both atomic and mass ratios of Pb to O during the conversion from Pb3O4 to PbO2. Furthermore, the mixed oxidation states of Pb in Pb3O4 comprise Pb (II) and Pb (IV) in a 2:1 ratio, while PbO2 exclusively contains Pb (IV) species.\nThe temporal evolution of these spectral characteristics provides compelling evidence of the gradual chemical transformation from Pb3O4 to PbO2 with prolonged reaction duration. This experimental observation aligns well with the proposed reaction mechanism that Pb3O4 serves as the precursor material undergoing oxidative conversion to PbO2.\n## 4 Conclusions It has been demonstrated that the reaction of Pb3O4 with superoxide radicals over varying durations produces the mixtures of partially oxidized Pb3O4 and PbO2 in distinct ratios. The singlet oxygen and superoxide radical made the main contribution to Pb3O4 oxidation under the experimental conditions.\nOver extended temporal scales, these radicals continuously react with the red lead pigments through oxidation mechanisms, ultimately resulting in the observed blackened lead dioxide formations seen in historical artifacts.", "score": 0.3482212424278259, "snippets": [{"text": "This energy shift provides direct evidence of the chemical transformation from Pb3O4 to PbO2 during the radical-mediated oxidation process. To quantitatively analyze this conversion, peak deconvolution was performed on the Pb 4f spectra at different reaction intervals. The spectral components were assigned to either Pb3O4 (137.7/142.7 eV) or PbO2 (137.0/142.0 eV) through Gaussian-Lorentzian curve fitting, as presented in Figure 4b-f. The progressive enhancement of PbO2-associated peak intensities (137.0 eV and 142.0 eV) relative to the diminishing Pb3O4 components demonstrates a time-dependent increase in PbO2 formation. This observation aligns with the hypothesis that superoxide radicals facilitate the oxidation of Pb (II) in Pb3O4 to Pb (IV) in PbO2 through electron transfer processes.", "score": 0.45448803901672363, "metadata": {"ingest_kind": "existing_chroma", "journal": "Molecules", "doi": "10.3390/molecules30102136", "source_file": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "year": "2025", "title": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions", "source": "markdown_output/Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "chunk_index": 33, "authors": [{"family": "Zhang", "given": "Zhehan"}, {"family": "Huang", "given": "Qin"}, {"family": "Sun", "given": "Jiaxing"}, {"family": "Hao", "given": "Qilong"}, {"family": "Zhang", "given": "Wenyuan"}, {"family": "Yu", "given": "Zongren"}, {"family": "Su", "given": "Bomin"}, {"family": "Zhang", "given": "Haixia"}], "volume": "30", "issue": "10", "pages": "2136", "url": "https://doi.org/10.3390/molecules30102136"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "This energy shift provides direct evidence of the chemical transformation from Pb3O4 to PbO2 during the radical-mediated oxidation process. To quantitatively analyze this conversion, peak deconvolution was performed on the Pb 4f spectra at different reaction intervals. The spectral components were assigned to either Pb3O4 (137.7/142.7 eV) or PbO2 (137.0/142.0 eV) through Gaussian-Lorentzian curve fitting, as presented in Figure 4b-f. The progressive enhancement of PbO2-associated peak intensities (137.0 eV and 142.0 eV) relative to the diminishing Pb3O4 components demonstrates a time-dependent increase in PbO2 formation. This observation aligns with the hypothesis that superoxide radicals facilitate the oxidation of Pb (II) in Pb3O4 to Pb (IV) in PbO2 through electron transfer processes.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Pb3O4", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The quantitative correlation between reaction duration and PbO2/Pb3O4 ratio, as revealed by peak area analysis, further confirms the gradual conversion mechanism. The systematic transition in Pb oxidation states provides spectroscopic evidence for the formation of PbO2 as the primary product in the superoxide-mediated oxidation of Pb3O4.", "score": 0.45488297939300537, "metadata": {"year": "2025", "doi": "10.3390/molecules30102136", "chunk_index": 34, "source_file": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "ingest_kind": "existing_chroma", "journal": "Molecules", "title": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions", "source": "markdown_output/Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "authors": [{"family": "Zhang", "given": "Zhehan"}, {"family": "Huang", "given": "Qin"}, {"family": "Sun", "given": "Jiaxing"}, {"family": "Hao", "given": "Qilong"}, {"family": "Zhang", "given": "Wenyuan"}, {"family": "Yu", "given": "Zongren"}, {"family": "Su", "given": "Bomin"}, {"family": "Zhang", "given": "Haixia"}], "volume": "30", "issue": "10", "pages": "2136", "url": "https://doi.org/10.3390/molecules30102136"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The quantitative correlation between reaction duration and PbO2/Pb3O4 ratio, as revealed by peak area analysis, further confirms the gradual conversion mechanism. The systematic transition in Pb oxidation states provides spectroscopic evidence for the formation of PbO2 as the primary product in the superoxide-mediated oxidation of Pb3O4.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Pb3O4", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "These trends are consistent with the stoichiometric transformation from Pb3O4 to PbO2, related to the oxidation of Pb3O4.", "score": 0.45956385135650635, "metadata": {"ingest_kind": "existing_chroma", "doi": "10.3390/molecules30102136", "chunk_index": 42, "title": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions", "source_file": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "journal": "Molecules", "source": "markdown_output/Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "year": "2025", "authors": [{"family": "Zhang", "given": "Zhehan"}, {"family": "Huang", "given": "Qin"}, {"family": "Sun", "given": "Jiaxing"}, {"family": "Hao", "given": "Qilong"}, {"family": "Zhang", "given": "Wenyuan"}, {"family": "Yu", "given": "Zongren"}, {"family": "Su", "given": "Bomin"}, {"family": "Zhang", "given": "Haixia"}], "volume": "30", "issue": "10", "pages": "2136", "url": "https://doi.org/10.3390/molecules30102136"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "These trends are consistent with the stoichiometric transformation from Pb3O4 to PbO2, related to the oxidation of Pb3O4.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Pb3O4", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "These ratios indicate a progressive decrease in both atomic and mass ratios of Pb to O during the conversion from Pb3O4 to PbO2. Furthermore, the mixed oxidation states of Pb in Pb3O4 comprise Pb (II) and Pb (IV) in a 2:1 ratio, while PbO2 exclusively contains Pb (IV) species.", "score": 0.4636874794960022, "metadata": {"title": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions", "ingest_kind": "existing_chroma", "journal": "Molecules", "source": "markdown_output/Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "source_file": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "doi": "10.3390/molecules30102136", "year": "2025", "chunk_index": 39, "authors": [{"family": "Zhang", "given": "Zhehan"}, {"family": "Huang", "given": "Qin"}, {"family": "Sun", "given": "Jiaxing"}, {"family": "Hao", "given": "Qilong"}, {"family": "Zhang", "given": "Wenyuan"}, {"family": "Yu", "given": "Zongren"}, {"family": "Su", "given": "Bomin"}, {"family": "Zhang", "given": "Haixia"}], "volume": "30", "issue": "10", "pages": "2136", "url": "https://doi.org/10.3390/molecules30102136"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "These ratios indicate a progressive decrease in both atomic and mass ratios of Pb to O during the conversion from Pb3O4 to PbO2. Furthermore, the mixed oxidation states of Pb in Pb3O4 comprise Pb (II) and Pb (IV) in a 2:1 ratio, while PbO2 exclusively contains Pb (IV) species.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Pb3O4", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The temporal evolution of these spectral characteristics provides compelling evidence of the gradual chemical transformation from Pb3O4 to PbO2 with prolonged reaction duration. This experimental observation aligns well with the proposed reaction mechanism that Pb3O4 serves as the precursor material undergoing oxidative conversion to PbO2.", "score": 0.4752335548400879, "metadata": {"year": "2025", "source_file": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "source": "markdown_output/Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "chunk_index": 38, "doi": "10.3390/molecules30102136", "ingest_kind": "existing_chroma", "journal": "Molecules", "title": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions", "authors": [{"family": "Zhang", "given": "Zhehan"}, {"family": "Huang", "given": "Qin"}, {"family": "Sun", "given": "Jiaxing"}, {"family": "Hao", "given": "Qilong"}, {"family": "Zhang", "given": "Wenyuan"}, {"family": "Yu", "given": "Zongren"}, {"family": "Su", "given": "Bomin"}, {"family": "Zhang", "given": "Haixia"}], "volume": "30", "issue": "10", "pages": "2136", "url": "https://doi.org/10.3390/molecules30102136"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The temporal evolution of these spectral characteristics provides compelling evidence of the gradual chemical transformation from Pb3O4 to PbO2 with prolonged reaction duration. This experimental observation aligns well with the proposed reaction mechanism that Pb3O4 serves as the precursor material undergoing oxidative conversion to PbO2.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Pb3O4", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "## 4 Conclusions It has been demonstrated that the reaction of Pb3O4 with superoxide radicals over varying durations produces the mixtures of partially oxidized Pb3O4 and PbO2 in distinct ratios. The singlet oxygen and superoxide radical made the main contribution to Pb3O4 oxidation under the experimental conditions.", "score": 0.4973753094673157, "metadata": {"chunk_index": 52, "ingest_kind": "existing_chroma", "journal": "Molecules", "year": "2025", "source_file": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "title": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions", "doi": "10.3390/molecules30102136", "source": "markdown_output/Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "authors": [{"family": "Zhang", "given": "Zhehan"}, {"family": "Huang", "given": "Qin"}, {"family": "Sun", "given": "Jiaxing"}, {"family": "Hao", "given": "Qilong"}, {"family": "Zhang", "given": "Wenyuan"}, {"family": "Yu", "given": "Zongren"}, {"family": "Su", "given": "Bomin"}, {"family": "Zhang", "given": "Haixia"}], "volume": "30", "issue": "10", "pages": "2136", "url": "https://doi.org/10.3390/molecules30102136"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "## 4 Conclusions It has been demonstrated that the reaction of Pb3O4 with superoxide radicals over varying durations produces the mixtures of partially oxidized Pb3O4 and PbO2 in distinct ratios. The singlet oxygen and superoxide radical made the main contribution to Pb3O4 oxidation under the experimental conditions.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Pb3O4", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Over extended temporal scales, these radicals continuously react with the red lead pigments through oxidation mechanisms, ultimately resulting in the observed blackened lead dioxide formations seen in historical artifacts.", "score": 0.3482212424278259, "metadata": {"ingest_kind": "existing_chroma", "source": "markdown_output/Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "title": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions", "journal": "Molecules", "year": "2025", "chunk_index": 49, "source_file": "Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions.md", "doi": "10.3390/molecules30102136", "authors": [{"family": "Zhang", "given": "Zhehan"}, {"family": "Huang", "given": "Qin"}, {"family": "Sun", "given": "Jiaxing"}, {"family": "Hao", "given": "Qilong"}, {"family": "Zhang", "given": "Wenyuan"}, {"family": "Yu", "given": "Zongren"}, {"family": "Su", "given": "Bomin"}, {"family": "Zhang", "given": "Haixia"}], "volume": "30", "issue": "10", "pages": "2136", "url": "https://doi.org/10.3390/molecules30102136"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Over extended temporal scales, these radicals continuously react with the red lead pigments through oxidation mechanisms, ultimately resulting in the observed blackened lead dioxide formations seen in historical artifacts.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "lead dioxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Lead (Pb) has four valence electrons distributed in 6s orbital and 6p orbitals and Pb3O4 is made of PbO2 and PbO; therefore, minium pigment contains both Pb(II) and Pb(IV) oxides, but only Pb(II) can absorb ultraviolet light energy to form an excitation state with high energy, which makes Pb(II) lose the lone pair electrons in the 6s orbital to form Pb(IV) and then oxidize to black beta-PbO2 by ozone (oxygen ionization under ultraviolet radiation) or oxygen.", "score": 0.5008012056350708, "snippets": [{"text": "Lead (Pb) has four valence electrons distributed in 6s orbital and 6p orbitals and Pb3O4 is made of PbO2 and PbO; therefore, minium pigment contains both Pb(II) and Pb(IV) oxides, but only Pb(II) can absorb ultraviolet light energy to form an excitation state with high energy, which makes Pb(II) lose the lone pair electrons in the 6s orbital to form Pb(IV) and then oxidize to black beta-PbO2 by ozone (oxygen ionization under ultraviolet radiation) or oxygen.", "score": 0.5008012056350708, "metadata": {"source": "markdown_output/Degradation of red lead pigment in the oil painting during UV aging.md", "ingest_kind": "existing_chroma", "doi": "10.1002/col.22386", "journal": "Color Research & Application", "chunk_index": 35, "title": "Degradation of red lead pigment in the oil painting during UV aging", "source_file": "Degradation of red lead pigment in the oil painting during UV aging.md", "year": "2019"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "resolver", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Lead (Pb) has four valence electrons distributed in 6s orbital and 6p orbitals and Pb3O4 is made of PbO2 and PbO; therefore, minium pigment contains both Pb(II) and Pb(IV) oxides, but only Pb(II) can absorb ultraviolet light energy to form an excitation state with high energy, which makes Pb(II) lose the lone pair electrons in the 6s orbital to form Pb(IV) and then oxidize to black beta-PbO2 by ozone (oxygen ionization under ultraviolet radiation) or oxygen.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "minium", "product_span": "beta-PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The darkening of red lead containing paintings from antique Chinese wall paintings has been attributed to the pigment oxidation into plattnerite by microbial activity [69].\nThe transformation of red lead into black lead dioxide (beta-PbO2, plattnerite), however, is generally stated as the main cause of red lead darkening in paintings. This compound was identified on numerous artworks, such as polychrome sculptures [8] and wall paintings [56, 57, 58]. The hypothesis of red lead oxidation into plattnerite is commonly invoked when darkened sample analyses are inefficient [59].", "score": 0.5071769952774048, "snippets": [{"text": "The darkening of red lead containing paintings from antique Chinese wall paintings has been attributed to the pigment oxidation into plattnerite by microbial activity [69].", "score": 0.5071769952774048, "metadata": {"year": "2008", "doi": "10.1080/01411590701514326", "title": "Chromatic alterations of red lead pigments in artworks: a review", "chunk_index": 18, "source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md", "journal": "Phase Transitions", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The darkening of red lead containing paintings from antique Chinese wall paintings has been attributed to the pigment oxidation into plattnerite by microbial activity [69].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The transformation of red lead into black lead dioxide (beta-PbO2, plattnerite), however, is generally stated as the main cause of red lead darkening in paintings. This compound was identified on numerous artworks, such as polychrome sculptures [8] and wall paintings [56, 57, 58]. The hypothesis of red lead oxidation into plattnerite is commonly invoked when darkened sample analyses are inefficient [59].", "score": null, "metadata": {"year": "2008", "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md", "title": "Chromatic alterations of red lead pigments in artworks: a review", "source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "chunk_index": 14, "ingest_kind": "existing_chroma", "journal": "Phase Transitions", "doi": "10.1080/01411590701514326"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The transformation of red lead into black lead dioxide (beta-PbO2, plattnerite), however, is generally stated as the main cause of red lead darkening in paintings. This compound was identified on numerous artworks, such as polychrome sculptures [8] and wall paintings [56, 57, 58]. The hypothesis of red lead oxidation into plattnerite is commonly invoked when darkened sample analyses are inefficient [59].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "red lead", "product_span": "beta-PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "No oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2.", "score": 0.470892071723938, "snippets": [{"text": "No oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2.", "score": 0.470892071723938, "metadata": {"journal": "Journal of Raman Spectroscopy", "source_file": "Blackening of lead white: Study of model paintings.md", "doi": "10.1002/jrs.5879", "year": "2020", "ingest_kind": "existing_chroma", "title": "Blackening of lead white: Study of model paintings", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "chunk_index": 3}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "No oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound. As an oxidising agent, PbO2 should be highly susceptible to the reducing power of H2S, but in red lead, the structure consists of chains of PbIVO6 edge-sharing octahedra linked pyramidally to each other by Pb(II) atoms [11, 12].", "score": null, "snippets": [{"text": "The sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound. As an oxidising agent, PbO2 should be highly susceptible to the reducing power of H2S, but in red lead, the structure consists of chains of PbIVO6 edge-sharing octahedra linked pyramidally to each other by Pb(II) atoms [11, 12].", "score": null, "metadata": {"source": "markdown_output/The role of H2S in pigment blackening.md", "year": "2002", "source_file": "The role of H2S in pigment blackening.md", "journal": "Journal of Cultural Heritage", "title": "The role of H2S in pigment blackening", "doi": "10.1016/s1296-2074(02)01173-1", "ingest_kind": "existing_chroma", "chunk_index": 22}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound. As an oxidising agent, PbO2 should be highly susceptible to the reducing power of H2S, but in red lead, the structure consists of chains of PbIVO6 edge-sharing octahedra linked pyramidally to each other by Pb(II) atoms [11, 12].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "red lead", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34]. Scrutinyite was also not used as a pigment. The presence of hydrocerussite and creussite in the wall paintings in Saint George church could indicate that the lead white pigment originally used had converted to plattnerite, the evidence for this being that no red lead was found. But, as we found earlier, strong oxidizing agents, are necessary to enable this conversion. On the other hand, red lead darkening was found as the most common reaction of red lead in our laboratory experiments and it is possible and probable that during hundreds of years its conversion to plattnerite and creussite was total.\nBased on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite\nPhase abbreviations: Ca: calcite (CaCO3); Ce: cervasite (PbCO3); H: hydrocervasite (Pb9(CO3)2(OH)2); L: PbMg(CO3)2; P: plattrerite (PbO2). Figure 7: X-ray pattern of reaction product of red lead pigment with solution of MgSO4 and (NH4)2CO3. The reaction mixture reacted for six months. Phase abbreviations: Ce: cervasite (PbCO3); L: PbMg(CO3)2; M: minimum (Pb3O4); P: plattrerite (PbO2). Lead white (hydrocerussite) darkened immediately when in contact with a solution of NaClO due to its oxidation to brown-black plattrerite (PbO2).", "score": null, "snippets": [{"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "score": null, "metadata": {"title": "Degradation of lead-based pigments by salt solutions", "year": "2009", "doi": "10.1016/j.culher.2008.11.001", "source_file": "Degradation of lead-based pigments by salt solutions.md", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "chunk_index": 42, "journal": "Journal of Cultural Heritage", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34]. Scrutinyite was also not used as a pigment. The presence of hydrocerussite and creussite in the wall paintings in Saint George church could indicate that the lead white pigment originally used had converted to plattnerite, the evidence for this being that no red lead was found. But, as we found earlier, strong oxidizing agents, are necessary to enable this conversion. On the other hand, red lead darkening was found as the most common reaction of red lead in our laboratory experiments and it is possible and probable that during hundreds of years its conversion to plattnerite and creussite was total.", "score": null, "metadata": {"year": "2009", "title": "Degradation of lead-based pigments by salt solutions", "chunk_index": 43, "ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "doi": "10.1016/j.culher.2008.11.001", "source_file": "Degradation of lead-based pigments by salt solutions.md", "journal": "Journal of Cultural Heritage"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34]. Scrutinyite was also not used as a pigment. The presence of hydrocerussite and creussite in the wall paintings in Saint George church could indicate that the lead white pigment originally used had converted to plattnerite, the evidence for this being that no red lead was found. But, as we found earlier, strong oxidizing agents, are necessary to enable this conversion. On the other hand, red lead darkening was found as the most common reaction of red lead in our laboratory experiments and it is possible and probable that during hundreds of years its conversion to plattnerite and creussite was total.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "score": null, "metadata": {"chunk_index": 44, "journal": "Journal of Cultural Heritage", "source_file": "Degradation of lead-based pigments by salt solutions.md", "doi": "10.1016/j.culher.2008.11.001", "year": "2009", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "ingest_kind": "existing_chroma", "title": "Degradation of lead-based pigments by salt solutions"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Based on all these results, we concluded that the original pigment used for the now darkened parts of the wall paintings was red lead, which had completely transformed to plattnerite", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phase abbreviations: Ca: calcite (CaCO3); Ce: cervasite (PbCO3); H: hydrocervasite (Pb9(CO3)2(OH)2); L: PbMg(CO3)2; P: plattrerite (PbO2). Figure 7: X-ray pattern of reaction product of red lead pigment with solution of MgSO4 and (NH4)2CO3. The reaction mixture reacted for six months. Phase abbreviations: Ce: cervasite (PbCO3); L: PbMg(CO3)2; M: minimum (Pb3O4); P: plattrerite (PbO2). Lead white (hydrocerussite) darkened immediately when in contact with a solution of NaClO due to its oxidation to brown-black plattrerite (PbO2).", "score": null, "metadata": {"title": "Degradation of lead-based pigments by salt solutions", "year": "2009", "chunk_index": 53, "source_file": "Degradation of lead-based pigments by salt solutions.md", "ingest_kind": "existing_chroma", "journal": "Journal of Cultural Heritage", "doi": "10.1016/j.culher.2008.11.001", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phase abbreviations: Ca: calcite (CaCO3); Ce: cervasite (PbCO3); H: hydrocervasite (Pb9(CO3)2(OH)2); L: PbMg(CO3)2; P: plattrerite (PbO2). Figure 7: X-ray pattern of reaction product of red lead pigment with solution of MgSO4 and (NH4)2CO3. The reaction mixture reacted for six months. Phase abbreviations: Ce: cervasite (PbCO3); L: PbMg(CO3)2; M: minimum (Pb3O4); P: plattrerite (PbO2). Lead white (hydrocerussite) darkened immediately when in contact with a solution of NaClO due to its oxidation to brown-black plattrerite (PbO2).", "reactant_match": "alias", "product_match": "exact", "reactant_span": "red lead", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 10, "resolver_scanned": 2314, "resolver_candidates": 64, "resolver_kept": 16, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 9, "lexical_scanned": 2314, "lexical_candidates": 209, "lexical_kept": 16, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/873a843f9a7abe55bc17f3ccb7ab99552af1f96d.json b/rag_report_cache/873a843f9a7abe55bc17f3ccb7ab99552af1f96d.json
new file mode 100644
index 0000000000000000000000000000000000000000..81bc334133a1a4135418dd645c0daf03e9061566
--- /dev/null
+++ b/rag_report_cache/873a843f9a7abe55bc17f3ccb7ab99552af1f96d.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Binder]--> CuC2O4", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["LLUVERAS A, BOULARAND S, ANDREOTTI A, et al. Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR [J/OL]. Applied Physics A, 2010. DOI: 10.1007/s00339-010-5673-5."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "LLUVERAS A, BOULARAND S, ANDREOTTI A, et al. Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR [J/OL]. Applied Physics A, 2010. DOI: 10.1007/s00339-010-5673-5.", "snippet": "###### Abstract This article illustrates the analysis by synchrotron micro-analytical techniques of an azurite painting presenting greenish chromatic degradation. The challenge of the experiments was to obtain the spatial distribution of the degradation products of azurite. Copper hydroxchlorides, carbonates and copper oxalates have been mapped by SR FTIR imaging of cross sections in transmission mode. To complement the information, Py/GC/MS and GC/MS techniques were applied in order to characterize the binding media and organic materials present as well as their degradation products. Results contribute to a better understanding of the decay of blue areas in ancient paintings not only from the particular point of view of azurite weathering, but also by adding information regarding the oxalates' formation and their distribution in painting samples. Synchrotron radiation demonstrates its capability for the mapping in painting cross sections.", "retrieval_origin": "crn_provenance", "match": {"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuC2O4", "condition": "Binder", "evidence_scope": "edge", "verdict": "qualified", "score": 0.67, "window": "The challenge of the experiments was to obtain the spatial distribution of the degradation products of azurite. Copper hydroxchlorides, carbonates and copper oxalates have been mapped by SR FTIR imaging of cross sections in transmission mode. To complement the information, Py/GC/MS and GC/MS techniques were applied in order to characterize the binding media and organic materials present as well as their degradation products.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "copper oxalates", "relation_basis": "product_identification", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 12, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 253, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/899ef353b5481eecb11e2e85586ca7eafecae0a1.json b/rag_report_cache/899ef353b5481eecb11e2e85586ca7eafecae0a1.json
new file mode 100644
index 0000000000000000000000000000000000000000..08732cbbb2d99848d3fe39bafaf67e9b7f290549
--- /dev/null
+++ b/rag_report_cache/899ef353b5481eecb11e2e85586ca7eafecae0a1.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[H2S]--> CuS", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nPage 14 of 25Coccato et al. Herit Sci (2017) 5:12 bluish sulphide covellite, which is formed on the pure malachite pigment [126, 139], although in paint layers this has not yet been identified [124, 126]. On the other hand, it seems that Cu act as a biocide towards microor - ganisms that produce sulphuric acid, leading to a selec - tive H2S attack on non-copper pigments [124].", "ref_list": ["On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:14. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "SMITH GD, CLARK RJH. The role of H2S in pigment blackening [J/OL]. Journal of Cultural Heritage, 2002. DOI: 10.1016/s1296-2074(02)01173-1."], "ref_snippets": [{"text": "Page 14 of 25Coccato et al. Herit Sci (2017) 5:12 bluish sulphide covellite, which is formed on the pure malachite pigment [126, 139], although in paint layers this has not yet been identified [124, 126]. On the other hand, it seems that Cu act as a biocide towards microor - ganisms that produce sulphuric acid, leading to a selec - tive H2S attack on non-copper pigments [124].", "score": null, "snippets": [{"text": "Page 14 of 25Coccato et al. Herit Sci (2017) 5:12 bluish sulphide covellite, which is formed on the pure malachite pigment [126, 139], although in paint layers this has not yet been identified [124, 126]. On the other hand, it seems that Cu act as a biocide towards microor - ganisms that produce sulphuric acid, leading to a selec - tive H2S attack on non-copper pigments [124].", "score": null, "metadata": {"title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "page": "14", "chunk_index": "43", "doi": "10.1186/s40494-017-0125-6", "source_file": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "ingest_kind": "pdf_fulltext"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuS", "condition": "H2S", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Page 14 of 25Coccato et al. Herit Sci (2017) 5:12 bluish sulphide covellite, which is formed on the pure malachite pigment [126, 139], although in paint layers this has not yet been identified [124, 126]. On the other hand, it seems that Cu act as a biocide towards microor - ganisms that produce sulphuric acid, leading to a selec - tive H2S attack on non-copper pigments [124].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "covellite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 28, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 186, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/936613ee735959d1be19b18b49d944a7f4d78e4d.json b/rag_report_cache/936613ee735959d1be19b18b49d944a7f4d78e4d.json
new file mode 100644
index 0000000000000000000000000000000000000000..5e0d92d1d6bc7579df83196c0e618797ca07509a
--- /dev/null
+++ b/rag_report_cache/936613ee735959d1be19b18b49d944a7f4d78e4d.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Uv]--> Cu2O", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nOn exposure to laser light, pure malachite darkens [139], as a consequence of reduction of Cu 2+ to form dark cuprite Cu2O and black tenorite CuO [141, 142].", "ref_list": ["On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:14. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "CHAPPÉ M, HILDENHAGEN J, DICKMANN K, et al. Laser irradiation of medieval pigments at IR, VIS and UV wavelengths [J/OL]. Journal of Cultural Heritage, 2003. DOI: 10.1016/s1296-2074(02)01206-2."], "ref_snippets": [{"text": "On exposure to laser light, pure malachite darkens [139], as a consequence of reduction of Cu 2+ to form dark cuprite Cu2O and black tenorite CuO [141, 142].", "score": null, "snippets": [{"text": "On exposure to laser light, pure malachite darkens [139], as a consequence of reduction of Cu 2+ to form dark cuprite Cu2O and black tenorite CuO [141, 142].", "score": null, "metadata": {"title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "page": "14", "chunk_index": "43", "doi": "10.1186/s40494-017-0125-6", "source_file": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "ingest_kind": "pdf_fulltext"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2O", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "On exposure to laser light, pure malachite darkens [139], as a consequence of reduction of Cu 2+ to form dark cuprite Cu2O and black tenorite CuO [141, 142].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "cuprite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 31, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 180, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/94a0dfe8ed5c38548a0b03b75e18709eca22e0a8.json b/rag_report_cache/94a0dfe8ed5c38548a0b03b75e18709eca22e0a8.json
new file mode 100644
index 0000000000000000000000000000000000000000..7de41ff5629cd8c4f61da401ee47b558a12dfdec
--- /dev/null
+++ b/rag_report_cache/94a0dfe8ed5c38548a0b03b75e18709eca22e0a8.json
@@ -0,0 +1 @@
+{"root_material": "Na8[Al6Si6O24]S3", "path_str": "Na8[Al6Si6O24]S3 --[Acids]--> H2S", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["DEL FEDERICO E, SHÖFBERGER W, SCHELVIS J, et al. Insight into Framework Destruction in Ultramarine Pigments [J/OL]. Inorganic Chemistry, 2006, 45(3):1270-1276. DOI: 10.1021/ic050903z."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "DEL FEDERICO E, SHÖFBERGER W, SCHELVIS J, et al. Insight into Framework Destruction in Ultramarine Pigments [J/OL]. Inorganic Chemistry, 2006, 45(3):1270-1276. DOI: 10.1021/ic050903z.", "snippet": "e chemical shifts as our peak B. Therefore, it can be concluded that the fading mechanism is due to aluminum framework destruction rather than in situ conversion of the chromophores. This also explains the absence of B-type peaks in the 29Si spectra. In both the fresco environment and under acidic conditions, a yellow precipitate is found for the green ultramarine pigment, whereas the blue pigments turn gray in acidic medium and the violets turn white. Significant H 2S is also released during acidic degrada- tion. It is assumed that both elemental sulfur, as well as sulfates, may be generated during degradation as well. 1 Efforts are underway to identify the chromophore degradation products in an alkaline medium. Conclusions The NMR data suggest that there is a substantial diamag- netic region, as well as a paramagnetic region, which do not mix to an appreciable extent. The paramagnetic NMR shifts correlate well with the S 3-¥ Raman signals. The colorimetric parameters L* and C* correlate well with the paramagnetic shifts and linebroadenings, while the parameter h is rather unaffected. This is a strong indication that color in ultrama- rines is regulated via the concentration of paramagnetic species in the cages. These studies form the basis for the analysis of faded pigments in which the concentration of the major chromophores clearly decreases. In simulated fresco environments, these pigments lose their color and the NMR (30) Fritzgerald, J. E. Solid-state NMR spectroscopy of inorganic materials American Chemical Society: Washington, DC, 1999. (31) Yoshida, A.;", "retrieval_origin": "crn_provenance", "match": {"edge_index": 1, "reactant": "Na8[Al6Si6O24]S3", "product": "H2S", "condition": "Acids", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "This also explains the absence of B-type peaks in the 29Si spectra. In both the fresco environment and under acidic conditions, a yellow precipitate is found for the green ultramarine pigment, whereas the blue pigments turn gray in acidic medium and the violets turn white. Significant H2S is also released during acidic degrada- tion. It is assumed that both elemental sulfur, as well as sulfates, may be generated during degradation as well. 1 Efforts are underway to identify the chromophore degradation products in an alkaline medium.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "ultramarine", "product_span": "H2S", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:5. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "Reaction without colour change [53, 119, 127, 129] Reaction without colour change [53, 103, 119, 121, 123, 126–129] Discol‐ ouration [black, 126] Decomposition [13–138], further reaction of Cu 2+ ions [126] Bluish discol‐ ouration on pure pig‐ ment; selec‐ tive attack on other pigments in the mixture if H 2S is of biological origin [124, 126, 139] Green Verdigris xCu(CH 3COO2)· yCu(OH)2·zH2O Hydrolysis of the organic moieties [133, 147] Formation of Cu salts [119, 123, 133, 146] Browning [peroxide species, 146] Formation of blue copper hydrox‐ ides [20] Formation of oxalates [32] Bluish discol‐ ouration on pure pigment [20, 124] Green Copper resinate cop‐ per salts of abietic acid Darkening [132] Green Cu chlorides Cu 2Cl(OH)3 Polymorphism [115, 119, 121, 158, 160, 165–167] Polymor‐ phism [115, 119, 121, 158, 160, 165–167] Polymor‐ phism [115, 119, 121, 158, 160, 165–167] Formation of Cu salts [167] Formation of (unsta‐ ble) blue Cu(OH) 2 [115] Oxalates [127] Green Cu sulphates CuSO 4·yCu (OH)2·zH2O Polymorphism [127, 129, 168] Polymor‐ phism [127, 129, 168] Polymorphism [127, 129, 168] Formation of Cu salts [127, 129, 168] Oxalates [127] Blue Ultramarine Na 8[Al6Si6O24]Sn Discolouration [grey, 9] Stable [20, 30, 31]. Discol‐ ouration [grey, 31] Stable [20, 30, 31]. Discolouration (grey, [31, 35, 36, 38, 39])", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "Na8[Al6Si6O24]S3", "product": "H2S", "condition": "Acids", "evidence_scope": "edge", "verdict": "unsupported", "score": 0.75, "window": "Reaction without colour change [53, 119, 127, 129] Reaction without colour change [53, 103, 119, 121, 123, 126–129] Discol‐ ouration [black, 126] Decomposition [13–138], further reaction of Cu 2+ ions [126] Bluish discol‐ ouration on pure pig‐ ment; selec‐ tive attack on other pigments in the mixture if H2S is of biological origin [124, 126, 139] Green Verdigris xCu(CH 3COO2)· yCu(OH)2·zH2O Hydrolysis of the organic moieties [133, 147] Formation of Cu salts [119, 123, 133, 146] Browning [peroxide species, 146] Formation of blue copper hydrox‐ ides [20] Formation of oxalates [32] Bluish discol‐ ouration on pure pigment [20, 124] Green Copper resinate cop‐ per salts of abietic acid Darkening [132] Green Cu chlorides Cu2Cl(OH)3 Polymorphism [115, 119, 121, 158, 160, 165–167] Polymor‐ phism [115, 119, 121, 158, 160, 165–167] Polymor‐ phism [115, 119, 121, 158, 160, 165–167] Formation of Cu salts [167] Formation of (unsta‐ ble) blue Cu(OH)2 [115] Oxalates [127] Green Cu sulphates CuSO 4·yCu (OH)2·zH2O Polymorphism [127, 129, 168] Polymor‐ phism [127, 129, 168] Polymorphism [127, 129, 168] Formation of Cu salts [127, 129, 168] Oxalates [127] Blue Ultramarine Na 8[Al6Si6O24]Sn Discolouration [grey, 9] Stable [20, 30, 31].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "ultramarine", "product_span": "H2S", "relation_basis": "reverse_or_ambiguous", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_reverse_or_ambiguous"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:10. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "Page 10 of 25Coccato et al. Herit Sci (2017) 5:12 condensation) is present [9 ]. The sulphur present in the crystalline matrix of lazurite does not affect pigments that are otherwise sensitive to hydrogen sulphide (H 2S), such as leadwhite [20]. No alteration could be observed on decorative plasterworks in the Alhambra (Spain) [33], neither on manuscripts [24]. However, a greyish altera - tion of the paint surface (“ultramarine sickness”) can be sometimes detected, but it seems that many factors can cause discolouration of lazurite paint layers, such as the oil degradation in presence of humidity [20], or the discolouration of smalt in case of mixtures [20, 34]. It is reported in literature that ultramarine sickness is related to an acidic attack of the pigment by pollutants, biologi - cal metabolites, or even acidity of the binder [35, 36]. This hypothesis seems to be confirmed by the fact that, in oil medium, when the basic pigment leadwhite was added to the mixture (to enhance curing, increase opac - ity and adjust the shade), no visible alteration can be detected, the leadwhite somehow protecting the other pigment [35]. The zeolitic structure of the mineral allows for ion exchanges [20], and for trapping volatile mole - cules, such as the S 3 − chromophore [37], and CO2 whose presence was recently related to natural ultramarine from Afghanistan [38]. Artificial ultramarine discoloura - tion revealed a variation in the aluminium coordination, resulting in the opening of the cage and release of the chromophore [31, 39, 40].", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "Na8[Al6Si6O24]S3", "product": "H2S", "condition": "Acids", "evidence_scope": "edge", "verdict": "contradicted", "score": 0.75, "window": "Page 10 of 25Coccato et al. Herit Sci (2017) 5:12 condensation) is present [9 ]. The sulphur present in the crystalline matrix of lazurite does not affect pigments that are otherwise sensitive to hydrogen sulphide (H2S), such as leadwhite [20]. No alteration could be observed on decorative plasterworks in the Alhambra (Spain) [33], neither on manuscripts [24]. However, a greyish altera - tion of the paint surface (“ultramarine sickness”) can be sometimes detected, but it seems that many factors can cause discolouration of lazurite paint layers, such as the oil degradation in presence of humidity [20], or the discolouration of smalt in case of mixtures [20, 34]. It is reported in literature that ultramarine sickness is related to an acidic attack of the pigment by pollutants, biologi - cal metabolites, or even acidity of the binder [35, 36].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "ultramarine", "product_span": "hydrogen sulphide", "relation_basis": "negative", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_negative"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 11, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 97, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/94ff0a27dd25dfbb794e569f9e5ae43b31896ebb.json b/rag_report_cache/94ff0a27dd25dfbb794e569f9e5ae43b31896ebb.json
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index 0000000000000000000000000000000000000000..8625dd1c1638de269397993fb3db420521cd65df
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@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[12000lux+0.85W/m2+50℃+90%RH]--> 2PbCO3·Pb(OH)2 --[Fresco]--> β-PbO", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nthrough successive water and carbonate losses [25] (reactions 1.3 to 1.5). At higher temperature and in oxidizing conditions, litharge was finally converted into minium (Pb3O4, reaction 1.6). \\mathrm{Pb(s)+2CH3COOH\\to Pb(CH3COO)2+H2} \\tag{1} \\mathrm{3Pb(CH3COO)2+12O2\\to 2PbCO3\\cdot Pb(OH)2+10CO2+8H2O} \\tag{2} \\mathrm{2PbCO3\\cdot Pb(OH)2\\to 2PbCO3\\cdot PbO+H2O} \\tag{3} \\mathrm{2PbCO3\\cdot PbO\\to CO2+PbCO3\\cdot 2PbO} \\tag{4} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} According to Brown and Nees [26], litharge may be converted into minium through transitional steps, corresponding to intermediate oxidation states.\n\n[1] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nAccording to various authors, minium reduction into massicot is initiated in air over 512{}^{\\circ}C [25], 650{}^{\\circ}C [32], 535{}^{\\circ}C [33], 560{}^{\\circ}C [34].\n\n[2] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nThe parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244].\n\n[2] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nThe PbO formed by laser irra - diation can be re-oxidized to minium [142].\n\n[3] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nFormation of PbO (which can be re‐oxidised to minium, [142]) [215, 240] Formation of litharge [1, 240] Green Green earths glauconite (K,Na) (Fe 3+,Al,Mg)2 (Si,Al)4O10(OH)2) celadonite (K[(Al,Fe3+), (Fe2+,Mg)] (AlSi3,Si4) O10(OH)2 Browning [74], discolouration of oil layers [75] Green Malachite CuCO 3·Cu(OH)2 Cu acts as a biocide [124].\n\n[4] Evidence classification: pathway endpoints Pb3O4 -> beta-PbO: direct\nThe sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound.\n\n[5] Evidence classification: edge 2: direct\nUpon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.\n\n[5] Evidence classification: edge 2: direct, pathway endpoints Pb3O4 -> beta-PbO: direct\nUnder a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "ref_list": ["AZE S, VALLET JM, DETALLE V, et al. Chromatic alterations of red lead pigments in artworks: a review [J/OL]. Phase Transitions, 2008. DOI: 10.1080/01411590701514326.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:19. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:8. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "SMITH GD, CLARK RJH. The role of H2S in pigment blackening [J/OL]. Journal of Cultural Heritage, 2002. DOI: 10.1016/s1296-2074(02)01173-1.", "VAGNINI M, VIVANI R, SGAMELLOTTI A, et al. Blackening of lead white: Study of model paintings [J/OL]. Journal of Raman Spectroscopy, 2020. DOI: 10.1002/jrs.5879.", "ZHAO Y, WANG J, PAN A, et al. Degradation of red lead pigment in the oil painting during UV aging [J/OL]. Color Research & Application, 2019. DOI: 10.1002/col.22386."], "ref_snippets": [{"text": "through successive water and carbonate losses [25] (reactions 1.3 to 1.5). At higher temperature and in oxidizing conditions, litharge was finally converted into minium (Pb3O4, reaction 1.6). \\mathrm{Pb(s)+2CH3COOH\\to Pb(CH3COO)2+H2} \\tag{1} \\mathrm{3Pb(CH3COO)2+12O2\\to 2PbCO3\\cdot Pb(OH)2+10CO2+8H2O} \\tag{2} \\mathrm{2PbCO3\\cdot Pb(OH)2\\to 2PbCO3\\cdot PbO+H2O} \\tag{3} \\mathrm{2PbCO3\\cdot PbO\\to CO2+PbCO3\\cdot 2PbO} \\tag{4} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} According to Brown and Nees [26], litharge may be converted into minium through transitional steps, corresponding to intermediate oxidation states.\nAccording to various authors, minium reduction into massicot is initiated in air over 512{}^{\\circ}C [25], 650{}^{\\circ}C [32], 535{}^{\\circ}C [33], 560{}^{\\circ}C [34].", "score": 0.39539217948913574, "snippets": [{"text": "through successive water and carbonate losses [25] (reactions 1.3 to 1.5). At higher temperature and in oxidizing conditions, litharge was finally converted into minium (Pb3O4, reaction 1.6). \\mathrm{Pb(s)+2CH3COOH\\to Pb(CH3COO)2+H2} \\tag{1} \\mathrm{3Pb(CH3COO)2+12O2\\to 2PbCO3\\cdot Pb(OH)2+10CO2+8H2O} \\tag{2} \\mathrm{2PbCO3\\cdot Pb(OH)2\\to 2PbCO3\\cdot PbO+H2O} \\tag{3} \\mathrm{2PbCO3\\cdot PbO\\to CO2+PbCO3\\cdot 2PbO} \\tag{4} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} According to Brown and Nees [26], litharge may be converted into minium through transitional steps, corresponding to intermediate oxidation states.", "score": 0.39539217948913574, "metadata": {"source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "doi": "10.1080/01411590701514326", "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md", "journal": "Phase Transitions", "year": "2008", "title": "Chromatic alterations of red lead pigments in artworks: a review", "ingest_kind": "existing_chroma", "chunk_index": 7}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "through successive water and carbonate losses [25] (reactions 1.3 to 1.5). At higher temperature and in oxidizing conditions, litharge was finally converted into minium (Pb3O4, reaction 1.6). \\mathrm{Pb(s)+2CH3COOH\\to Pb(CH3COO)2+H2} \\tag{1} \\mathrm{3Pb(CH3COO)2+12O2\\to 2PbCO3\\cdot Pb(OH)2+10CO2+8H2O} \\tag{2} \\mathrm{2PbCO3\\cdot Pb(OH)2\\to 2PbCO3\\cdot PbO+H2O} \\tag{3} \\mathrm{2PbCO3\\cdot PbO\\to CO2+PbCO3\\cdot 2PbO} \\tag{4} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} \\mathrm{PbCO3\\cdot 2PbO\\to CO2+3alpha-PbO} \\tag{5} \\mathrm{3alpha-PbO+1/2O2\\to Pb3O4}. \\tag{6} According to Brown and Nees [26], litharge may be converted into minium through transitional steps, corresponding to intermediate oxidation states.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "minium", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "According to various authors, minium reduction into massicot is initiated in air over 512{}^{\\circ}C [25], 650{}^{\\circ}C [32], 535{}^{\\circ}C [33], 560{}^{\\circ}C [34].", "score": 0.40655964612960815, "metadata": {"source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "ingest_kind": "existing_chroma", "doi": "10.1080/01411590701514326", "chunk_index": 8, "journal": "Phase Transitions", "year": "2008", "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md", "title": "Chromatic alterations of red lead pigments in artworks: a review"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "According to various authors, minium reduction into massicot is initiated in air over 512{}^{\\circ}C [25], 650{}^{\\circ}C [32], 535{}^{\\circ}C [33], 560{}^{\\circ}C [34].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "minium", "product_span": "massicot", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244].\nThe PbO formed by laser irra - diation can be re-oxidized to minium [142].", "score": 0.3573569059371948, "snippets": [{"text": "The parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244].", "score": 0.3573569059371948, "metadata": {"page": "19", "source_file": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "chunk_index": "68", "ingest_kind": "pdf_fulltext", "doi": "10.1186/s40494-017-0125-6", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "red lead", "product_span": "PbO", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The PbO formed by laser irra - diation can be re-oxidized to minium [142].", "score": null, "metadata": {"doi": "10.1186/s40494-017-0125-6", "journal": "Heritage Science", "source_file": "On the stability of mediaeval inorganic pigments - a review", "chunk_index": "69", "source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "19", "ingest_kind": "pdf_fulltext"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The PbO formed by laser irra - diation can be re-oxidized to minium [142].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "minium", "product_span": "PbO", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Formation of PbO (which can be re‐oxidised to minium, [142]) [215, 240] Formation of litharge [1, 240] Green Green earths glauconite (K,Na) (Fe 3+,Al,Mg)2 (Si,Al)4O10(OH)2) celadonite (K[(Al,Fe3+), (Fe2+,Mg)] (AlSi3,Si4) O10(OH)2 Browning [74], discolouration of oil layers [75] Green Malachite CuCO 3·Cu(OH)2 Cu acts as a biocide [124].", "score": 0.43764787912368774, "snippets": [{"text": "Formation of PbO (which can be re‐oxidised to minium, [142]) [215, 240] Formation of litharge [1, 240] Green Green earths glauconite (K,Na) (Fe 3+,Al,Mg)2 (Si,Al)4O10(OH)2) celadonite (K[(Al,Fe3+), (Fe2+,Mg)] (AlSi3,Si4) O10(OH)2 Browning [74], discolouration of oil layers [75] Green Malachite CuCO 3·Cu(OH)2 Cu acts as a biocide [124].", "score": 0.43764787912368774, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "ingest_kind": "pdf_fulltext", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source_file": "On the stability of mediaeval inorganic pigments - a review", "page": "8", "journal": "Heritage Science", "chunk_index": "20", "doi": "10.1186/s40494-017-0125-6"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Formation of PbO (which can be re‐oxidised to minium, [142]) [215, 240] Formation of litharge [1, 240] Green Green earths glauconite (K,Na) (Fe 3+,Al,Mg)2 (Si,Al)4O10(OH)2) celadonite (K[(Al,Fe3+), (Fe2+,Mg)] (AlSi3,Si4) O10(OH)2 Browning [74], discolouration of oil layers [75] Green Malachite CuCO 3·Cu(OH)2 Cu acts as a biocide [124].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "minium", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound.", "score": null, "snippets": [{"text": "The sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound.", "score": null, "metadata": {"title": "The role of H2S in pigment blackening", "source": "markdown_output/The role of H2S in pigment blackening.md", "year": "2002", "ingest_kind": "existing_chroma", "journal": "Journal of Cultural Heritage", "doi": "10.1016/s1296-2074(02)01173-1", "source_file": "The role of H2S in pigment blackening.md", "chunk_index": 21}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The sluggish reaction of red lead when exposed to H2S reveals that a modest degree of protection is offered to the component PbO and PbO2 moieties by the crystal structure of this compound.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "red lead", "product_span": "PbO", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.\nUnder a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "score": null, "snippets": [{"text": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.", "score": null, "metadata": {"journal": "Journal of Raman Spectroscopy", "source_file": "Blackening of lead white: Study of model paintings.md", "title": "Blackening of lead white: Study of model paintings", "ingest_kind": "existing_chroma", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "year": "2020", "doi": "10.1002/jrs.5879", "chunk_index": 21}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO", "condition": "Fresco", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Upon comparison of the Raman spectra recorded at both the beginning and the end of degradation (Figure 3c) with that of pure hydrocerussite, it can be inferred that after 370 days, hydrocerussite is transformed into a mixture of red lead, as the main component, and massicot.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "massicot", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "score": null, "metadata": {"ingest_kind": "existing_chroma", "doi": "10.1002/jrs.5879", "title": "Blackening of lead white: Study of model paintings", "chunk_index": 35, "journal": "Journal of Raman Spectroscopy", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "source_file": "Blackening of lead white: Study of model paintings.md", "year": "2020"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO", "condition": "Fresco", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Under a fresco conditions, hydrocerussite resulted more reactive than cerussite being the former partially oxidized to red-lead (minimum, Pb3O4 with Pb (II)/Pb (IV)), whereas cerussite simply turns into litharge (alpha-PbO, Pb (II)) without changing its oxidation number.", "reactant_match": "exact", "product_match": "alias", "reactant_span": "Pb3O4", "product_span": "litharge", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 4, "resolver_scanned": 2314, "resolver_candidates": 82, "resolver_kept": 5, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 349, "lexical_kept": 8, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/9c4d05500555463399322d19279bbd04d7db8ed8.json b/rag_report_cache/9c4d05500555463399322d19279bbd04d7db8ed8.json
new file mode 100644
index 0000000000000000000000000000000000000000..6a0c413f21ed6a89a9c679c29acc94b729151bc9
--- /dev/null
+++ b/rag_report_cache/9c4d05500555463399322d19279bbd04d7db8ed8.json
@@ -0,0 +1 @@
+{"root_material": "2PbCO3·Pb(OH)2", "path_str": "2PbCO3·Pb(OH)2 --[Sulfate]--> PbSO4", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["PASTORELLI G, MIRANDA ASO, CLERICI EA, et al. Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation [J/OL]. Microchemical Journal, 2024. DOI: 10.1016/j.microc.2024.109912."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:17. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "Page 17 of 25 Coccato et al. Herit Sci (2017) 5:12 Hg–S–Cl species, as well as grey mercury chlorides) [33, 73, 199, 207]. In tempera, vermillion is only slightly sensi- tive to 248 nm laser pulses, while in oil medium it shows the lowest discolouration threshold for that laser wave - length compared to a selection of pigments [19, 193, 199, 210]. It is also reported that in oil medium the darkening is worse than in watercolour [194]. In this latter case, ver - million is reported to be sensitive to light, with oxygen and humidity accelerating the darkening [66]. No mer - cury oxalates were ever identified on vermillion paint lay- ers [56]. Lead (Z = 82) Lead pigments are not suitable for use in fresco, but they were still used due to their good hiding properties and to the low prices compared to other pigments [5, 123, 200, 211–213]. The degradation processes of the various Pb pigments yield a range of compounds which cause discolouration, strongly affecting the readability of the polychromy [200]. Lead pigments on ceramic arte - facts are sensitive to sulphur containing pollutants, to acidic solutions (rain; CO 2; microbial activity), to light and air: anglesite PbSO 4, cerussite PbCO 3, hydrocerus - site 2PbCO3·Pb(OH)2 and lead sulphide PbS are formed [166]. Anglesite, attributed to lead pigment degradation was identified on wall paintings as well [214]. To laser irradiation, reduction of the lead compounds (lead - white, massicot, red lead) occurs on the surface, so that the dark colour is attributed to formation of metallic lead, or Pb 2O [150].", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbSO4", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "Lead pigments on ceramic arte - facts are sensitive to sulphur containing pollutants, to acidic solutions (rain; CO 2; microbial activity), to light and air: anglesite PbSO 4, cerussite PbCO 3, hydrocerus - site 2PbCO3·Pb(OH)2 and lead sulphide PbS are formed [166]. Anglesite, attributed to lead pigment degradation was identified on wall paintings as well [214].", "reactant_match": "exact", "product_match": "alias", "reactant_span": "2PbCO3·Pb(OH)2", "product_span": "anglesite", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "SMITH GD, CLARK RJH. The role of H2S in pigment blackening [J/OL]. Journal of Cultural Heritage, 2002. DOI: 10.1016/s1296-2074(02)01173-1.", "snippet": "The lack of reactivity of lead(II) sulphate, an even less basic compound than PbCO3, has been previously documented, although its surface is said to react with H2S when moist. This is perhaps seen here in the rapid degradation of the hydrated crystal PbSO4\\(\\cdot\\)3PbO-H2O when exposed to H2S, although the presence of the incorporated basic PbO, which is shown in Table 1 to darken readily in response to treatment with H2S, may also explain the greater tendency of hydrated tribasic lead(II) sulphate to blacken. Lead(II) sulphate and its tribasic monohydrate are not historical pigments, although they might appear on modern art or on a restored artwork as a result of the ethereal peroxide treatment of blackened lead white [3]. These data show that complex or hydrated forms of the white lead sulphate product, which are almost certainly formed during the partly aqueous restoration treatment, are likely to darken again", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbSO4", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "contradicted", "score": 0.75, "window": "Lead(II) sulphate and its tribasic monohydrate are not historical pigments, although they might appear on modern art or on a restored artwork as a result of the ethereal peroxide treatment of blackened lead white [3]. These data show that complex or hydrated forms of the white lead sulphate product, which are almost certainly formed during the partly aqueous restoration treatment, are likely to darken again", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "lead sulphate", "relation_basis": "negative", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_negative"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:18. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "m litharge denotes a variety of compounds derived from lead oxidation, and other compounds. It is now recognized as the low temperature polymorph of PbO, which is tetragonal [1]. As a pigment, it was identified on manuscripts and mural paintings [1]. It is less stable than massicot to water and to saline solutions commonly found in wall paintings [218]. As a pigment, litharge is stable to infrared (1064 nm) and red lasers (632, 647 nm) irradiation for Raman spectro - scopic studies [215, 233]. Using a 632 nm laser with a power above 9 mW (calculated fluence of approximately 45 kW/cm 2) degradation is recorded [215]. For shorter wavelengths, and laser fluence at the sample above 2 kW/ cm 2, litharge degrades to massicot [215]. In oil and tem - pera binder, lead carboxylates are observed, showing stronger intensities compared to those formed from lead white [55]. This increased reactivity was probably well known to artists and artisans, as PbO was often used as a siccative for binders and varnishes [1]. Litharge was as well used for the preparation of other pigments [236]. It degrades to cerussite and hydrocerussite, as well as to lead sulphate and phosphate, in archaeological sites attributed to the production of painting materials in Thera, Greece [236]. Massicot (PbO, yellow) Also in this case, as for litharge, nomenclature is com - plex and confusion may arise. Massicot corresponds to orthorhombic PbO, the high temperature polymorph of this compound [1]. It is reported as a pigment in Egyp - tian artefacts, mural paintings and manuscripts [1].", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbSO4", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "unsupported", "score": 0.75, "window": "In oil and tem - pera binder, lead carboxylates are observed, showing stronger intensities compared to those formed from lead white [55]. This increased reactivity was probably well known to artists and artisans, as PbO was often used as a siccative for binders and varnishes [1]. Litharge was as well used for the preparation of other pigments [236]. It degrades to cerussite and hydrocerussite, as well as to lead sulphate and phosphate, in archaeological sites attributed to the production of painting materials in Thera, Greece [236]. Massicot (PbO, yellow) Also in this case, as for litharge, nomenclature is com - plex and confusion may arise.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "lead sulphate", "relation_basis": "direction_unresolved", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_direction_unresolved"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 12, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 212, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/a007570ff4049764ff9a7cf314d6e82e128e7226.json b/rag_report_cache/a007570ff4049764ff9a7cf314d6e82e128e7226.json
new file mode 100644
index 0000000000000000000000000000000000000000..920b32cb1cad53761381cef3edfa2577f933a2bf
--- /dev/null
+++ b/rag_report_cache/a007570ff4049764ff9a7cf314d6e82e128e7226.json
@@ -0,0 +1 @@
+{"root_material": "As4S4", "path_str": "As4S4 --[Uv+Oxidant]--> p-As4S4 --[Uv+Oxidant]--> As2O3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThis means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).\n\n[1] Evidence classification: edge 1: direct\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As4S5) and arsenolite (As2O3) are obtained (step 1).\n\n[1] Evidence classification: edge 1: direct\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.\n\n[1] Evidence classification: edge 1: direct\nFigure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).\n\n[1] Evidence classification: edge 1: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\n\n[1] Evidence classification: edge 1: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).\n\n[2] Evidence classification: edge 2: direct, pathway endpoints As4S4 -> As2O3: direct\nThe highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "ref_list": ["JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9.", "KEUNE K, MASS J, MEHTA A, et al. Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues [J/OL]. Heritage Science, 2016. DOI: 10.1186/s40494-016-0078-1."], "ref_snippets": [{"text": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As4S5) and arsenolite (As2O3) are obtained (step 1).\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.\nFigure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": 0.44365543127059937, "snippets": [{"text": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).", "score": 0.4943835735321045, "metadata": {"year": "2020", "journal": "ChemTexts", "chunk_index": 61, "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "doi": "10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As4S5) and arsenolite (As2O3) are obtained (step 1).", "score": 0.44497865438461304, "metadata": {"title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "journal": "ChemTexts", "chunk_index": 1, "doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "year": "2020", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As4S5) and arsenolite (As2O3) are obtained (step 1).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.", "score": 0.44365543127059937, "metadata": {"chunk_index": 2, "year": "2020", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "ingest_kind": "existing_chroma", "doi": "10.1007/s40828-019-0100-9", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Figure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).", "score": null, "metadata": {"chunk_index": 67, "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "ingest_kind": "existing_chroma", "year": "2020", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Figure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "score": null, "metadata": {"journal": "ChemTexts", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "year": "2020", "chunk_index": 73, "ingest_kind": "existing_chroma", "doi": "10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": null, "metadata": {"chunk_index": 75, "doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "year": "2020", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "score": null, "snippets": [{"text": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "score": null, "metadata": {"year": "2016", "title": "Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues", "source_file": "s40494-016-0078-1.pdf", "doi": "10.1186/s40494-016-0078-1", "journal": "Heritage Science", "source": "pdf_direct/s40494-016-0078-1", "ingest_kind": "pdf_direct", "chunk_index": 4, "authors": [{"family": "Keune", "given": "Katrien"}, {"family": "Mass", "given": "Jennifer"}, {"family": "Mehta", "given": "Apurva"}, {"family": "Church", "given": "Jonathan"}, {"family": "Meirer", "given": "Florian"}], "volume": "4", "issue": "1", "article_number": "10", "url": "https://doi.org/10.1186/s40494-016-0078-1"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "p-As4S4", "product": "As2O3", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "pararealgar", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "As4S4", "product": "As2O3", "condition": "Uv+Oxidant", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 3, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 7, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 179, "lexical_kept": 7, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/a15ff104c0567deaf364f12b0e3499aefc92c695.json b/rag_report_cache/a15ff104c0567deaf364f12b0e3499aefc92c695.json
new file mode 100644
index 0000000000000000000000000000000000000000..5f15f9a97e68b9fe5b425b10c5a4493d33051c3e
--- /dev/null
+++ b/rag_report_cache/a15ff104c0567deaf364f12b0e3499aefc92c695.json
@@ -0,0 +1 @@
+{"root_material": "As4S4", "path_str": "As4S4 --[Uv]--> As4S5", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9.", "snippet": "According to the studies performed by Bonazzi et al. [46] and Kyono et al. [49] the transition proceeds with a linear increase of the unit cell volume of about 10 A\\({}^{3}\\). The recent detailed diffraction studies by Bonazzi et al. [52; 53] of light-induced transformation of solid solutions of intermediate compositions between \\(\\beta\\)-As\\({}_{4}\\)S\\({}_{4}\\) and As\\({}_{8}\\)S\\({}_{9}\\) (the latter is known as the mineral alcarnite, composed of equal amounts of As\\({}_{4}\\)S\\({}_{4}\\) and As\\({}_{4}\\)S\\({}_{5}\\) cages) identified the intermediate \\(\\chi\\) phase as \\(\\beta\\)-As\\({}_{4}\\)S\\({}_{4}\\). Thereby it was suggested that the light-induced cell expansion of realgar is caused by formation of As\\({}_{4}\\)S\\({}_{5}\\) molecules [50; 54]. This has been recently evidenced for the case of photoirradiated \\(\\beta\\)-As\\({}_{5}\\)S\\({}_{4}\\) and its solid solutions by single-crystal XRD [53]. The product As\\({}_{4}\\)S\\({}_{5}\\) (uzonite) is insensitive to light [55], but in the lattice", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "As4S4", "product": "As4S5", "condition": "Uv", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "The recent detailed diffraction studies by Bonazzi et al. [52; 53] of light-induced transformation of solid solutions of intermediate compositions between beta-As4S4 and As8S9 (the latter is known as the mineral alcarnite, composed of equal amounts of As4S4 and As4S5 cages) identified the intermediate \\chi phase as beta-As4S4.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "beta-As4S4", "product_span": "As4S5", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization [J/OL]. Heritage Science, 2024. DOI: 10.1186/s40494-024-01350-x. (bibliographic metadata partially available)", "snippet": ", with a reference spectrum of pararealgar (RRUFF database ID: R150123). d Raman spectra taken in locations E–H of sample SK-A-199_R9/4, with a reference spectrum of pararealgar (RRUFF database ID: R150123) Page 8 of 20De Keyser et al. Heritage Science (2024) 12:237 presence of arsenic and sulfur in these particles. Two representative Raman spectra from the more yellow particles are shown in Fig. 3d, E–F. Similar to the yellow particles in The Night Watch, these particles can be identified as pararealgar. For the orange to red particles again we observe a similar Raman spectrum (two representative spectra shown in Fig. 3d, G-H), but with a broadening of the peaks between 300 and 400 cm−1 and a relative decrease of the Raman specific peak at 275 cm−1, indicative of the presence of semi-amorphous pararealgar. The painting by Willem Kalf is dated about 15 years after The Night Watch and both painters lived in Amsterdam. This seems to suggest that a variety of different arsenic sulfide pigments were available to artists working in Amsterdam at the time. The source of the arsenic sulfides and their presence in Amsterdam is further discussed in the discussion section. Radiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2]. Light-induced degradation can also take place due to irradiation by the Raman laser. Literature shows that this mainly takes place upon irradiation with green light (506.0–544.0 nm) [77]. On the", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "As4S4", "product": "As4S5", "condition": "Uv", "evidence_scope": "edge", "verdict": "unsupported", "score": 0.75, "window": "For the orange to red particles again we observe a similar Raman spectrum (two representative spectra shown in Fig. 3d, G-H), but with a broadening of the peaks between 300 and 400 cm−1 and a relative decrease of the Raman specific peak at 275 cm−1, indicative of the presence of semi-amorphous pararealgar. The painting by Willem Kalf is dated about 15 years after The Night Watch and both painters lived in Amsterdam. This seems to suggest that a variety of different arsenic sulfide pigments were available to artists working in Amsterdam at the time. The source of the arsenic sulfides and their presence in Amsterdam is further discussed in the discussion section. Radiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "alacranite", "relation_basis": "direction_unresolved", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_direction_unresolved"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 18, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 146, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/a1b7b7c73b2f410e9edf9c58795cd62d00ebaf22.json b/rag_report_cache/a1b7b7c73b2f410e9edf9c58795cd62d00ebaf22.json
new file mode 100644
index 0000000000000000000000000000000000000000..a90f5f100f4e6882ddf01d2ee4d35502208d4bb7
--- /dev/null
+++ b/rag_report_cache/a1b7b7c73b2f410e9edf9c58795cd62d00ebaf22.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[12000lux+0.85W/m2+50℃+90%RH]--> 2PbCO3·Pb(OH)2", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["ZHAO Y, WANG J, PAN A, et al. Degradation of red lead pigment in the oil painting during UV aging [J/OL]. Color Research & Application, 2019. DOI: 10.1002/col.22386."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:19. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "Page 19 of 25 Coccato et al. Herit Sci (2017) 5:12 of minium and orpiment [186]. Moreover, it seems that minium promotes the blackening of leadwhite, when the pigments are mixed [204]. Some cases of red lead light - ening are reported as well, and are related to the forma - tion of lead sulphates and/or carbonates, according to the atmospheric pollutants and to the initial amount of PbO in red lead [68, 93, 200, 237, 238], via the formation of plumbonacrite [228]. The black discolouration of red lead due to light expo - sure was initially attributed to the formation of black PbO 2, but this compound is not stable to light [1], and it was rarely positively identified [93, 120, 238], while mixed oxides are also hypothesized [59]. PbO 2 could be a metabolite of microorganisms such as fungi [217, 239]. The parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244]. The PbO formed by laser irra - diation can be re-oxidized to minium [142]. A role of Cl − ions is also hypothesized [93, 245].", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "Pb3O4", "product": "2PbCO3·Pb(OH)2", "condition": "12000lux+0.85W/m2+50℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "The parameters responsible for the blackening of minium are identified as light [5, 240, 243], including laser light (514 and 488 nm, [215]), the pigment’s composition, and climate. These parameters all contribute to yield a grey discolouration at first, and finally a chocolate brown one [240]. Red lead semiconductor properties are responsi - ble for the reduction of Pb(IV) to Pb(II), and the forma - tion of PbO; the presence of bicarbonate ions (HCO 3 −) promotes then the formation of hydrocerussite and/or cerussite [123, 218, 244].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "hydrocerussite", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "ZHAO Y, WANG J, PAN A, et al. Degradation of red lead pigment in the oil painting during UV aging [J/OL]. Color Research & Application, 2019. DOI: 10.1002/col.22386.", "snippet": "Figure 5: FE-SEM images of model paint samples A, before aging; B, UV aging for 10 days, C, 23 days, and D, 30 days. E, the magnified image of red area in D. F, the schematic diagram of hydrocerussite. FE-SEM, field emission scanning electron microscopy Figure 6: Schematic diagram of minium degradation mechanism under UV light accelerating the discoloration of minium pigment, and finally forming hydrocerussite. ### The elucidated degradation mechanism of red lead", "retrieval_origin": "crn_provenance", "match": {"edge_index": 1, "reactant": "Pb3O4", "product": "2PbCO3·Pb(OH)2", "condition": "12000lux+0.85W/m2+50℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "FE-SEM, field emission scanning electron microscopy Figure 6: Schematic diagram of minium degradation mechanism under UV light accelerating the discoloration of minium pigment, and finally forming hydrocerussite.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "minium", "product_span": "hydrocerussite", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "VAGNINI M, VIVANI R, SGAMELLOTTI A, et al. Blackening of lead white: Study of model paintings [J/OL]. Journal of Raman Spectroscopy, 2020. DOI: 10.1002/jrs.5879.", "snippet": "(\\(\\beta\\)-PbO\\({}_{2}\\)), although the causes and the mechanism of this transformation still remain unknown.[10, 11, 12, 13] Some tests have been carried out to understand this phenomenon by monitoring the effect of some selected salts, comparing those naturally occurring (sulphates, nitrates and carbonates) with the synthetic ones (sodium, ammonium and potassium bicarbonate) that have often been used for mulant painting cleaning and conservation purposes.[14] In such experiments, lead white, cerussite (Pb (CO\\({}_{3}\\))), mascitor (\\(\\alpha\\)-PbO) and red lead (minimum, Pb\\({}_{3}\\)O\\({}_{4}\\)) were suspended with different salt solutions and left reacting for several months. No oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H\\({}_{2}\\)O\\({}_{2}\\). Lead white blackens very quickly only in the presence of NaClO,", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "Pb3O4", "product": "2PbCO3·Pb(OH)2", "condition": "12000lux+0.85W/m2+50℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "No oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "lead white", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 60, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 200, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
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+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Moisture]--> CuCO3·Cu(OH)2 --[Biogenic+Chloride]--> Cu2Cl(OH)3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nThe alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).\n\n[2] Evidence classification: edge 1: direct\nBlack colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.\n\n[2] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].\n\n[3] Evidence classification: edge 2: direct, pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nMinerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\n\n[3] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nCavallo, Alteration of azurite into paratacamite at the St.\n\n[4] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nSeveral authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.\n\n[5] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nBesides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.\n\n[6] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).\n\n[6] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.\n\n[7] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAzurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].\n\n[8] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nHowever, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].\n\n[9] Evidence classification: pathway endpoints 2CuCO3·Cu(OH)2 -> Cu2Cl(OH)3: direct\nAlteration of azurite into paratacamite at the St.", "ref_list": ["MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1.", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001.", "VAGNINI M, VIVANI R, VISCUSO E, et al. Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi [J/OL]. Vibrational Spectroscopy, 2018. DOI: 10.1016/j.vibspec.2018.07.006.", "LLUVERAS A, BOULARAND S, ANDREOTTI A, et al. Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR [J/OL]. Applied Physics A, 2010. DOI: 10.1007/s00339-010-5673-5.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:15. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:22. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)"], "ref_snippets": [{"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": 0.45361262559890747, "snippets": [{"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": 0.45361262559890747, "metadata": {"ingest_kind": "pdf_reextract", "year": "2008", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "journal": "Journal of Raman Spectroscopy", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "chunk_index": 2, "title": "Raman spectroscopic analysis of azurite blackening", "doi": "10.1002/jrs.1845"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "clinoatacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.\nAlso, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "score": 0.4220160245895386, "snippets": [{"text": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "score": 0.4220160245895386, "metadata": {"year": "2020", "ingest_kind": "pdf_direct", "chunk_index": 7, "journal": "Minerals", "doi": "10.3390/min10050424", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "source": "pdf_direct/min10050424_part2.pdf"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCO3·Cu(OH)2", "condition": "Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "malachite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "score": null, "metadata": {"title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "doi": "10.3390/min10050424", "ingest_kind": "pdf_direct", "journal": "Minerals", "year": "2020", "chunk_index": 5, "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "source": "pdf_direct/min10050424_part2.pdf"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Also, the exposure of historical azurite tempera paints to chloride-rich water (like those of rivers or sea floods) can lead to precipitation of green paratacamite ((Cu 2+)3(Cu,Zn)(OH)6Cl2) [33].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\nCavallo, Alteration of azurite into paratacamite at the St.", "score": null, "snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "metadata": {"source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "license": "https://creativecommons.org/licenses/by/4.0", "chunk_index": 22, "doi": "10.1007/s00339-024-07954-1", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "journal": "Applied Physics A", "ingest_kind": "pdf_fulltext", "page": 11, "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "year": "2024", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "authors": [{"family": "Purdy", "given": "Ellen H."}, {"family": "Critchley", "given": "Sarah"}, {"family": "Holé", "given": "Clément"}, {"family": "Cotte", "given": "Marine"}, {"family": "Kirkham", "given": "Andrea"}, {"family": "Casford", "given": "Michael"}], "volume": "130", "issue": "11", "article_number": "817", "url": "https://doi.org/10.1007/s00339-024-07954-1"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Biogenic+Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Cavallo, Alteration of azurite into paratacamite at the St.", "score": null, "metadata": {"year": "2024", "doi": "10.1007/s00339-024-07954-1", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "ingest_kind": "pdf_fulltext", "journal": "Applied Physics A", "chunk_index": 43, "source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "page": 19, "license": "https://creativecommons.org/licenses/by/4.0", "authors": [{"family": "Purdy", "given": "Ellen H."}, {"family": "Critchley", "given": "Sarah"}, {"family": "Holé", "given": "Clément"}, {"family": "Cotte", "given": "Marine"}, {"family": "Kirkham", "given": "Andrea"}, {"family": "Casford", "given": "Michael"}], "volume": "130", "issue": "11", "article_number": "817", "url": "https://doi.org/10.1007/s00339-024-07954-1"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Cavallo, Alteration of azurite into paratacamite at the St.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": null, "snippets": [{"text": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "score": null, "metadata": {"ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "title": "Degradation of lead-based pigments by salt solutions", "journal": "Journal of Cultural Heritage", "year": "2009", "source_file": "Degradation of lead-based pigments by salt solutions.md", "doi": "10.1016/j.culher.2008.11.001", "chunk_index": 0}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Several authors [5, 6, 7] have reported on the alteration of the blue pigment azurite to green atacamite due to its reaction with NaCl solution; such a colour change profoundly distorts the character and artistic impression of the art work.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": null, "snippets": [{"text": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "score": null, "metadata": {"ingest_kind": "existing_chroma", "source_file": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "doi": "10.1016/j.vibspec.2018.07.006", "source": "markdown_output/Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "title": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi", "journal": "Vibrational Spectroscopy", "year": "2018", "chunk_index": 38}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Besides, it emerges clearly that the painting has been heavily contaminated by one or more chlorine compounds; in fact, not only the degradation of azurite to basic copper chlorides (namely, the two polymorph forms atacamite and clinonatacamite), but also the partial alteration of hematite to iron oxide chloride has been found. All these findings suggest an interesting hypothesis that deserves to be deepened: a chlorine compound could have played a role in the degradation of the Cimabue's paintings examined in this work as it has been recently observed for cinnabar [2, 40] and for the alteration of azurite [41, 42] in panel paintings.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).\nAzurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "score": null, "snippets": [{"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).", "score": null, "metadata": {"source": "markdown_output/Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "year": "2010", "ingest_kind": "existing_chroma", "title": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR", "journal": "Applied Physics A", "doi": "10.1007/s00339-010-5673-5", "source_file": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "chunk_index": 4}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "score": null, "metadata": {"year": "2010", "doi": "10.1007/s00339-010-5673-5", "title": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR", "journal": "Applied Physics A", "source_file": "Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "ingest_kind": "existing_chroma", "source": "markdown_output/Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR.md", "chunk_index": 6}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite, although being stable to light and atmosphere, presents frequent chromatic alterations to greenish tonalities due to transformation into paratacamite and atacamite (Cu2Cl(OH)3) [2, 3, 8, 9] and also malachite (CuCO3\\cdotCu(OH)2) [1], not yet completely understood. Samples analyzed come from a gypsum shield on top of a door in the Monastery of Santos Creus (Catalonia, Spain) dating from the 1605 AD. The shield is depicted mainly in blue and brown in order to underline the relieves with the monastery insignias. In the blue areas, green shades could easily be identified (Fig. 1a). Synchrotron radiation X-ray diffraction and synchrotron IR microscopy have been used to produce maps of phases and high contrast chemical imaging.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": null, "snippets": [{"text": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "score": null, "metadata": {"journal": "Heritage Science", "year": "2017", "page": "13", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "ingest_kind": "pdf_fulltext", "source_file": "On the stability of mediaeval inorganic pigments - a review", "chunk_index": "38", "doi": "10.1186/s40494-017-0125-6", "source": "On the stability of mediaeval inorganic pigments - a review"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Azurite degrades to green compounds: mal - achite (CuCO 3·Cu(OH)2) and paratacamite/atacamite (Cu2Cl(OH)3) are some examples [28, 64, 111, 112, 115–118]. Humidity and chloride ions from various sources cause the formation of black copper oxides (CuO) and green chlorides (nantokite CuCl, para - tacamite/atacamite or botallackite Cu2Cl(OH)3 [ 103, 116, 118–121]). Azurite degrades to black tenorite CuO when exposed to heat in presence of alkali [20, 68, 91, 103, 113, 114, 121–123], while cold alkaline conditions might not affect it [111], or cause conver - sion to malachite [119], or the formation of tenorite via formation of copper hydroxide Cu(OH)2 [ 35, 64, 114]. On the other hand, it is decomposed by acids, such as oxalic acid to form oxalates (CuC 2O4·nH2O, mooloite) [32, 55, 116]. It has been reported that the combination of oxalic acid and chlorides in wall paintings results in Cu-hydroxychlorides Cu2Cl(OH)3 and Ca-oxalates [59]; and that no Cu-oxalates were observed in azurite paint layers [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "score": null, "snippets": [{"text": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "score": null, "metadata": {"chunk_index": "49", "year": "2017", "source_file": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "15", "ingest_kind": "pdf_fulltext", "doi": "10.1186/s40494-017-0125-6", "source": "On the stability of mediaeval inorganic pigments - a review"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "However, an interesting example is reported in literature: after the 1966 flood in Florence, green paratacamite was formed on azurite-containing wall paintings [115].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Alteration of azurite into paratacamite at the St.", "score": null, "snippets": [{"text": "Alteration of azurite into paratacamite at the St.", "score": null, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "chunk_index": "91", "doi": "10.1186/s40494-017-0125-6", "year": "2017", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "page": "22", "source_file": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Alteration of azurite into paratacamite at the St.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "paratacamite", "relation_basis": "observed_conversion", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 6, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 7, "lexical_scanned": 2314, "lexical_candidates": 302, "lexical_kept": 12, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/af029c12c4ed3ef7bc146362b20bc1fef52652d9.json b/rag_report_cache/af029c12c4ed3ef7bc146362b20bc1fef52652d9.json
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index 0000000000000000000000000000000000000000..64add16bc1130c8fc678f1fdffa095b6e58a087e
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@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[12000lux+1.5W/m2+60℃+90%RH]--> CuCO3·Cu(OH)2 --[Biogenic+Sulfate]--> Cu4SO4(OH)6 --[Biogenic+Sulfate]--> Cu3SO4(OH)4", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CRN source: In-house aging experiment"], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}], "related_context": [{"source": "CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w.", "snippet": "sively used during the 19th century with very adverse conse- quences to people’s health and wallpaper-manufacturing-industry workers. 13 Copper pigments are very sensitive to environmental pollutants. For example, brochantite (basic copper sulfate, Cu 4(SO4)(OH)6) was found by Raman spectroscopy in a wallpaper sample from the 19th century. This pigment was found together with antlerite (another copper sulfate, Cu 3(SO4)(OH)4). The pollution level in the area (SO x gases) where the sample was found seemed to be responsible for the degradation/transformation of the brochantite into antlerite. 14 Other degradations of copper pigments have been described in the literature, such as the decay suffered by malachite in the presence of chloride and humidity 15 or its degradation induced by a decayed calcite -gypsum mortar. 16 In this work, the degradation mechanism of green copper pigments due to the presence of microorganisms excreting oxalic acid is described. Chemical Systems Studied. The study was performed by analyzing Raman and X-ray fluorescence (XRF) spectra collected from different artworks with a variety of supports and pathologies. On the one hand, a map printed by the Blaeu family (Amsterdam, Holland) in the 17th century was taken into account. The map showed different green areas with different shades as well as an important degradation process of the cellulose due to the presence of green pigments (chemical system 1).", "retrieval_origin": "bge_m3", "match": {"edge_index": 3, "reactant": "Cu4SO4(OH)6", "product": "Cu3SO4(OH)4", "condition": "Biogenic+Sulfate", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "The pollution level in the area (SO x gases) where the sample was found seemed to be responsible for the degradation/transformation of the brochantite into antlerite. 14 Other degradations of copper pigments have been described in the literature, such as the decay suffered by malachite in the presence of chloride and humidity 15 or its degradation induced by a decayed calcite -gypsum mortar. 16 In this work, the degradation mechanism of green copper pigments due to the presence of microorganisms excreting oxalic acid is described.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "brochantite", "product_span": "antlerite", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:15. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "nce of degraded azurite [115]. Copper sulphates (brochantite, antlerite, langite, posnjakite: CuSO4·yCu(OH)2·zH2O, green) Green copper sulphates are commonly found as degra - dation products on copper artefacts exposed to polluted environments [105]. Brochantite was identified as a pig - ment as well [1], but it can transform into the more stable polymorphs, antlerite, langite or posnjakite, according to the given conditions of relative humidity, inorganic pol - lutants (SO x) and biological activity (affecting the pH and the type of acids) [127, 129, 168]. Posnjakite was also identified as a pigment [162, 169]. Brochantite, as well as posnjakite and antlerite are also intermediate reaction products between copper carbonates and copper oxa - lates, and are therefore sensitive to oxalic acid [127]. Arsenic (Z = 33) Geologically, orpiment (As 2S3) and realgar (As 4S4) occur together, and are often associated with antimonates and other sulphides [1, 30]. Orpiment and realgar were highly appreciated especially in Egypt and China for their rich yellow and red–orange shades [1, 170–174], even though the pigments were considered “unpleasant” by many art - ists, and not recommended to use in combination with copper and lead based pigments, such as verdigris and leadwhite [1, 30, 170]. Orpiment and realgar exist as minerals, as well as synthetic pigments [175], and of the two arsenic sulphide pigments, the first one is the most stable. Realgar, being unstable, was less often reported in works of art [1, 176–179]. It has a polymorphic pho - todegradation product, pararealgar As 4S4.", "retrieval_origin": "resolver", "match": {"edge_index": 3, "reactant": "Cu4SO4(OH)6", "product": "Cu3SO4(OH)4", "condition": "Biogenic+Sulfate", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "Brochantite was identified as a pig - ment as well [1], but it can transform into the more stable polymorphs, antlerite, langite or posnjakite, according to the given conditions of relative humidity, inorganic pol - lutants (SO x) and biological activity (affecting the pH and the type of acids) [127, 129, 168].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "brochantite", "product_span": "antlerite", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 29, "dense_candidates": 580, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 163, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 294, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/afa79ec4c5f4946b5ea360df40d35168863fe99d.json b/rag_report_cache/afa79ec4c5f4946b5ea360df40d35168863fe99d.json
new file mode 100644
index 0000000000000000000000000000000000000000..5641d247d947d050b4959f9f30ac18195548cc59
--- /dev/null
+++ b/rag_report_cache/afa79ec4c5f4946b5ea360df40d35168863fe99d.json
@@ -0,0 +1 @@
+{"root_material": "α-Fe2O3", "path_str": "α-Fe2O3 --[Sulfate]--> Fe2(SO4)3·9H2O", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["MAGUREGUI M, KNUUTINEN U, CASTRO K, et al. Raman spectroscopy as a tool to diagnose the impact and conservation state of Pompeian second and fourth style wall paintings exposed to diverse environments (House of Marcus Lucretius) [J/OL]. Journal of Raman Spectroscopy, 2010. DOI: 10.1002/jrs.2671."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "MAGUREGUI M, KNUUTINEN U, CASTRO K, et al. Raman spectroscopy as a tool to diagnose the impact and conservation state of Pompeian second and fourth style wall paintings exposed to diverse environments (House of Marcus Lucretius) [J/OL]. Journal of Raman Spectroscopy, 2010. DOI: 10.1002/jrs.2671.", "snippet": "In the red pigment of sample 16/59 (Room 16), white-reddish color grains around the red pigment hematite were identified. The same pattern was observed in the red pigment remains of the wall fragment W-2 from the same room (also fourth style). These white-reddish grains gave, together with the main Raman band of gypsum and those of hematite, an additional band at 1025 cm\\({}^{-1}\\), which was attributed to the iron(III) sulfate nonhydrate (Fe2(SO4)3: 9H2O) (see Fig. 1(A)). Among the minerals with this formula, two polymorphs can be found: cojunthite and paracoquimbite. Surprisingly, the Raman spectra of both polymorphs are very similar or almost identical. Taking into account that not all the Raman bands of the coquimbite or paracoquimbite are present in the acquired spectrum (only Raman bands at 1025, 605 and 495 cm\\({}^{-1}\\), the last two overlap some bands of hematite), it cannot be concluded whether the iron sulfate is coquimbite or paracoquimbite, but it can be affirmed that an", "retrieval_origin": "crn_provenance", "match": {"edge_index": 1, "reactant": "alpha-Fe2O3", "product": "Fe2(SO4)3·9H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "In the red pigment of sample 16/59 (Room 16), white-reddish color grains around the red pigment hematite were identified. The same pattern was observed in the red pigment remains of the wall fragment W-2 from the same room (also fourth style). These white-reddish grains gave, together with the main Raman band of gypsum and those of hematite, an additional band at 1025 cm{}^{-1}, which was attributed to the iron(III) sulfate nonhydrate (Fe2(SO4)3: 9H2O) (see Fig. 1(A)).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hematite", "product_span": "iron(iii) sulfate", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:11. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "he presence of tarry materials and other impurities [12]. As for the red and yellow ochres, burning produces a darker shade (burnt umber, burnt Sienna) [1]. Ochres are sta - ble to light, moisture, alkali, and dilute acids, and are inert in mixtures. Their stability to acids is testified upon oxalic acid exposure, which causes only the formation of Ca-oxalates, from the other components of the ochre [32, 67]. They are, however, sensitive to high temperatures, such as fires [12, 68], or local heating effects related to the use of lasers for cleaning [19, 69, 70] or for spectroscopi - cal analysis (i.e. Raman spectroscopy, [62, 63, 71, 72]). A UV (248 nm) laser showed darkening of yellow ochre and raw Sienna, as a result of dehydration, conversion to haematite and modification of the manganese phases present [69], but low fluences of the same laser caused little modification of this ochre [19]. High fluence of 355 and 633 nm laser, caused the conversion of yellow ochre to haematite [29, 72]. The effect of NIR laser irradiation (1064 nm) was as well investigated, showing significant discolouration of both yellow and red ochres when mixed with gypsum (no organic binder) [18], and an increase of haematite content after irradiation of ochres [70]. More - over, some issues are encountered on wall paintings. In fact, coquimbite/paracoquimbite Fe 2(SO4)3·9(H2O) were identified in Pompeii, together with magnetite Fe 3O4 and gypsum CaSO 4·2H2O, as a result of the degrada - tion of the fresco paint layer due to SO 2 pollution [73].", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "alpha-Fe2O3", "product": "Fe2(SO4)3·9H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "qualified", "score": 0.67, "window": "High fluence of 355 and 633 nm laser, caused the conversion of yellow ochre to haematite [29, 72]. The effect of NIR laser irradiation (1064 nm) was as well investigated, showing significant discolouration of both yellow and red ochres when mixed with gypsum (no organic binder) [18], and an increase of haematite content after irradiation of ochres [70]. More - over, some issues are encountered on wall paintings. In fact, coquimbite/paracoquimbite Fe2(SO4)3·9(H2O) were identified in Pompeii, together with magnetite Fe3O4 and gypsum CaSO 4·2H2O, as a result of the degrada - tion of the fresco paint layer due to SO 2 pollution [73].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "haematite", "product_span": "paracoquimbite", "relation_basis": "product_identification", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["relation_product_identification", "condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 6, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 61, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/b12af9f27c86dd5c10e0d73aaff7211c240c5784.json b/rag_report_cache/b12af9f27c86dd5c10e0d73aaff7211c240c5784.json
new file mode 100644
index 0000000000000000000000000000000000000000..7fd8ebf0684e5faad5f2569fe08789e3eaa591b0
--- /dev/null
+++ b/rag_report_cache/b12af9f27c86dd5c10e0d73aaff7211c240c5784.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Uv+Oxidant]--> HgSO4 --[Uv+Oxidant]--> Hg2SO4", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CHAPPÉ M, HILDENHAGEN J, DICKMANN K, et al. Laser irradiation of medieval pigments at IR, VIS and UV wavelengths [J/OL]. Journal of Cultural Heritage, 2003. DOI: 10.1016/s1296-2074(02)01206-2.", "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "snippet": "the intensity and type of radiation having a rate-determining influence. Besides, schuettetic has been found in cinnabar deposits exposed to natural sunlight in numerous locations, including Almaden (Spain), California and Nevada (USA), Bolivia, Moravia (Czech Republic), and Sonora (Mexico) [48]. According to Bailey et al. [19], this mineral forms through photooxidation of sunlight-exposed cinnabar in the presence of oxygen-bearing surface water. Importantly, the authors acknowledged that HgSO\\({}_{4}\\) might be an intermediate phase during schuettetic formation. In any case, sulfate formation is not limited to cinnabar deposits. Radeport et al. [2, 17] acknowledged the possible oxidation of mercury sulfide to sulfate upon cinnabar degradation in the case of a Gothic wall painting from the monastery of Pedralbes (Barcelona, Spain) and detected mercury sulfate in artificially aged cinnabar pellets.", "retrieval_origin": "crn_provenance", "match": {"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Oxidant", "evidence_scope": "edge", "verdict": "inferred", "score": 0.87, "window": "According to Bailey et al. [19], this mineral forms through photooxidation of sunlight-exposed cinnabar in the presence of oxygen-bearing surface water. Importantly, the authors acknowledged that HgSO4 might be an intermediate phase during schuettetic formation. In any case, sulfate formation is not limited to cinnabar deposits. Radeport et al. [2, 17] acknowledged the possible oxidation of mercury sulfide to sulfate upon cinnabar degradation in the case of a Gothic wall painting from the monastery of Pedralbes (Barcelona, Spain) and detected mercury sulfate in artificially aged cinnabar pellets.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "mercury sulfide", "product_span": "mercury sulfate", "relation_basis": "author_proposal", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_author_proposal"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 20, "dense_candidates": 400, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 15, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 203, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/b155ec1086feffc2d4a7fd998f3c36b805866ad3.json b/rag_report_cache/b155ec1086feffc2d4a7fd998f3c36b805866ad3.json
new file mode 100644
index 0000000000000000000000000000000000000000..704fe2cf1281c03db100ea91591ee85310255542
--- /dev/null
+++ b/rag_report_cache/b155ec1086feffc2d4a7fd998f3c36b805866ad3.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[12000lux+1.5W/m2+60℃+90%RH]--> CuCO3·Cu(OH)2 --[Biogenic+Sulfate]--> Cu4SO4(OH)6", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CRN source: In-house aging experiment"], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}], "related_context": [{"source": "The Use of X-Ray Photoelectron Spectroscopy in Studying Azurite and Malachite as Minerals, Pigments and in Secondary Products on Copper Objects [J/OL]. JOJ Material Science, 2026:9. DOI: 10.19080/jojms.2026.10.555788. (bibliographic metadata partially available)", "snippet": "e changes in binding energies during the degradation process Figure 3. During the initial corrosion process, metallic copper (Cu0) is converted to Cu2O (cuprite). The Cu 2p core level spectrum is characterized by binding energies around 932.5eV [45]. The XPS analysis on copper surfaces exposed for long durations in different atmospheric conditions showed that during the initial stages, cuprite is the dominant corrosion product, where copper in Cu2O has a lower binding energy compared to Cu (II). When copper is exposed to the atmosphere for long durations, the corrosion products gradually change due to the presence of sulfur dioxide in the atmosphere. During this period, copper is converted from Cu2O to brochantite (Cu4SO4(OH)6·2H2O). The Cu (II) in brochantite is characterized by binding energies ranging from 934-935eV, showing an increase in the copper oxidation state, similar to the binding energies in the azurite and malachite minerals, as discussed in the literature by Kloprogge & Wood [40]. A particularly illustrative case of the evolution of binding energies during the process of corrosion can be exemplified by the depth profiling of multi-layered systems of patina. In the urban atmospheric environment with mixed acid rain-induced acceleration of the corrosion process, the top layer of the patina contains Cu (II)-based compounds such as sulfates, oxides, and hydroxy oxides. In the interfacial region of the corrosion product layer and the underlying Cu metal, Cu 2O is found to be favored.", "retrieval_origin": "bge_m3", "match": {"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu4SO4(OH)6", "condition": "", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "During this period, copper is converted from Cu2O to brochantite (Cu4SO4(OH)6·2H2O). The Cu (II) in brochantite is characterized by binding energies ranging from 934-935eV, showing an increase in the copper oxidation state, similar to the binding energies in the azurite and malachite minerals, as discussed in the literature by Kloprogge & Wood [40].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "brochantite", "relation_basis": "product_identification", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w.", "snippet": "Unfortunately no other bands could be obtained from the green area. As in the previous cases, these sculptures seem to have suffered a biological attack, as the presence of calcium oxalate suggests. Unfortunately, the raw green pigment was completely decayed (it was quantitatively transformed into moolooite) and it was not possible to identify it. Thermodynamic Modeling, Degradation Mechanisms, and Reactions. According to the experimental data obtained, it is possible to propose several degradation routes (mecha- nisms) for copper green pigments, such as malachite (Cu 2- CO3(OH)2) to moolooite (CuC 2O4·nH2O), passing through copper hydroxysulphates posnjakite (Cu 4SO4(OH)6·H2O), bro - chantite (Cu 4SO4(OH)6), antlerite (Cu 3SO4(OH)4), etc., and/ or copper hydroxychlorides atacamite (Cu 2Cl(OH) 3), parata - camite (Cu 2Cl(OH) 3), etc., depending on the chemical condi- tions. In order to assess the degradation pathways and confirm the thermodynamic stability of all the solid phases identified from the experimental data obtained, we have performed a chemical reaction simulation using the MEDUSA software. This modeling Figure 3. Chemical simulation by MEDUSA software of a micro- biological attack (continuous increasing of oxalic acid concentration) over malachite in the presence of high levels of sulfate. Malachite (Cu 2CO3(OH)2), atacamite (CuCl 2·3Cu(OH)2), brochantite (Cu 4SO4- (OH)6), and antlerite (Cu 3SO4(OH)4) are the solids appearing as predominant species. Figure 4.", "retrieval_origin": "bge_m3", "match": {"edge_index": 2, "reactant": "CuCO3·Cu(OH)2", "product": "Cu4SO4(OH)6", "condition": "Biogenic+Sulfate", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "According to the experimental data obtained, it is possible to propose several degradation routes (mecha- nisms) for copper green pigments, such as malachite (Cu 2- CO3(OH)2) to moolooite (CuC 2O4·nH2O), passing through copper hydroxysulphates posnjakite (Cu4SO4(OH)6·H2O), bro - chantite (Cu4SO4(OH)6), antlerite (Cu3SO4(OH)4), etc., and/ or copper hydroxychlorides atacamite (Cu2Cl(OH)3), parata - camite (Cu2Cl(OH)3), etc., depending on the chemical condi- tions. In order to assess the degradation pathways and confirm the thermodynamic stability of all the solid phases identified from the experimental data obtained, we have performed a chemical reaction simulation using the MEDUSA software. This modeling Figure 3. Chemical simulation by MEDUSA software of a micro- biological attack (continuous increasing of oxalic acid concentration) over malachite in the presence of high levels of sulfate. Malachite (Cu2CO3(OH)2), atacamite (CuCl 2·3Cu(OH)2), brochantite (Cu4SO4- (OH)6), and antlerite (Cu3SO4(OH)4) are the solids appearing as predominant species.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "copper green", "product_span": "brochantite", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:15. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "nce of degraded azurite [115]. Copper sulphates (brochantite, antlerite, langite, posnjakite: CuSO4·yCu(OH)2·zH2O, green) Green copper sulphates are commonly found as degra - dation products on copper artefacts exposed to polluted environments [105]. Brochantite was identified as a pig - ment as well [1], but it can transform into the more stable polymorphs, antlerite, langite or posnjakite, according to the given conditions of relative humidity, inorganic pol - lutants (SO x) and biological activity (affecting the pH and the type of acids) [127, 129, 168]. Posnjakite was also identified as a pigment [162, 169]. Brochantite, as well as posnjakite and antlerite are also intermediate reaction products between copper carbonates and copper oxa - lates, and are therefore sensitive to oxalic acid [127]. Arsenic (Z = 33) Geologically, orpiment (As 2S3) and realgar (As 4S4) occur together, and are often associated with antimonates and other sulphides [1, 30]. Orpiment and realgar were highly appreciated especially in Egypt and China for their rich yellow and red–orange shades [1, 170–174], even though the pigments were considered “unpleasant” by many art - ists, and not recommended to use in combination with copper and lead based pigments, such as verdigris and leadwhite [1, 30, 170]. Orpiment and realgar exist as minerals, as well as synthetic pigments [175], and of the two arsenic sulphide pigments, the first one is the most stable. Realgar, being unstable, was less often reported in works of art [1, 176–179]. It has a polymorphic pho - todegradation product, pararealgar As 4S4.", "retrieval_origin": "lexical", "match": {"edge_index": 0, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu4SO4(OH)6", "condition": "", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "nce of degraded azurite [115]. Copper sulphates (brochantite, antlerite, langite, posnjakite: CuSO4·yCu(OH)2·zH2O, green) Green copper sulphates are commonly found as degra - dation products on copper artefacts exposed to polluted environments [105]. Brochantite was identified as a pig - ment as well [1], but it can transform into the more stable polymorphs, antlerite, langite or posnjakite, according to the given conditions of relative humidity, inorganic pol - lutants (SO x) and biological activity (affecting the pH and the type of acids) [127, 129, 168].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "brochantite", "relation_basis": "product_identification", "condition_status": "not_applicable", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 159, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 292, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/b2ebad8a53fcfd0c1ce350cf32b92f3fff246748.json b/rag_report_cache/b2ebad8a53fcfd0c1ce350cf32b92f3fff246748.json
new file mode 100644
index 0000000000000000000000000000000000000000..1805d2a04f311b4a35c0e89bb8c3865b6fb091ad
--- /dev/null
+++ b/rag_report_cache/b2ebad8a53fcfd0c1ce350cf32b92f3fff246748.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Chloride]--> Hg --[Chloride]--> HgCl2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 2: direct\nunder normal light into HgCl2 and Hg(0).[23] The metallic mercury, derived from the photoreuction in the first step, the corderoite, and the (HgCl)2, react with chloride to form mercuric chloride HgCl2.\n\n[1] Evidence classification: edge 1: direct\nThe residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.\n\n[1] Evidence classification: edge 2: direct\nIn vitro, HgCl2 can be formed from metallic mercury via the reaction with chlorine gas or by the formation of mercury(II) sulfate.[24] The white end product is found around the black product, which means that external sources, light, and a higher concentration of chloride are necessary to create the white product. Figure 7 illustrates the scheme of the proposed mechanisms of the degradation process of the red vermilion into the black and subsequently the white reaction product. The scheme describes the degradation phenomena qualitatively to clarify the process. The products observed in the paint cross sections are mixed phases and consequently cannot be classified in a single category in the scheme. For example, the black product in sample MH251/26 has a relatively higher concentration of chloride compared to the intact red vermillion.\n\n[2] Evidence classification: edge 1: direct\nAdditionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "ref_list": ["KEUNE K, BOON JJ. Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings [J/OL]. Analytical Chemistry, 2005. DOI: 10.1021/ac048158f.", "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2."], "ref_snippets": [{"text": "under normal light into HgCl2 and Hg(0).[23] The metallic mercury, derived from the photoreuction in the first step, the corderoite, and the (HgCl)2, react with chloride to form mercuric chloride HgCl2.\nThe residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.\nIn vitro, HgCl2 can be formed from metallic mercury via the reaction with chlorine gas or by the formation of mercury(II) sulfate.[24] The white end product is found around the black product, which means that external sources, light, and a higher concentration of chloride are necessary to create the white product. Figure 7 illustrates the scheme of the proposed mechanisms of the degradation process of the red vermilion into the black and subsequently the white reaction product. The scheme describes the degradation phenomena qualitatively to clarify the process. The products observed in the paint cross sections are mixed phases and consequently cannot be classified in a single category in the scheme. For example, the black product in sample MH251/26 has a relatively higher concentration of chloride compared to the intact red vermillion.", "score": 0.43797171115875244, "snippets": [{"text": "under normal light into HgCl2 and Hg(0).[23] The metallic mercury, derived from the photoreuction in the first step, the corderoite, and the (HgCl)2, react with chloride to form mercuric chloride HgCl2.", "score": 0.43797171115875244, "metadata": {"source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "journal": "Analytical Chemistry", "chunk_index": 46, "doi": "10.1021/ac048158f", "year": "2005", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "ingest_kind": "existing_chroma", "authors": [{"family": "Keune", "given": "Katrien"}, {"family": "Boon", "given": "Jaap J."}], "volume": "77", "issue": "15", "pages": "4742-4750", "url": "https://doi.org/10.1021/ac048158f"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "Hg", "product": "HgCl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "under normal light into HgCl2 and Hg(0).[23] The metallic mercury, derived from the photoreuction in the first step, the corderoite, and the (HgCl)2, react with chloride to form mercuric chloride HgCl2.", "reactant_match": "exact", "product_match": "alias", "reactant_span": "Hg", "product_span": "mercuric chloride", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.49005985260009766, "metadata": {"source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "year": "2005", "journal": "Analytical Chemistry", "ingest_kind": "existing_chroma", "source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "doi": "10.1021/ac048158f", "chunk_index": 44, "authors": [{"family": "Keune", "given": "Katrien"}, {"family": "Boon", "given": "Jaap J."}], "volume": "77", "issue": "15", "pages": "4742-4750", "url": "https://doi.org/10.1021/ac048158f"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "Hg", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "In vitro, HgCl2 can be formed from metallic mercury via the reaction with chlorine gas or by the formation of mercury(II) sulfate.[24] The white end product is found around the black product, which means that external sources, light, and a higher concentration of chloride are necessary to create the white product. Figure 7 illustrates the scheme of the proposed mechanisms of the degradation process of the red vermilion into the black and subsequently the white reaction product. The scheme describes the degradation phenomena qualitatively to clarify the process. The products observed in the paint cross sections are mixed phases and consequently cannot be classified in a single category in the scheme. For example, the black product in sample MH251/26 has a relatively higher concentration of chloride compared to the intact red vermillion.", "score": null, "metadata": {"title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "doi": "10.1021/ac048158f", "source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "year": "2005", "chunk_index": 47, "journal": "Analytical Chemistry", "ingest_kind": "existing_chroma", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "authors": [{"family": "Keune", "given": "Katrien"}, {"family": "Boon", "given": "Jaap J."}], "volume": "77", "issue": "15", "pages": "4742-4750", "url": "https://doi.org/10.1021/ac048158f"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "Hg", "product": "HgCl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "In vitro, HgCl2 can be formed from metallic mercury via the reaction with chlorine gas or by the formation of mercury(II) sulfate.[24] The white end product is found around the black product, which means that external sources, light, and a higher concentration of chloride are necessary to create the white product. Figure 7 illustrates the scheme of the proposed mechanisms of the degradation process of the red vermilion into the black and subsequently the white reaction product. The scheme describes the degradation phenomena qualitatively to clarify the process. The products observed in the paint cross sections are mixed phases and consequently cannot be classified in a single category in the scheme. For example, the black product in sample MH251/26 has a relatively higher concentration of chloride compared to the intact red vermillion.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "metallic mercury", "product_span": "HgCl2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": 0.4224860668182373, "snippets": [{"text": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": 0.4224860668182373, "metadata": {"ingest_kind": "existing_chroma", "year": "2021", "journal": "Communications Chemistry", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "doi": "10.1038/s42004-021-00610-2", "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "chunk_index": 4, "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "Hg", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 16, "dense_candidates": 320, "dense_kept": 3, "resolver_scanned": 2314, "resolver_candidates": 114, "resolver_kept": 3, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 3, "lexical_scanned": 2314, "lexical_candidates": 231, "lexical_kept": 4, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/b4687d8953290d95dbed3194de640af5b551c617.json b/rag_report_cache/b4687d8953290d95dbed3194de640af5b551c617.json
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@@ -0,0 +1 @@
+{"root_material": "As2S3", "path_str": "As2S3 --[Uv]--> As2O3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThe orpiment in paint directly exposed to light showed the formation of arsenolite.\n\n[1] Evidence classification: edge 1: direct\nWe therefore conclude that, in agreement with previous literature, the formation of arsenolite from orpiment is a light-induced degradation process. The light-aged orpiment (RH 95%) was also studied using tomographic full field TXM at SSRL beamline 6-2c to study the light degradation on the nanoscale. Figure 4a shows the 3D reconstruction of the entire field of view recorded at 12,000 eV, that is, at an energy ca. 100 eV above the As-K edge. In the middle left and at the top of the reconstruction in Figure 4a, cubic arsenolite crystals can be recognized. These crystals were also observed with SEM, by monitoring the same area of orpiment before and after aging.\n\n[1] Evidence classification: edge 1: direct\nLooking back at Figure 2, this means that the transformation of orpiment in the presence of a medium either follows reaction steps B, E, and F (dissolution and oxidation followed by precipitation) or A, C, E, and F (formation of arsenolite, dissolution, and oxidation, followed by precipitation). The former can take place in either dark or light conditions, and the latter can only take place in the presence of light.\n\n[1] Evidence classification: edge 1: direct\n• If the orpiment is in a “dry” environment and exposed to light, the formation of arsenolite crystals was observed.\n\n[2] Evidence classification: edge 1: direct\nOrpiment degradation can occur upon exposure to light, which causes the formation of arsenic trioxide [66].\n\n[2] Evidence classification: edge 1: direct\nArsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.\n\n[3] Evidence classification: edge 1: direct\nLight exposure causes discolouration [30, 128, 182, 185, 186]. Orpiment darkens upon heating, it burns in air producing white arsenolite (As2O3) and volatile SO2, and it decomposes in water (the artificial product having smaller particles, dis - solves faster).", "ref_list": ["BROERS FTH, JANSSENS K, WEKER JN, et al. Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings [J/OL]. Journal of the American Chemical Society, 2023. DOI: 10.1021/jacs.2c12271.", "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization [J/OL]. Heritage Science, 2024. DOI: 10.1186/s40494-024-01350-x. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:16. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)"], "ref_snippets": [{"text": "The orpiment in paint directly exposed to light showed the formation of arsenolite.\nWe therefore conclude that, in agreement with previous literature, the formation of arsenolite from orpiment is a light-induced degradation process. The light-aged orpiment (RH 95%) was also studied using tomographic full field TXM at SSRL beamline 6-2c to study the light degradation on the nanoscale. Figure 4a shows the 3D reconstruction of the entire field of view recorded at 12,000 eV, that is, at an energy ca. 100 eV above the As-K edge. In the middle left and at the top of the reconstruction in Figure 4a, cubic arsenolite crystals can be recognized. These crystals were also observed with SEM, by monitoring the same area of orpiment before and after aging.\nLooking back at Figure 2, this means that the transformation of orpiment in the presence of a medium either follows reaction steps B, E, and F (dissolution and oxidation followed by precipitation) or A, C, E, and F (formation of arsenolite, dissolution, and oxidation, followed by precipitation). The former can take place in either dark or light conditions, and the latter can only take place in the presence of light.\n• If the orpiment is in a “dry” environment and exposed to light, the formation of arsenolite crystals was observed.", "score": 0.4410678744316101, "snippets": [{"text": "The orpiment in paint directly exposed to light showed the formation of arsenolite.", "score": 0.47296810150146484, "metadata": {"source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "page": 11, "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "ingest_kind": "pdf_fulltext", "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "chunk_index": 28, "journal": "Journal of the American Chemical Society", "doi": "10.1021/jacs.2c12271", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "license": "https://creativecommons.org/licenses/by/4.0/", "year": "2023", "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The orpiment in paint directly exposed to light showed the formation of arsenolite.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "We therefore conclude that, in agreement with previous literature, the formation of arsenolite from orpiment is a light-induced degradation process. The light-aged orpiment (RH 95%) was also studied using tomographic full field TXM at SSRL beamline 6-2c to study the light degradation on the nanoscale. Figure 4a shows the 3D reconstruction of the entire field of view recorded at 12,000 eV, that is, at an energy ca. 100 eV above the As-K edge. In the middle left and at the top of the reconstruction in Figure 4a, cubic arsenolite crystals can be recognized. These crystals were also observed with SEM, by monitoring the same area of orpiment before and after aging.", "score": 0.4410678744316101, "metadata": {"license": "https://creativecommons.org/licenses/by/4.0/", "doi": "10.1021/jacs.2c12271", "page": 4, "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "year": "2023", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "chunk_index": 8, "journal": "Journal of the American Chemical Society", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "ingest_kind": "pdf_fulltext", "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "We therefore conclude that, in agreement with previous literature, the formation of arsenolite from orpiment is a light-induced degradation process. The light-aged orpiment (RH 95%) was also studied using tomographic full field TXM at SSRL beamline 6-2c to study the light degradation on the nanoscale. Figure 4a shows the 3D reconstruction of the entire field of view recorded at 12,000 eV, that is, at an energy ca. 100 eV above the As-K edge. In the middle left and at the top of the reconstruction in Figure 4a, cubic arsenolite crystals can be recognized. These crystals were also observed with SEM, by monitoring the same area of orpiment before and after aging.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Looking back at Figure 2, this means that the transformation of orpiment in the presence of a medium either follows reaction steps B, E, and F (dissolution and oxidation followed by precipitation) or A, C, E, and F (formation of arsenolite, dissolution, and oxidation, followed by precipitation). The former can take place in either dark or light conditions, and the latter can only take place in the presence of light.", "score": 0.44244587421417236, "metadata": {"title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "year": "2023", "ingest_kind": "pdf_fulltext", "page": 12, "chunk_index": 30, "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "doi": "10.1021/jacs.2c12271", "journal": "Journal of the American Chemical Society", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "license": "https://creativecommons.org/licenses/by/4.0/", "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Looking back at Figure 2, this means that the transformation of orpiment in the presence of a medium either follows reaction steps B, E, and F (dissolution and oxidation followed by precipitation) or A, C, E, and F (formation of arsenolite, dissolution, and oxidation, followed by precipitation). The former can take place in either dark or light conditions, and the latter can only take place in the presence of light.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "• If the orpiment is in a “dry” environment and exposed to light, the formation of arsenolite crystals was observed.", "score": 0.45754724740982056, "metadata": {"doi": "10.1021/jacs.2c12271", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings", "chunk_index": 26, "page": 11, "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "ingest_kind": "pdf_fulltext", "journal": "Journal of the American Chemical Society", "year": "2023", "license": "https://creativecommons.org/licenses/by/4.0/", "authors": [{"family": "Broers", "given": "Fréderique T. H."}, {"family": "Janssens", "given": "Koen"}, {"family": "Nelson Weker", "given": "Johanna"}, {"family": "Webb", "given": "Samuel M."}, {"family": "Mehta", "given": "Apurva"}, {"family": "Meirer", "given": "Florian"}, {"family": "Keune", "given": "Katrien"}], "volume": "145", "issue": "16", "pages": "8847-8859", "url": "https://doi.org/10.1021/jacs.2c12271"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "• If the orpiment is in a “dry” environment and exposed to light, the formation of arsenolite crystals was observed.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Orpiment degradation can occur upon exposure to light, which causes the formation of arsenic trioxide [66].\nArsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.", "score": null, "snippets": [{"text": "Orpiment degradation can occur upon exposure to light, which causes the formation of arsenic trioxide [66].", "score": null, "metadata": {"chunk_index": 7, "journal": "Heritage Science", "source_file": "s40494-024-01350-x.pdf", "ingest_kind": "pdf_direct", "doi": "10.1186/s40494-024-01350-x", "source": "pdf_direct/s40494-024-01350-x", "year": "2024", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Orpiment degradation can occur upon exposure to light, which causes the formation of arsenic trioxide [66].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "arsenic trioxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Arsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.", "score": null, "metadata": {"title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization", "source_file": "s40494-024-01350-x.pdf", "year": "2024", "journal": "Heritage Science", "ingest_kind": "pdf_direct", "doi": "10.1186/s40494-024-01350-x", "chunk_index": 22, "source": "pdf_direct/s40494-024-01350-x"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Arsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Light exposure causes discolouration [30, 128, 182, 185, 186]. Orpiment darkens upon heating, it burns in air producing white arsenolite (As2O3) and volatile SO2, and it decomposes in water (the artificial product having smaller particles, dis - solves faster).", "score": null, "snippets": [{"text": "Light exposure causes discolouration [30, 128, 182, 185, 186]. Orpiment darkens upon heating, it burns in air producing white arsenolite (As2O3) and volatile SO2, and it decomposes in water (the artificial product having smaller particles, dis - solves faster).", "score": null, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "page": "16", "ingest_kind": "pdf_fulltext", "chunk_index": "53", "source_file": "On the stability of mediaeval inorganic pigments - a review", "doi": "10.1186/s40494-017-0125-6", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "journal": "Heritage Science"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As2S3", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Light exposure causes discolouration [30, 128, 182, 185, 186]. Orpiment darkens upon heating, it burns in air producing white arsenolite (As2O3) and volatile SO2, and it decomposes in water (the artificial product having smaller particles, dis - solves faster).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "orpiment", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 4, "resolver_scanned": 2314, "resolver_candidates": 44, "resolver_kept": 7, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 117, "lexical_kept": 7, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/bc9ac8dcb6bc6c825c5001b44c37c64c7ca409c7.json b/rag_report_cache/bc9ac8dcb6bc6c825c5001b44c37c64c7ca409c7.json
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index 0000000000000000000000000000000000000000..1d4a4713b4790ef8f74d68c599a8d0ff748037d3
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@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Sulfate]--> 2CuSO4·Cu(OH)2·4H2O", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O. size and the type and amount of binder present in the paints, as all these factors influenced the color of the paint and the roughness of its surface [19–22]. Other recent research has reported that the impurities found in the historic mineral pigments used in tempera paints might significantly alter their optical, chem ical, and physical properties [22–24].\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Azurite, Quartz, Malachite. Phases identified after SO2 exposure: Azurite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O.\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite.\n\n[1] Evidence classification: edge 1: direct\nThe SO 2 aged rabbit glue-based mock-ups showed microscopically important crack formation and binder loss and fewer sulfated salts precipitated on the surface of the paints. Keywords: tempera paint; azurite; malachite; artificial aging; Sulfur dioxide; cultural heritage XRD phase comparison for AZ-C. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O.\n\n[1] Evidence classification: edge 1: direct\nDespite the fact that the concentration of SO 2 gas in the atmosphere has been reduced in some regions Minerals 2020, 10, 424 2 of 24 XRD phase comparison for AZ-M. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "ref_list": ["POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424."], "ref_snippets": [{"text": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O. size and the type and amount of binder present in the paints, as all these factors influenced the color of the paint and the roughness of its surface [19–22]. Other recent research has reported that the impurities found in the historic mineral pigments used in tempera paints might significantly alter their optical, chem ical, and physical properties [22–24].\nPhases identified before SO2 exposure: Azurite, Quartz, Malachite. Phases identified after SO2 exposure: Azurite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O.\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite.\nThe SO 2 aged rabbit glue-based mock-ups showed microscopically important crack formation and binder loss and fewer sulfated salts precipitated on the surface of the paints. Keywords: tempera paint; azurite; malachite; artificial aging; Sulfur dioxide; cultural heritage XRD phase comparison for AZ-C. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O.\nDespite the fact that the concentration of SO 2 gas in the atmosphere has been reduced in some regions Minerals 2020, 10, 424 2 of 24 XRD phase comparison for AZ-M. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "score": 0.4091482162475586, "snippets": [{"text": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O. size and the type and amount of binder present in the paints, as all these factors influenced the color of the paint and the roughness of its surface [19–22]. Other recent research has reported that the impurities found in the historic mineral pigments used in tempera paints might significantly alter their optical, chem ical, and physical properties [22–24].", "score": 0.4091482162475586, "metadata": {"doi": "10.3390/min10050424", "ingest_kind": "xrd_phase_table", "source": "xrd_phase_table/min10050424_part2", "table_sample": "AZ-ST", "source_file": "min10050424_part2_table1.pdf", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "year": "2020", "journal": "Minerals", "table_page": 5, "chunk_index": 4, "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O. size and the type and amount of binder present in the paints, as all these factors influenced the color of the paint and the roughness of its surface [19–22]. Other recent research has reported that the impurities found in the historic mineral pigments used in tempera paints might significantly alter their optical, chem ical, and physical properties [22–24].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Azurite, Quartz, Malachite. Phases identified after SO2 exposure: Azurite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O.", "score": 0.4123240113258362, "metadata": {"year": "2020", "table_sample": "AZ-EC", "chunk_index": 0, "source_file": "min10050424_part2_table1.pdf", "journal": "Minerals", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "source": "xrd_phase_table/min10050424_part2", "ingest_kind": "xrd_phase_table", "table_page": 5, "doi": "10.3390/min10050424", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Azurite, Quartz, Malachite. Phases identified after SO2 exposure: Azurite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "score": 0.41247349977493286, "metadata": {"doi": "10.3390/min10050424", "source_file": "min10050424_part2_table1.pdf", "table_page": 5, "ingest_kind": "xrd_phase_table", "chunk_index": 3, "year": "2020", "table_sample": "AZ-EF", "journal": "Minerals", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "source": "xrd_phase_table/min10050424_part2", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "score": 0.41430288553237915, "metadata": {"title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "doi": "10.3390/min10050424", "ingest_kind": "xrd_phase_table", "source_file": "min10050424_part2_table1.pdf", "table_page": 5, "journal": "Minerals", "chunk_index": 2, "source": "xrd_phase_table/min10050424_part2", "table_sample": "AZ-M", "year": "2020", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite.", "score": 0.4183335304260254, "metadata": {"chunk_index": 1, "ingest_kind": "xrd_phase_table", "source_file": "min10050424_part2_table1.pdf", "source": "xrd_phase_table/min10050424_part2", "year": "2020", "journal": "Minerals", "table_page": 5, "table_sample": "AZ-C", "doi": "10.3390/min10050424", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The SO 2 aged rabbit glue-based mock-ups showed microscopically important crack formation and binder loss and fewer sulfated salts precipitated on the surface of the paints. Keywords: tempera paint; azurite; malachite; artificial aging; Sulfur dioxide; cultural heritage XRD phase comparison for AZ-C. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O.", "score": null, "metadata": {"doi": "10.3390/min10050424", "journal": "Minerals", "year": "2020", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "chunk_index": 0, "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "source": "pdf_direct/min10050424_part2.pdf", "ingest_kind": "pdf_direct", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The SO 2 aged rabbit glue-based mock-ups showed microscopically important crack formation and binder loss and fewer sulfated salts precipitated on the surface of the paints. Keywords: tempera paint; azurite; malachite; artificial aging; Sulfur dioxide; cultural heritage XRD phase comparison for AZ-C. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Despite the fact that the concentration of SO 2 gas in the atmosphere has been reduced in some regions Minerals 2020, 10, 424 2 of 24 XRD phase comparison for AZ-M. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "score": null, "metadata": {"journal": "Minerals", "ingest_kind": "pdf_direct", "doi": "10.3390/min10050424", "chunk_index": 1, "source": "pdf_direct/min10050424_part2.pdf", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "year": "2020", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Despite the fact that the concentration of SO 2 gas in the atmosphere has been reduced in some regions Minerals 2020, 10, 424 2 of 24 XRD phase comparison for AZ-M. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 5, "resolver_scanned": 2314, "resolver_candidates": 6, "resolver_kept": 4, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 5, "lexical_scanned": 2314, "lexical_candidates": 227, "lexical_kept": 7, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/c14b6f8a08392d3ddcb99179053a9813b980b166.json b/rag_report_cache/c14b6f8a08392d3ddcb99179053a9813b980b166.json
new file mode 100644
index 0000000000000000000000000000000000000000..7b375d460530c4b60a333534e84a78a5571fcbc2
--- /dev/null
+++ b/rag_report_cache/c14b6f8a08392d3ddcb99179053a9813b980b166.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[12000lux+0.85W/m2+50℃+90%RH]--> 2PbCO3·Pb(OH)2 --[12000lux+0.85W/m2+50℃+90%RH]--> β-PbO2", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CRN source: In-house aging experiment"], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}], "related_context": [{"source": "ZHANG Z, HUANG Q, SUN J, et al. Aging and Discoloration of Red Lead (Pb3O4) Caused by Reactive Oxygen Species Under Alkaline Conditions [J/OL]. Molecules, 2025. DOI: 10.3390/molecules30102136.", "snippet": "### Ratio of Lead and Oxygen Elements in Aging Products Systematic elemental characterization was performed on reaction products obtained at different durations to investigate the inorganic transformation mechanism. Based on stoichiometric calculations, Pb\\({}_{3}\\)O\\({}_{4}\\) exhibits a Pb:O atomic ratio of 3:4, whereas PbO\\({}_{2}\\) demonstrates a reduced ratio of 1:2. These ratios indicate a progressive decrease in both atomic and mass ratios of Pb to O during the conversion from Pb\\({}_{3}\\)O\\({}_{4}\\) to PbO\\({}_{2}\\). Furthermore, the mixed oxidation states of Pb in Pb\\({}_{3}\\)O\\({}_{4}\\) comprise Pb (II) and Pb (IV) in a 2:1 ratio, while PbO\\({}_{2}\\) exclusively contains Pb (IV) species. This distinct oxidation state distribution implies a systematic decline in the Pb (II)/Pb (IV) ratio during the transformation process.", "retrieval_origin": "bge_m3", "match": {"edge_index": 0, "reactant": "Pb3O4", "product": "beta-PbO2", "condition": "12000lux+0.85W/m2+50℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "These ratios indicate a progressive decrease in both atomic and mass ratios of Pb to O during the conversion from Pb3O4 to PbO2.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Pb3O4", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "ZHAO Y, WANG J, PAN A, et al. Degradation of red lead pigment in the oil painting during UV aging [J/OL]. Color Research & Application, 2019. DOI: 10.1002/col.22386.", "snippet": "is a semiconductor pigment with mixed valence (II, IV) lead oxides, valence bands and conduction bands can be produced under ultraviolet light. In the model paint samples, Pb\\({}_{3}\\)O\\({}_{4}\\) is excited by UV light to form electrons and holes between the conduction and valence band. These electron-and-hole pairs will form a redox system, to further oxidize the ester and carboxyl groups in tung oil binder into CO\\({}_{2}\\) and H\\({}^{+}\\). At the same time, these electrons also are able to reduce Pb(IV) in Pb\\({}_{3}\\)O\\({}_{4}\\) into Pb(II), and the formed Pb(II) reacts with obtained CO\\({}_{2}\\) and H\\({}^{+}\\) to yield the final white product of 2PbCO\\({}_{3}\\)Pb(OH)\\({}_{2}\\).", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "Pb3O4", "product": "2PbCO3·Pb(OH)2", "condition": "12000lux+0.85W/m2+50℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "At the same time, these electrons also are able to reduce Pb(IV) in Pb3O4 into Pb(II), and the formed Pb(II) reacts with obtained CO2 and H{}^{+} to yield the final white product of 2PbCO3Pb(OH)2.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Pb3O4", "product_span": "2PbCO3Pb(OH)2", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "ROSADO T, GIL M, MIRÃO J, et al. Darkening on lead‐based pigments: Microbiological contribution [J/OL]. Color Research & Application, 2016. DOI: 10.1002/col.22014.", "snippet": "## Introduction Since Antiquity, admixtures of lead white (2PbCO\\({}_{3}\\)PbOH\\({}_{2}\\)) and red pigments like red lead (Pb\\({}_{3}\\)O\\({}_{4}\\)) were employed on mural paintings to produce flesh tones/carnations. Unfortunately, these pigments can suffer transformations due to natural aging or light interaction. Promoted by several environmental parameters, where humidity plays an important role in the activation of chemical processes, as well as in the support of microbial development. Color alterations of lead-based pigments may be generated inducing whitening or darkening processes [1]. In the case of the whitening process, compounds like hydrocerussite (2PbCO\\({}_{3}\\)Pb(OH)\\({}_{2}\\)), corussite (PbCO\\({}_{3}\\)) and anglesite (PbSO\\({}_{4}\\)) can appear in artworks as pigment degradation products, whereas plattnerite (PbO\\({}_{2}\\)) and galena (PbS), a black/brown product are associated to the darkening of some areas [2, 3, 4].", "retrieval_origin": "bge_m3", "match": {"edge_index": 2, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "12000lux+0.85W/m2+50℃+90%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "In the case of the whitening process, compounds like hydrocerussite (2PbCO3Pb(OH)2), corussite (PbCO3) and anglesite (PbSO4) can appear in artworks as pigment degradation products, whereas plattnerite (PbO2) and galena (PbS), a black/brown product are associated to the darkening of some areas [2, 3, 4].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 84, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 348, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/c5cb7808ac8d7ba09ac3d80680559fbeb13176a8.json b/rag_report_cache/c5cb7808ac8d7ba09ac3d80680559fbeb13176a8.json
new file mode 100644
index 0000000000000000000000000000000000000000..139a3418ba42ca2f186a7dfba75fd5496ebe65cb
--- /dev/null
+++ b/rag_report_cache/c5cb7808ac8d7ba09ac3d80680559fbeb13176a8.json
@@ -0,0 +1 @@
+{"root_material": "C16H10N2O2", "path_str": "C16H10N2O2 --[Uv]--> C8H5NO2 --[Uv]--> C8H5NO3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nVerification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin\n\n[1] Evidence classification: edge 1: direct\nPage 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.\n\n[2] Evidence classification: edge 1: direct\nPage 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "ref_list": ["A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions [J/OL]. Heritage Science, 2023:8. DOI: 10.1186/s40494-023-00887-7. (bibliographic metadata partially available)", "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions [J/OL]. Heritage Science, 2023:9. DOI: 10.1186/s40494-023-00887-7. (bibliographic metadata partially available)", "RONDÃO R, SEIXAS DE MELO JS, BONIFÁCIO VDB, et al. Dehydroindigo, the Forgotten Indigo and Its Contribution to the Color of Maya Blue [J/OL]. The Journal of Physical Chemistry A, 2010, 114(4):1699-1708. DOI: 10.1021/jp907718k.", "DELGADO MC. El índigo en la pintura de caballete novohispana: mecanismos de deterioro [J/OL]. Intervención, Revista Internacional de Conservación, Restauración y Museología, 2019. DOI: 10.30763/intervencion.2019.19.206."], "ref_snippets": [{"text": "Verification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin\nPage 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.", "score": 0.45905983448028564, "snippets": [{"text": "Verification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin", "score": 0.4852132201194763, "metadata": {"source": "Indigo oxidation mechanism in grottoes murals by ozone", "doi": "10.1186/s40494-023-00887-7", "chunk_index": "24", "year": "2023", "ingest_kind": "pdf_fulltext", "source_file": "Indigo oxidation mechanism in grottoes murals by ozone", "page": "8", "title": "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions", "journal": "Heritage Science"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C8H5NO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Verification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "isatin", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Page 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.", "score": 0.45905983448028564, "metadata": {"journal": "Heritage Science", "chunk_index": "22", "year": "2023", "source_file": "Indigo oxidation mechanism in grottoes murals by ozone", "source": "Indigo oxidation mechanism in grottoes murals by ozone", "doi": "10.1186/s40494-023-00887-7", "page": "8", "ingest_kind": "pdf_fulltext", "title": "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C8H5NO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Page 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "isatin", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Page 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "score": null, "snippets": [{"text": "Page 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "score": null, "metadata": {"ingest_kind": "pdf_fulltext", "chunk_index": "25", "year": "2023", "doi": "10.1186/s40494-023-00887-7", "page": "9", "source": "Indigo oxidation mechanism in grottoes murals by ozone", "title": "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions", "journal": "Heritage Science", "source_file": "Indigo oxidation mechanism in grottoes murals by ozone"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C8H5NO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Page 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "isatin", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 46, "resolver_kept": 3, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 169, "lexical_kept": 3, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/c917900e9814dfa17f76c8f79d2554059b49e126.json b/rag_report_cache/c917900e9814dfa17f76c8f79d2554059b49e126.json
new file mode 100644
index 0000000000000000000000000000000000000000..2e64f833757a041616476f8e73218b536b1f1012
--- /dev/null
+++ b/rag_report_cache/c917900e9814dfa17f76c8f79d2554059b49e126.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[H2S]--> CuS", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nFig. 1 shows the Raman spectrum of (a) a CuS reference material compared to that of (b) azurite (2CuCO3-Cu(OH)2), and (c) blackened azurite. The transformation of Cu(II) salts to CuS when exposed to H2S is well attested in the chemistry [2] and art [7] literature.", "ref_list": ["SMITH GD, CLARK RJH. The role of H2S in pigment blackening [J/OL]. Journal of Cultural Heritage, 2002. DOI: 10.1016/s1296-2074(02)01173-1."], "ref_snippets": [{"text": "Fig. 1 shows the Raman spectrum of (a) a CuS reference material compared to that of (b) azurite (2CuCO3-Cu(OH)2), and (c) blackened azurite. The transformation of Cu(II) salts to CuS when exposed to H2S is well attested in the chemistry [2] and art [7] literature.", "score": 0.4454317092895508, "snippets": [{"text": "Fig. 1 shows the Raman spectrum of (a) a CuS reference material compared to that of (b) azurite (2CuCO3-Cu(OH)2), and (c) blackened azurite. The transformation of Cu(II) salts to CuS when exposed to H2S is well attested in the chemistry [2] and art [7] literature.", "score": 0.4454317092895508, "metadata": {"year": "2002", "source_file": "The role of H2S in pigment blackening.md", "chunk_index": 9, "doi": "10.1016/s1296-2074(02)01173-1", "ingest_kind": "existing_chroma", "title": "The role of H2S in pigment blackening", "source": "markdown_output/The role of H2S in pigment blackening.md", "journal": "Journal of Cultural Heritage", "authors": [{"family": "Smith", "given": "Gregory D."}, {"family": "Clark", "given": "Robin J.H."}], "volume": "3", "issue": "2", "pages": "101-105", "url": "https://doi.org/10.1016/s1296-2074(02)01173-1"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "resolver", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuS", "condition": "H2S", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Fig. 1 shows the Raman spectrum of (a) a CuS reference material compared to that of (b) azurite (2CuCO3-Cu(OH)2), and (c) blackened azurite. The transformation of Cu(II) salts to CuS when exposed to H2S is well attested in the chemistry [2] and art [7] literature.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "azurite", "product_span": "CuS", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 37, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 230, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
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diff --git a/rag_report_cache/d00aaadca8ea66fb490eb5fe0825dc6f44289101.json b/rag_report_cache/d00aaadca8ea66fb490eb5fe0825dc6f44289101.json
new file mode 100644
index 0000000000000000000000000000000000000000..a9fb666120f641da604496fbc4ecf65937569b15
--- /dev/null
+++ b/rag_report_cache/d00aaadca8ea66fb490eb5fe0825dc6f44289101.json
@@ -0,0 +1 @@
+{"root_material": "α-FeO(OH)", "path_str": "α-FeO(OH) --[Heat]--> α-Fe2O3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThey are, however, sensitive to high temperatures, such as fires [12, 68], or local heating effects related to the use of lasers for cleaning [19, 69, 70] or for spectroscopi - cal analysis (i.e. Raman spectroscopy, [62, 63, 71, 72]). A UV (248 nm) laser showed darkening of yellow ochre and raw Sienna, as a result of dehydration, conversion to haematite and modification of the manganese phases present [69], but low fluences of the same laser caused little modification of this ochre [19].", "ref_list": ["On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:11. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "GIACHI G, CAROLIS ED, PALLECCHI P. Raw Materials in Pompeian Paintings: Characterization of Some Colors from the Archaeological Site [J/OL]. Materials and Manufacturing Processes, 2009. DOI: 10.1080/10426910902982631."], "ref_snippets": [{"text": "They are, however, sensitive to high temperatures, such as fires [12, 68], or local heating effects related to the use of lasers for cleaning [19, 69, 70] or for spectroscopi - cal analysis (i.e. Raman spectroscopy, [62, 63, 71, 72]). A UV (248 nm) laser showed darkening of yellow ochre and raw Sienna, as a result of dehydration, conversion to haematite and modification of the manganese phases present [69], but low fluences of the same laser caused little modification of this ochre [19].", "score": null, "snippets": [{"text": "They are, however, sensitive to high temperatures, such as fires [12, 68], or local heating effects related to the use of lasers for cleaning [19, 69, 70] or for spectroscopi - cal analysis (i.e. Raman spectroscopy, [62, 63, 71, 72]). A UV (248 nm) laser showed darkening of yellow ochre and raw Sienna, as a result of dehydration, conversion to haematite and modification of the manganese phases present [69], but low fluences of the same laser caused little modification of this ochre [19].", "score": null, "metadata": {"page": "11", "source_file": "On the stability of mediaeval inorganic pigments - a review", "doi": "10.1186/s40494-017-0125-6", "journal": "Heritage Science", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "chunk_index": "30", "source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "ingest_kind": "pdf_fulltext"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "alpha-FeO(OH)", "product": "alpha-Fe2O3", "condition": "Heat", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "They are, however, sensitive to high temperatures, such as fires [12, 68], or local heating effects related to the use of lasers for cleaning [19, 69, 70] or for spectroscopi - cal analysis (i.e. Raman spectroscopy, [62, 63, 71, 72]). A UV (248 nm) laser showed darkening of yellow ochre and raw Sienna, as a result of dehydration, conversion to haematite and modification of the manganese phases present [69], but low fluences of the same laser caused little modification of this ochre [19].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "yellow ochre", "product_span": "haematite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 11, "dense_candidates": 220, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 13, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 18, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/d131b42d407b7fd2c8ec354fdddaa8540d425ee5.json b/rag_report_cache/d131b42d407b7fd2c8ec354fdddaa8540d425ee5.json
new file mode 100644
index 0000000000000000000000000000000000000000..744cd3ef9ccd34c4ef8d9f510b32595f64514698
--- /dev/null
+++ b/rag_report_cache/d131b42d407b7fd2c8ec354fdddaa8540d425ee5.json
@@ -0,0 +1 @@
+{"root_material": "2PbCO3·Pb(OH)2", "path_str": "2PbCO3·Pb(OH)2 --[Oxidant]--> α-PbO2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nNo oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2. Lead white blackens very quickly only in the presence of NaClO, order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2. Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]\n\n[1] Evidence classification: edge 1: direct\nLead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]\n\n[1] Evidence classification: edge 1: direct\nAze{}^{130} showed that lead white oxidation, due to lime alkalinity, leads to the formation of red lead besides massicot and litharge, whereas no plattnerite is observed.\n\n[1] Evidence classification: edge 1: direct\nFigure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).\n\n[1] Evidence classification: edge 1: direct\nFigure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite). Inset: (I) corussite and (II) hydrocerussite before (left) and after (right) treatment with NaClO [Colour figure can be viewed at wileyoInlinelibrary.com] hydrocerussite were separately applied with a proteinaceous binder. The choice of a secoo application is based on the evidence that because NaClO is effective with both corussite and hydrocerussite as powders, then it could be opportune to examine the possible role of a binder in protecting the pigment particles from external oxidation.\n\n[1] Evidence classification: edge 1: direct\nHydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.\n\n[1] Evidence classification: edge 1: direct\nThe different behaviours detected between the two lead white components is crucial for understanding not only the current state of its alteration in artworks but also its genesis, being endogenous (environmental alkalinity) for massicot and red-lead and exogenous (oxiding agent) for plattnerite or scrutinyite.\n\n[2] Evidence classification: edge 1: direct\nStrong oxidizing agents were added to water suspensions to induce the lead-based pigments' darkening. X-ray patterns of original lead white and its reaction products with NaClO and hydrogen peroxide are in Fig. 5. Lead white reacted with NaClO very quickly and it turned black-brown almost immediately. The product of this reaction contained remnants of original phases (hydrocerussite, lead acetate oxide hydrate (PDF card 18-1740), and additionally new-formed phases of plattnerite, scrutinyite and cerussite. Plattnerite and poorly crystalline scrutinyite were responsible for the black-brown colour.\n\n[2] Evidence classification: edge 1: direct\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\n\n[2] Evidence classification: edge 1: direct\nLead white (hydrocerussite) darkened immediately when in contact with a solution of NaClO due to its oxidation to brown-black plattrerite (PbO2).\n\n[3] Evidence classification: edge 1: direct\n## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.", "ref_list": ["VAGNINI M, VIVANI R, SGAMELLOTTI A, et al. Blackening of lead white: Study of model paintings [J/OL]. Journal of Raman Spectroscopy, 2020. DOI: 10.1002/jrs.5879.", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001.", "VAGNINI M, VIVANI R, VISCUSO E, et al. Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi [J/OL]. Vibrational Spectroscopy, 2018. DOI: 10.1016/j.vibspec.2018.07.006."], "ref_snippets": [{"text": "No oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2. Lead white blackens very quickly only in the presence of NaClO, order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2. Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]\nLead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]\nAze{}^{130} showed that lead white oxidation, due to lime alkalinity, leads to the formation of red lead besides massicot and litharge, whereas no plattnerite is observed.\nFigure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).\nFigure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite). Inset: (I) corussite and (II) hydrocerussite before (left) and after (right) treatment with NaClO [Colour figure can be viewed at wileyoInlinelibrary.com] hydrocerussite were separately applied with a proteinaceous binder. The choice of a secoo application is based on the evidence that because NaClO is effective with both corussite and hydrocerussite as powders, then it could be opportune to examine the possible role of a binder in protecting the pigment particles from external oxidation.\nHydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.\nThe different behaviours detected between the two lead white components is crucial for understanding not only the current state of its alteration in artworks but also its genesis, being endogenous (environmental alkalinity) for massicot and red-lead and exogenous (oxiding agent) for plattnerite or scrutinyite.", "score": null, "snippets": [{"text": "No oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2. Lead white blackens very quickly only in the presence of NaClO, order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2. Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]", "score": null, "metadata": {"year": "2020", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "doi": "10.1002/jrs.5879", "ingest_kind": "existing_chroma", "journal": "Journal of Raman Spectroscopy", "chunk_index": 4, "title": "Blackening of lead white: Study of model paintings", "source_file": "Blackening of lead white: Study of model paintings.md", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "No oxidation took place except for red lead, which turns into plattnerite independently of the salt used.[14] In order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2. Lead white blackens very quickly only in the presence of NaClO, order to accelerate the degradation process of lead white, two strong oxidants were used: commercial NaClO and H2O2. Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]", "score": null, "metadata": {"chunk_index": 5, "title": "Blackening of lead white: Study of model paintings", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "doi": "10.1002/jrs.5879", "year": "2020", "source_file": "Blackening of lead white: Study of model paintings.md", "ingest_kind": "existing_chroma", "journal": "Journal of Raman Spectroscopy", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Aze{}^{130} showed that lead white oxidation, due to lime alkalinity, leads to the formation of red lead besides massicot and litharge, whereas no plattnerite is observed.", "score": null, "metadata": {"doi": "10.1002/jrs.5879", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "source_file": "Blackening of lead white: Study of model paintings.md", "title": "Blackening of lead white: Study of model paintings", "ingest_kind": "existing_chroma", "year": "2020", "chunk_index": 22, "journal": "Journal of Raman Spectroscopy", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Aze{}^{130} showed that lead white oxidation, due to lime alkalinity, leads to the formation of red lead besides massicot and litharge, whereas no plattnerite is observed.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Figure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).", "score": null, "metadata": {"ingest_kind": "existing_chroma", "journal": "Journal of Raman Spectroscopy", "title": "Blackening of lead white: Study of model paintings", "chunk_index": 31, "year": "2020", "source_file": "Blackening of lead white: Study of model paintings.md", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "doi": "10.1002/jrs.5879", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Figure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "scrutinyite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Figure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite). Inset: (I) corussite and (II) hydrocerussite before (left) and after (right) treatment with NaClO [Colour figure can be viewed at wileyoInlinelibrary.com] hydrocerussite were separately applied with a proteinaceous binder. The choice of a secoo application is based on the evidence that because NaClO is effective with both corussite and hydrocerussite as powders, then it could be opportune to examine the possible role of a binder in protecting the pigment particles from external oxidation.", "score": null, "metadata": {"doi": "10.1002/jrs.5879", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "chunk_index": 32, "source_file": "Blackening of lead white: Study of model paintings.md", "journal": "Journal of Raman Spectroscopy", "ingest_kind": "existing_chroma", "title": "Blackening of lead white: Study of model paintings", "year": "2020", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Figure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite). Inset: (I) corussite and (II) hydrocerussite before (left) and after (right) treatment with NaClO [Colour figure can be viewed at wileyoInlinelibrary.com] hydrocerussite were separately applied with a proteinaceous binder. The choice of a secoo application is based on the evidence that because NaClO is effective with both corussite and hydrocerussite as powders, then it could be opportune to examine the possible role of a binder in protecting the pigment particles from external oxidation.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "scrutinyite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Hydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "score": null, "metadata": {"doi": "10.1002/jrs.5879", "ingest_kind": "existing_chroma", "source_file": "Blackening of lead white: Study of model paintings.md", "title": "Blackening of lead white: Study of model paintings", "year": "2020", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "chunk_index": 33, "journal": "Journal of Raman Spectroscopy", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Hydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "scrutinyite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The different behaviours detected between the two lead white components is crucial for understanding not only the current state of its alteration in artworks but also its genesis, being endogenous (environmental alkalinity) for massicot and red-lead and exogenous (oxiding agent) for plattnerite or scrutinyite.", "score": null, "metadata": {"journal": "Journal of Raman Spectroscopy", "chunk_index": 38, "doi": "10.1002/jrs.5879", "source_file": "Blackening of lead white: Study of model paintings.md", "ingest_kind": "existing_chroma", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "year": "2020", "title": "Blackening of lead white: Study of model paintings", "authors": [{"family": "Vagnini", "given": "Manuela"}, {"family": "Vivani", "given": "Riccardo"}, {"family": "Sgamellotti", "given": "Antonio"}, {"family": "Miliani", "given": "Costanza"}], "volume": "51", "issue": "7", "pages": "1118-1126", "url": "https://doi.org/10.1002/jrs.5879"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The different behaviours detected between the two lead white components is crucial for understanding not only the current state of its alteration in artworks but also its genesis, being endogenous (environmental alkalinity) for massicot and red-lead and exogenous (oxiding agent) for plattnerite or scrutinyite.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "scrutinyite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Strong oxidizing agents were added to water suspensions to induce the lead-based pigments' darkening. X-ray patterns of original lead white and its reaction products with NaClO and hydrogen peroxide are in Fig. 5. Lead white reacted with NaClO very quickly and it turned black-brown almost immediately. The product of this reaction contained remnants of original phases (hydrocerussite, lead acetate oxide hydrate (PDF card 18-1740), and additionally new-formed phases of plattnerite, scrutinyite and cerussite. Plattnerite and poorly crystalline scrutinyite were responsible for the black-brown colour.\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\nLead white (hydrocerussite) darkened immediately when in contact with a solution of NaClO due to its oxidation to brown-black plattrerite (PbO2).", "score": null, "snippets": [{"text": "Strong oxidizing agents were added to water suspensions to induce the lead-based pigments' darkening. X-ray patterns of original lead white and its reaction products with NaClO and hydrogen peroxide are in Fig. 5. Lead white reacted with NaClO very quickly and it turned black-brown almost immediately. The product of this reaction contained remnants of original phases (hydrocerussite, lead acetate oxide hydrate (PDF card 18-1740), and additionally new-formed phases of plattnerite, scrutinyite and cerussite. Plattnerite and poorly crystalline scrutinyite were responsible for the black-brown colour.", "score": null, "metadata": {"journal": "Journal of Cultural Heritage", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "title": "Degradation of lead-based pigments by salt solutions", "source_file": "Degradation of lead-based pigments by salt solutions.md", "chunk_index": 28, "year": "2009", "ingest_kind": "existing_chroma", "doi": "10.1016/j.culher.2008.11.001"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Strong oxidizing agents were added to water suspensions to induce the lead-based pigments' darkening. X-ray patterns of original lead white and its reaction products with NaClO and hydrogen peroxide are in Fig. 5. Lead white reacted with NaClO very quickly and it turned black-brown almost immediately. The product of this reaction contained remnants of original phases (hydrocerussite, lead acetate oxide hydrate (PDF card 18-1740), and additionally new-formed phases of plattnerite, scrutinyite and cerussite. Plattnerite and poorly crystalline scrutinyite were responsible for the black-brown colour.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "scrutinyite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "score": null, "metadata": {"title": "Degradation of lead-based pigments by salt solutions", "year": "2009", "doi": "10.1016/j.culher.2008.11.001", "source_file": "Degradation of lead-based pigments by salt solutions.md", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "chunk_index": 42, "journal": "Journal of Cultural Heritage", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Lead white (hydrocerussite) darkened immediately when in contact with a solution of NaClO due to its oxidation to brown-black plattrerite (PbO2).", "score": null, "metadata": {"chunk_index": 52, "source_file": "Degradation of lead-based pigments by salt solutions.md", "journal": "Journal of Cultural Heritage", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "ingest_kind": "existing_chroma", "title": "Degradation of lead-based pigments by salt solutions", "doi": "10.1016/j.culher.2008.11.001", "year": "2009"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Lead white (hydrocerussite) darkened immediately when in contact with a solution of NaClO due to its oxidation to brown-black plattrerite (PbO2).", "reactant_match": "alias", "product_match": "exact", "reactant_span": "hydrocerussite", "product_span": "PbO2", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.", "score": null, "snippets": [{"text": "## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.", "score": null, "metadata": {"chunk_index": 37, "title": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi", "journal": "Vibrational Spectroscopy", "doi": "10.1016/j.vibspec.2018.07.006", "source": "markdown_output/Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "source_file": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "year": "2018", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "alpha-PbO2", "condition": "Oxidant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "lead dioxide", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 42, "resolver_kept": 11, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 227, "lexical_kept": 11, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/d29d6a50fecd5abd1c8967dac304f630641c2812.json b/rag_report_cache/d29d6a50fecd5abd1c8967dac304f630641c2812.json
new file mode 100644
index 0000000000000000000000000000000000000000..e0874f0c9d0dba8d8333b3d99e27b4de382b7c53
--- /dev/null
+++ b/rag_report_cache/d29d6a50fecd5abd1c8967dac304f630641c2812.json
@@ -0,0 +1 @@
+{"root_material": "As4S4", "path_str": "As4S4 --[5000lux+1.65W/m2+30℃+60%RH]--> p-As4S4 --[5000lux+1.65W/m2+30℃+60%RH]--> As2O3", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CRN source: In-house aging experiment"], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}], "related_context": [{"source": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization [J/OL]. Heritage Science, 2024. DOI: 10.1186/s40494-024-01350-x. (bibliographic metadata partially available)", "snippet": "elemental analysis. With these methods, it is not always possible to distinguish arsenic-bearing minerals from synthetic arsenic sulfides and secondary phases. As for the latter, the degradation of realgar into pararealgar was not described in detail until 1996. Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72]. It is important to realize that to differentiate between the three classes of arsenic compounds, additional analytical methods of high specificity such as Raman spectroscopy and X-ray powder diffraction are essential. In this article, two types of arsenic sulfide pigments discovered in Rembrandt’s oeuvre are presented: (regular) pararealgar, which is yellow, and a semi- amorphous variant that is orange to red. The historic use, complexity of identification and interpretation of arsenic sulfides is studied in relevant historical sources to explain their use by Rembrandt. The presence of arsenic sulfides in The Night Watch was first detected by non-invasive imaging when the entire surface of the painting was scanned with macroscopic X-ray fluorescence imaging spectroscopy (MA-XRF) (Fig. 1c). Subsequent examination of the paint surface with stereomicroscopy revealed small areas of bright orange paint (Fig. 1d) in several areas at the surface and in the underpainting of the embroidery of Willem van Ruytenburch’s buff coat (the figure dressed in yellow in the mi", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "5000lux+1.65W/m2+30℃+60%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "KEUNE K, MASS J, MEHTA A, et al. Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues [J/OL]. Heritage Science, 2016. DOI: 10.1186/s40494-016-0078-1.", "snippet": "tue and vice, wisdom and strength, and mars and venus united by love. In: Metropolitan museum studies in art, science, and technology; 2010. p 83–108. 5. Keune K, Mass J, Meirer F, Pottasch C, van Loon A, Hull A, Church J, Pouyet E, Cotte M, Mehta A. Tracking the transformation and transport of arsenic sulfide pigments in paints: synchrotron-based X-ray micro-analysis. J Anal At Spectrom. 2015;30:813–27. 6. Douglass DL, Shing C, Wang G. The light-induced alteration of realgar to pararealgar. American Mineralolist. 1992;77:1266–74. 7. Ballirano P , Maras A. Preliminary results on the ligh-induced alteration of realgar: kinetics of the process. Plinius. 2002;28:35–6. 8. Mass J. Personal observations; 2015. 9. Trentelman K, Stodulski L, Pavlosky M. Characterization of pararealgar and other light-induced transformation products from realgar by Raman microspectroscopy. Anal Chem. 1996;68:1755–61. 10. Rötter C, Grundmann G, Richter M, van Loon A, Keune K, Boersma A, Rapp K. The occurrence of artificial orpiment (dry process) in northern European painting and polychromy and evidence in historical sources. In: Schuller M, Emmerling E, Nerdinger W, Verlag Anton Siegl, editors. Auripigment/Orpiment: Studien zu dem Mineral und den künstlichten Produkten. Fachbuchhandlung GmbH. München; 2007. 11. van Loon A: Colour changes and chemical reactivity in seventeenth-cen- tury oil paintings. In: Ph.D. Thesis. University of Amsterdam, Molart Series (14), AMOLF: Amsterdam; 2008. 12. Sheldon L, Woodcock S, Wallert A. Orpiment overlooked-expect the", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "5000lux+1.65W/m2+30℃+60%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "J Anal At Spectrom. 2015;30:813–27. 6. Douglass DL, Shing C, Wang G. The light-induced alteration of realgar to pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9.", "snippet": "This lecture text is aimed at teaching some insight into phase transitions of minerals. It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (\\(\\alpha\\)-As\\({}_{4}\\)S\\({}_{4}\\)) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy. The process of transformation takes place in four steps. The initiating photoreaction step requires oxygen and thereby the intermediate azonite (As\\({}_{4}\\)S\\({}_{5}\\)) and arsenolite (As\\({}_{2}\\)O\\({}_{3}\\)) are obtained (step 1). The process continues through a set of cyclic reactions in which the sulfur atom released by the decomposition of As\\({}_{4}\\)S\\({}_{5}\\) (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "5000lux+1.65W/m2+30℃+60%RH", "evidence_scope": "edge", "verdict": "related", "score": 0.8, "window": "The process continues through a set of cyclic reactions in which the sulfur atom released by the decomposition of As4S5 (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 157, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/d38006202ffe404b63e97f58aa57b53882d429d7.json b/rag_report_cache/d38006202ffe404b63e97f58aa57b53882d429d7.json
new file mode 100644
index 0000000000000000000000000000000000000000..edea483c8b80ef2328354e37703cbdd001304c93
--- /dev/null
+++ b/rag_report_cache/d38006202ffe404b63e97f58aa57b53882d429d7.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Uv]--> CuO", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nOn exposure to laser light, pure malachite darkens [139], as a consequence of reduction of Cu 2+ to form dark cuprite Cu2O and black tenorite CuO [141, 142].\n\n[2] Evidence classification: edge 1: direct\nondary carbonates (malachite) 8,17–20.T h em o s tc o m m o n l y reported alteration, however, is blackening, generally attributed to the for- mation of tenorite (CuO) under conditions of high humidity and alkalinity in lime-based substrates2,21–27. Tenorite formation may also result from thermal damage28 or laser irradiation 29,30.I na d d i t i o n ,i n t e r a c t i o n sw i t h pollutant gases and acids can produce dark copper compounds such as copper sulphides (covellite) 31,32.", "ref_list": ["On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:14. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "Blackening of copper pigments in wall paintings: impact of the fresco technique and the chemical composition of the pigments [J/OL]. Heritage Science, 2026:2. DOI: 10.1038/s40494-026-02461-3. (bibliographic metadata partially available)", "CHAPPÉ M, HILDENHAGEN J, DICKMANN K, et al. Laser irradiation of medieval pigments at IR, VIS and UV wavelengths [J/OL]. Journal of Cultural Heritage, 2003. DOI: 10.1016/s1296-2074(02)01206-2."], "ref_snippets": [{"text": "On exposure to laser light, pure malachite darkens [139], as a consequence of reduction of Cu 2+ to form dark cuprite Cu2O and black tenorite CuO [141, 142].", "score": null, "snippets": [{"text": "On exposure to laser light, pure malachite darkens [139], as a consequence of reduction of Cu 2+ to form dark cuprite Cu2O and black tenorite CuO [141, 142].", "score": null, "metadata": {"title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "page": "14", "chunk_index": "43", "doi": "10.1186/s40494-017-0125-6", "source_file": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "ingest_kind": "pdf_fulltext"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuO", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "On exposure to laser light, pure malachite darkens [139], as a consequence of reduction of Cu 2+ to form dark cuprite Cu2O and black tenorite CuO [141, 142].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "tenorite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "ondary carbonates (malachite) 8,17–20.T h em o s tc o m m o n l y reported alteration, however, is blackening, generally attributed to the for- mation of tenorite (CuO) under conditions of high humidity and alkalinity in lime-based substrates2,21–27. Tenorite formation may also result from thermal damage28 or laser irradiation 29,30.I na d d i t i o n ,i n t e r a c t i o n sw i t h pollutant gases and acids can produce dark copper compounds such as copper sulphides (covellite) 31,32.", "score": null, "snippets": [{"text": "ondary carbonates (malachite) 8,17–20.T h em o s tc o m m o n l y reported alteration, however, is blackening, generally attributed to the for- mation of tenorite (CuO) under conditions of high humidity and alkalinity in lime-based substrates2,21–27. Tenorite formation may also result from thermal damage28 or laser irradiation 29,30.I na d d i t i o n ,i n t e r a c t i o n sw i t h pollutant gases and acids can produce dark copper compounds such as copper sulphides (covellite) 31,32.", "score": null, "metadata": {"year": "2026", "chunk_index": "5", "source_file": "Blackening of copper pigments in wall paintings", "ingest_kind": "pdf_fulltext", "journal": "Heritage Science", "title": "Blackening of copper pigments in wall paintings: impact of the fresco technique and the chemical composition of the pigments", "source": "Blackening of copper pigments in wall paintings", "page": "2", "doi": "10.1038/s40494-026-02461-3"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuO", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "ondary carbonates (malachite) 8,17–20.T h em o s tc o m m o n l y reported alteration, however, is blackening, generally attributed to the for- mation of tenorite (CuO) under conditions of high humidity and alkalinity in lime-based substrates2,21–27. Tenorite formation may also result from thermal damage28 or laser irradiation 29,30.I na d d i t i o n ,i n t e r a c t i o n sw i t h pollutant gases and acids can produce dark copper compounds such as copper sulphides (covellite) 31,32.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "tenorite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 28, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 182, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/d3a91112134754c219e8fea31e2ee7d5aca9b05c.json b/rag_report_cache/d3a91112134754c219e8fea31e2ee7d5aca9b05c.json
new file mode 100644
index 0000000000000000000000000000000000000000..b8aed173497a617d05815c25028297af731406bd
--- /dev/null
+++ b/rag_report_cache/d3a91112134754c219e8fea31e2ee7d5aca9b05c.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Biogenic+Sulfate]--> Cu4SO4(OH)6 --[Biogenic+Sulfate]--> Cu3SO4(OH)4", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [{"source": "CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w.", "snippet": "sively used during the 19th century with very adverse conse- quences to people’s health and wallpaper-manufacturing-industry workers. 13 Copper pigments are very sensitive to environmental pollutants. For example, brochantite (basic copper sulfate, Cu 4(SO4)(OH)6) was found by Raman spectroscopy in a wallpaper sample from the 19th century. This pigment was found together with antlerite (another copper sulfate, Cu 3(SO4)(OH)4). The pollution level in the area (SO x gases) where the sample was found seemed to be responsible for the degradation/transformation of the brochantite into antlerite. 14 Other degradations of copper pigments have been described in the literature, such as the decay suffered by malachite in the presence of chloride and humidity 15 or its degradation induced by a decayed calcite -gypsum mortar. 16 In this work, the degradation mechanism of green copper pigments due to the presence of microorganisms excreting oxalic acid is described. Chemical Systems Studied. The study was performed by analyzing Raman and X-ray fluorescence (XRF) spectra collected from different artworks with a variety of supports and pathologies. On the one hand, a map printed by the Blaeu family (Amsterdam, Holland) in the 17th century was taken into account. The map showed different green areas with different shades as well as an important degradation process of the cellulose due to the presence of green pigments (chemical system 1).", "retrieval_origin": "bge_m3", "match": {"edge_index": 2, "reactant": "Cu4SO4(OH)6", "product": "Cu3SO4(OH)4", "condition": "Biogenic+Sulfate", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "The pollution level in the area (SO x gases) where the sample was found seemed to be responsible for the degradation/transformation of the brochantite into antlerite. 14 Other degradations of copper pigments have been described in the literature, such as the decay suffered by malachite in the presence of chloride and humidity 15 or its degradation induced by a decayed calcite -gypsum mortar. 16 In this work, the degradation mechanism of green copper pigments due to the presence of microorganisms excreting oxalic acid is described.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "brochantite", "product_span": "antlerite", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:15. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "nce of degraded azurite [115]. Copper sulphates (brochantite, antlerite, langite, posnjakite: CuSO4·yCu(OH)2·zH2O, green) Green copper sulphates are commonly found as degra - dation products on copper artefacts exposed to polluted environments [105]. Brochantite was identified as a pig - ment as well [1], but it can transform into the more stable polymorphs, antlerite, langite or posnjakite, according to the given conditions of relative humidity, inorganic pol - lutants (SO x) and biological activity (affecting the pH and the type of acids) [127, 129, 168]. Posnjakite was also identified as a pigment [162, 169]. Brochantite, as well as posnjakite and antlerite are also intermediate reaction products between copper carbonates and copper oxa - lates, and are therefore sensitive to oxalic acid [127]. Arsenic (Z = 33) Geologically, orpiment (As 2S3) and realgar (As 4S4) occur together, and are often associated with antimonates and other sulphides [1, 30]. Orpiment and realgar were highly appreciated especially in Egypt and China for their rich yellow and red–orange shades [1, 170–174], even though the pigments were considered “unpleasant” by many art - ists, and not recommended to use in combination with copper and lead based pigments, such as verdigris and leadwhite [1, 30, 170]. Orpiment and realgar exist as minerals, as well as synthetic pigments [175], and of the two arsenic sulphide pigments, the first one is the most stable. Realgar, being unstable, was less often reported in works of art [1, 176–179]. It has a polymorphic pho - todegradation product, pararealgar As 4S4.", "retrieval_origin": "resolver", "match": {"edge_index": 2, "reactant": "Cu4SO4(OH)6", "product": "Cu3SO4(OH)4", "condition": "Biogenic+Sulfate", "evidence_scope": "edge", "verdict": "related", "score": 0.88, "window": "Brochantite was identified as a pig - ment as well [1], but it can transform into the more stable polymorphs, antlerite, langite or posnjakite, according to the given conditions of relative humidity, inorganic pol - lutants (SO x) and biological activity (affecting the pH and the type of acids) [127, 129, 168].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "brochantite", "product_span": "antlerite", "relation_basis": "observed_conversion", "condition_status": "partial", "provenance_level": "unspecified", "reasons": ["condition_partial"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 22, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 183, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/d65bdd451c1236b528a3078cc831af50a7389539.json b/rag_report_cache/d65bdd451c1236b528a3078cc831af50a7389539.json
new file mode 100644
index 0000000000000000000000000000000000000000..e10acd4a4bbda1a741a19eccd21ccea3078cd88c
--- /dev/null
+++ b/rag_report_cache/d65bdd451c1236b528a3078cc831af50a7389539.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Chloride]--> CuCl2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThe treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.\n\n[2] Evidence classification: edge 1: direct\nThe alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "ref_list": ["POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "DOMÉNECH‐CARBÓ MT, EDWARDS HGM, DOMÉNECH‐CARBÓ A, et al. An authentication case study: Antonio Palomino versus Vicente Guillo paintings in the vaulted ceiling of the Sant Joan del Mercat church (Valencia, Spain) [J/OL]. Journal of Raman Spectroscopy, 2012. DOI: 10.1002/jrs.3168."], "ref_snippets": [{"text": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "score": null, "snippets": [{"text": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "score": null, "metadata": {"source": "pdf_direct/min10050424_part2.pdf", "chunk_index": 6, "year": "2020", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "ingest_kind": "pdf_direct", "doi": "10.3390/min10050424", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "journal": "Minerals"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "copper chloride", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "snippets": [{"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "metadata": {"ingest_kind": "pdf_reextract", "year": "2008", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "chunk_index": 0, "journal": "Journal of Raman Spectroscopy", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "doi": "10.1002/jrs.1845", "title": "Raman spectroscopic analysis of azurite blackening"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "CuCl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "copper chloride", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 24, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 225, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/d6e57d84c6cd2c5561696c3d34b682c933200add.json b/rag_report_cache/d6e57d84c6cd2c5561696c3d34b682c933200add.json
new file mode 100644
index 0000000000000000000000000000000000000000..bb2a85b35a8568b809a01048530a847196d39bdf
--- /dev/null
+++ b/rag_report_cache/d6e57d84c6cd2c5561696c3d34b682c933200add.json
@@ -0,0 +1 @@
+{"root_material": "C16H10N2O2", "path_str": "C16H10N2O2 --[Uv]--> C8H5NO2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nVerification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin\n\n[1] Evidence classification: edge 1: direct\nPage 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.\n\n[2] Evidence classification: edge 1: direct\nPage 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "ref_list": ["A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions [J/OL]. Heritage Science, 2023:8. DOI: 10.1186/s40494-023-00887-7. (bibliographic metadata partially available)", "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions [J/OL]. Heritage Science, 2023:9. DOI: 10.1186/s40494-023-00887-7. (bibliographic metadata partially available)", "RONDÃO R, SEIXAS DE MELO JS, BONIFÁCIO VDB, et al. Dehydroindigo, the Forgotten Indigo and Its Contribution to the Color of Maya Blue [J/OL]. The Journal of Physical Chemistry A, 2010, 114(4):1699-1708. DOI: 10.1021/jp907718k.", "DELGADO MC. El índigo en la pintura de caballete novohispana: mecanismos de deterioro [J/OL]. Intervención, Revista Internacional de Conservación, Restauración y Museología, 2019. DOI: 10.30763/intervencion.2019.19.206."], "ref_snippets": [{"text": "Verification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin\nPage 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.", "score": 0.43492263555526733, "snippets": [{"text": "Verification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin", "score": 0.43492263555526733, "metadata": {"source": "Indigo oxidation mechanism in grottoes murals by ozone", "source_file": "Indigo oxidation mechanism in grottoes murals by ozone", "year": "2023", "ingest_kind": "pdf_fulltext", "page": "8", "chunk_index": "24", "title": "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions", "doi": "10.1186/s40494-023-00887-7", "journal": "Heritage Science"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C8H5NO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Verification of the reaction mechanism by experiment As shown in Fig. 2b, when the air was exposed to indigo at a constant flow rate for 2.5 h the colour of indigo barely changed and was subsequently dissolved in DMSO and Fig. 6 a HPLC of indigo before and after reaction with O3 and HPLC of isatin; b Fluorescence spectrum of indigo before and after reaction with O3 and fluorescence spectrum of isatin", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "isatin", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Page 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.", "score": 0.45905977487564087, "metadata": {"page": "8", "source": "Indigo oxidation mechanism in grottoes murals by ozone", "title": "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions", "ingest_kind": "pdf_fulltext", "source_file": "Indigo oxidation mechanism in grottoes murals by ozone", "doi": "10.1186/s40494-023-00887-7", "year": "2023", "journal": "Heritage Science", "chunk_index": "22"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C8H5NO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Page 8 of 12Li et al. Heritage Science (2023) 11:50 the O atoms on the C atom, the O atoms at the ends of the O3 molecule first combine with the C=C of the indigo molecule to form a five-membered ring, and O1 of the original O3 molecule breaks with O2, followed by a C–C break to form an isatin molecule and criegee radical, as shown in Additional file 1: Figure S6a.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "isatin", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Page 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "score": null, "snippets": [{"text": "Page 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "score": null, "metadata": {"ingest_kind": "pdf_fulltext", "chunk_index": "25", "year": "2023", "doi": "10.1186/s40494-023-00887-7", "page": "9", "source": "Indigo oxidation mechanism in grottoes murals by ozone", "title": "A study of the oxidation mechanism of the organic pigment indigo in grottoes murals by ozone under dark conditions", "journal": "Heritage Science", "source_file": "Indigo oxidation mechanism in grottoes murals by ozone"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C8H5NO2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Page 9 of 12 Li et al. Heritage Science (2023) 11:50 Fig. 7 a Mass spectra of indigo molecules detected in indigo standard solution; b Mass spectra of residual indigo molecules detected in indigo solution after reaction with O3; c Mass spectra of product isatin molecules detected in indigo solution after reaction with O3; d Mass spectra of product C8H6NO3 detected in indigo solution after reaction with O3; e Mass spectra of product molecules C16H10N2O3 detected in indigo solution after reaction with O3", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "isatin", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 46, "resolver_kept": 3, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 168, "lexical_kept": 3, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/d723e1421868ad4bd81008290ccf844f21eac500.json b/rag_report_cache/d723e1421868ad4bd81008290ccf844f21eac500.json
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index 0000000000000000000000000000000000000000..c808ee4f8f45170292bfbec8547e1b91dd9c22a9
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+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Chloride]--> CuCl2", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["DOMÉNECH‐CARBÓ MT, EDWARDS HGM, DOMÉNECH‐CARBÓ A, et al. An authentication case study: Antonio Palomino versus Vicente Guillo paintings in the vaulted ceiling of the Sant Joan del Mercat church (Valencia, Spain) [J/OL]. Journal of Raman Spectroscopy, 2012. DOI: 10.1002/jrs.3168."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [{"source": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:13. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "snippet": "is formed. The effect of laser irradiation on azurite is the formation of black CuO, which depends on the particle size and therefore on the temperature increase [112, 114, 125]. Selective biological activity is observed towards lead pigments [124]. Malachite (CuCO3·Cu(OH)2, green) Malachite (CuCO 3·Cu(OH)2) is more stable than azurite (2CuCO 3·Cu(OH)2) and verdigris (xCu(CH3COO2)·yCu(OH)2·zH2O), therefore showing less or slower reactivity towards many factors [119, 123]. It is known to be permanent in all binding media, light - fast and alkali proof. Its deeper colour is obtained by coarse grinding, and as a consequence of having relatively low refractive index, it shows better performances in tempera than in oil [50, 126]. Due to its chemical com - position, malachite is subject to interactions with acids, bases, humidity, temperature and circulating ions. In presence of humidity, malachite stains can be observed, which are actually caused by proteinaceous binders deg - radation [64]. Moreover, ions such as Cl − present in the mortar, sand or in the bricks, can react with the basic car- bonate to form copper hydroxychlorides ((Cu 2Cl(OH)3) atacamite, clinoatacamite, paratacamite botallackite) [119, 121, 123, 126–128] and the copper chloride nan - tokite [103]. Sulphate ions are also likely to be present in wall paintings, especially from the degradation of calcite to gypsum, from gypsum preparation layers [53], or from SO 2/SO3 pollution.", "retrieval_origin": "bge_m3", "match": {"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuCl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "In presence of humidity, malachite stains can be observed, which are actually caused by proteinaceous binders deg - radation [64]. Moreover, ions such as Cl − present in the mortar, sand or in the bricks, can react with the basic car- bonate to form copper hydroxychlorides ((Cu2Cl(OH)3) atacamite, clinoatacamite, paratacamite botallackite) [119, 121, 123, 126–128] and the copper chloride nan - tokite [103].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "copper chloride", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1.", "snippet": "Characterisation of rouaite, an unusual copper‐containing pigment in early modern English... Page 11 of 18 817 The sample pattern is much better represented by rouaite, while several significant gerhardtite peaks are not observed (2/u1D703 = 25.2, 34.1, 34.6). Rietveld refinement on diffraction data extracted from rouaite containing regions of T1 was carried out in TOPAS to further investigate the possible presence of gerhardtite, with results presented in Fig. 6e. While it is possible to fit gerhardtite with reasonable residuals, fewer peaks are accounted for and the quality of the fit is not as good as the fit when rouaite is used instead. The presence of rouaite rather than gerhardtite strongly supports a synthetic origin for the pigment, possibly from a failed blue verditer synthesis attempt. The basic copper chlorides atacamite and clinoatacamite have very similar diffraction patterns, and the difficulty of identifying specific polymorphs is compounded by the pres- ence of other phases and the influence of preferred orienta- tion on peak intensities. Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition. Cu and Cl ", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuCl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "copper chloride", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424.", "snippet": "of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups. Part 1 is entitled Accelerated aging of smalt- and lapis lazuli-based paints, while this paper, Part 2, studies azurite- and malachite-based paints, made by mixing one of the pigments with either egg yolk or rabbit glue binder, which were then exposed to SO2 for two months in order to examine the effect of this gas pollutant on the physical -chemical properties of the paints. We studied the physical (color, gloss, reflectance, and roughness values), mineralogical (XRD), molecular (FTIR), and chemical, micro-textural, and micro-morphological (SEM-EDS) characteristics of fresh and aged paint mock-ups in order to detect evidence of sulfation leading to the formation of new minerals in the paints. 2. Materials and Methods 2.1. Tempera Paint Mock-Ups Azurite (AZ h", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuCl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "copper chloride", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 15, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 184, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/d7c9f42ee4397d0a70ed8e6cf6f04640b3724ce4.json b/rag_report_cache/d7c9f42ee4397d0a70ed8e6cf6f04640b3724ce4.json
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index 0000000000000000000000000000000000000000..c17704b03f20e28b32c8a6b5a6e6dd78dc6230cf
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+{"root_material": "As4S4", "path_str": "As4S4 --[Uv]--> As4S5 --[Uv]--> p-As4S4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 2: direct\nTransformation of the intermediate As4S5 to pararealgar proceeds by dissociation of one sulfur atom (S2) and rebonding of the rest of the molecule, with the new sulfur atom (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2). This means that the fragment As2As3S4As4S3 is the half-molecule fragment that (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2). This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c). On the basis of the previously presented results, it was not possible to address entirely the issue of whether the photoinduced transformation of realgar is an intermolecular or intramolecular process. Although the bond distances in the two points probed here imply an intramolecular process, this hypothesis needed to be supported with a step-by-step structural analysis at several points of the transformation, which would afford the time-dependent changes of atom populations.\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nThis means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c). On the basis of the previously presented results, it was not possible to address entirely the issue of whether the photoinduced transformation of realgar is an intermolecular or intramolecular process.\n\n[1] Evidence classification: edge 2: direct\nTransformation of the intermediate As4S5 to pararealgar proceeds by dissociation of one sulfur atom (S2) and rebonding of the rest of the molecule, with the new sulfur atom (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2).\n\n[1] Evidence classification: edge 2: direct\nThe process continues through a set of cyclic reactions in which the sulfur atom released by the decomposition of As4S5 (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nThe photodiffraction (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.\n\n[1] Evidence classification: edge 2: direct\nAt point (d), the cell shrinks abruptly as a result of uzonite depletion due to the conversion to pararealgar (V/Z= 201.71 A{}^{3}) [34] (Table 1), which ultimately triggers crystal disintegration.\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nAlthough the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nAs it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].\n\n[1] Evidence classification: edge 2: direct\nReactions 3 and 4 proceed autocatalytically, and the cell expands slightly up to point (e) (t\\approx 80 h), which is close to point (d) of the light phase (t\\approx 85 h). After point (e), the uzonite transforms into pararealgar, and the cell shrinks up to point (f).\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\n\n[1] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).\n\n[2] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nThe Light-Induced Alteration of Realgar to Pararealgar.\n\n[3] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nSmall quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.\n\n[3] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nTherefore, the migrat uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.\n\n[3] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nuch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.\n\n[4] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nRealgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].\n\n[4] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nBefore this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].\n\n[4] Evidence classification: edge 2: direct, pathway endpoints As4S4 -> p-As4S4: direct\nRadiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].\n\n[5] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nExposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].\n\n[6] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nThe light‐induced alteration of realgar to pararealgar.\n\n[7] Evidence classification: pathway endpoints As4S4 -> p-As4S4: direct\nThe light-induced alteration of realgar to pararealgar.", "ref_list": ["JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9.", "BROERS FTH, JANSSENS K, WEKER JN, et al. Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings [J/OL]. Journal of the American Chemical Society, 2023. DOI: 10.1021/jacs.2c12271.", "VERMEULEN M, SAVERWYNS S, COUDRAY A, et al. Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments [J/OL]. Dyes and Pigments, 2018. DOI: 10.1016/j.dyepig.2017.10.009.", "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization [J/OL]. Heritage Science, 2024. DOI: 10.1186/s40494-024-01350-x. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:16. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:24. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "KEUNE K, MASS J, MEHTA A, et al. Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues [J/OL]. Heritage Science, 2016. DOI: 10.1186/s40494-016-0078-1."], "ref_snippets": [{"text": "Transformation of the intermediate As4S5 to pararealgar proceeds by dissociation of one sulfur atom (S2) and rebonding of the rest of the molecule, with the new sulfur atom (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2). This means that the fragment As2As3S4As4S3 is the half-molecule fragment that (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2). This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c). On the basis of the previously presented results, it was not possible to address entirely the issue of whether the photoinduced transformation of realgar is an intermolecular or intramolecular process. Although the bond distances in the two points probed here imply an intramolecular process, this hypothesis needed to be supported with a step-by-step structural analysis at several points of the transformation, which would afford the time-dependent changes of atom populations.\nThis means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c). On the basis of the previously presented results, it was not possible to address entirely the issue of whether the photoinduced transformation of realgar is an intermolecular or intramolecular process.\nTransformation of the intermediate As4S5 to pararealgar proceeds by dissociation of one sulfur atom (S2) and rebonding of the rest of the molecule, with the new sulfur atom (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2).\nThe process continues through a set of cyclic reactions in which the sulfur atom released by the decomposition of As4S5 (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\nThe photodiffraction (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.\nAt point (d), the cell shrinks abruptly as a result of uzonite depletion due to the conversion to pararealgar (V/Z= 201.71 A{}^{3}) [34] (Table 1), which ultimately triggers crystal disintegration.\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\nAlthough the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\nAs it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].\nReactions 3 and 4 proceed autocatalytically, and the cell expands slightly up to point (e) (t\\approx 80 h), which is close to point (d) of the light phase (t\\approx 85 h). After point (e), the uzonite transforms into pararealgar, and the cell shrinks up to point (f).\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": 0.43365395069122314, "snippets": [{"text": "Transformation of the intermediate As4S5 to pararealgar proceeds by dissociation of one sulfur atom (S2) and rebonding of the rest of the molecule, with the new sulfur atom (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2). This means that the fragment As2As3S4As4S3 is the half-molecule fragment that (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2). This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c). On the basis of the previously presented results, it was not possible to address entirely the issue of whether the photoinduced transformation of realgar is an intermolecular or intramolecular process. Although the bond distances in the two points probed here imply an intramolecular process, this hypothesis needed to be supported with a step-by-step structural analysis at several points of the transformation, which would afford the time-dependent changes of atom populations.", "score": 0.4976446032524109, "metadata": {"journal": "ChemTexts", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "year": "2020", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 61, "doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "As4S5", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Transformation of the intermediate As4S5 to pararealgar proceeds by dissociation of one sulfur atom (S2) and rebonding of the rest of the molecule, with the new sulfur atom (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2). This means that the fragment As2As3S4As4S3 is the half-molecule fragment that (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2). This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c). On the basis of the previously presented results, it was not possible to address entirely the issue of whether the photoinduced transformation of realgar is an intermolecular or intramolecular process. Although the bond distances in the two points probed here imply an intramolecular process, this hypothesis needed to be supported with a step-by-step structural analysis at several points of the transformation, which would afford the time-dependent changes of atom populations.", "reactant_match": "exact", "product_match": "alias", "reactant_span": "As4S5", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c). On the basis of the previously presented results, it was not possible to address entirely the issue of whether the photoinduced transformation of realgar is an intermolecular or intramolecular process.", "score": 0.4976446032524109, "metadata": {"journal": "ChemTexts", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "year": "2020", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 61, "doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c). On the basis of the previously presented results, it was not possible to address entirely the issue of whether the photoinduced transformation of realgar is an intermolecular or intramolecular process.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Transformation of the intermediate As4S5 to pararealgar proceeds by dissociation of one sulfur atom (S2) and rebonding of the rest of the molecule, with the new sulfur atom (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2).", "score": 0.5221474170684814, "metadata": {"year": "2020", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "chunk_index": 60, "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "As4S5", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Transformation of the intermediate As4S5 to pararealgar proceeds by dissociation of one sulfur atom (S2) and rebonding of the rest of the molecule, with the new sulfur atom (S5') taking the position of one of the As atoms (As1), which in turn (As1') has replaced the leaving sulfur atom (S2).", "reactant_match": "exact", "product_match": "alias", "reactant_span": "As4S5", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The process continues through a set of cyclic reactions in which the sulfur atom released by the decomposition of As4S5 (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "score": 0.43365395069122314, "metadata": {"chunk_index": 2, "year": "2020", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "doi": "10.1007/s40828-019-0100-9", "journal": "ChemTexts", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "As4S5", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The process continues through a set of cyclic reactions in which the sulfur atom released by the decomposition of As4S5 (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "reactant_match": "exact", "product_match": "alias", "reactant_span": "As4S5", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The photodiffraction (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "score": 0.43365395069122314, "metadata": {"chunk_index": 2, "year": "2020", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "doi": "10.1007/s40828-019-0100-9", "journal": "ChemTexts", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The photodiffraction (step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.", "score": 0.4369722008705139, "metadata": {"source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "journal": "ChemTexts", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "chunk_index": 1, "year": "2020", "doi": "10.1007/s40828-019-0100-9", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical", "resolver", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "At point (d), the cell shrinks abruptly as a result of uzonite depletion due to the conversion to pararealgar (V/Z= 201.71 A{}^{3}) [34] (Table 1), which ultimately triggers crystal disintegration.", "score": 0.45783889293670654, "metadata": {"source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "year": "2020", "chunk_index": 67, "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "As4S5", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "At point (d), the cell shrinks abruptly as a result of uzonite depletion due to the conversion to pararealgar (V/Z= 201.71 A{}^{3}) [34] (Table 1), which ultimately triggers crystal disintegration.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "uzonite", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "score": 0.5056250691413879, "metadata": {"title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 42, "ingest_kind": "existing_chroma", "doi": "10.1007/s40828-019-0100-9", "year": "2020", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Although the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.", "score": 0.4884721040725708, "metadata": {"source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 35, "ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "year": "2020", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Although the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "score": null, "metadata": {"journal": "ChemTexts", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "doi": "10.1007/s40828-019-0100-9", "chunk_index": 3, "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "ingest_kind": "existing_chroma", "year": "2020", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "score": null, "metadata": {"year": "2020", "doi": "10.1007/s40828-019-0100-9", "journal": "ChemTexts", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "chunk_index": 43, "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "As it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].", "score": null, "metadata": {"title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "year": "2020", "ingest_kind": "existing_chroma", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 62, "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "As it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Reactions 3 and 4 proceed autocatalytically, and the cell expands slightly up to point (e) (t\\approx 80 h), which is close to point (d) of the light phase (t\\approx 85 h). After point (e), the uzonite transforms into pararealgar, and the cell shrinks up to point (f).", "score": null, "metadata": {"source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 69, "ingest_kind": "existing_chroma", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "journal": "ChemTexts", "doi": "10.1007/s40828-019-0100-9", "year": "2020", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "As4S5", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Reactions 3 and 4 proceed autocatalytically, and the cell expands slightly up to point (e) (t\\approx 80 h), which is close to point (d) of the light phase (t\\approx 85 h). After point (e), the uzonite transforms into pararealgar, and the cell shrinks up to point (f).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "uzonite", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "score": null, "metadata": {"doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "chunk_index": 73, "year": "2020", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": null, "metadata": {"title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "journal": "ChemTexts", "year": "2020", "chunk_index": 75, "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "doi": "10.1007/s40828-019-0100-9", "ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The Light-Induced Alteration of Realgar to Pararealgar.", "score": 0.5079103708267212, "snippets": [{"text": "The Light-Induced Alteration of Realgar to Pararealgar.", "score": 0.5079103708267212, "metadata": {"chunk_index": 36, "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "page": 13, "doi": "10.1021/jacs.2c12271", "year": "2023", "license": "https://creativecommons.org/licenses/by/4.0/", "journal": "Journal of the American Chemical Society", "ingest_kind": "pdf_fulltext", "source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The Light-Induced Alteration of Realgar to Pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Small quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.\nTherefore, the migrat uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.\nuch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "score": null, "snippets": [{"text": "Small quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.", "score": null, "metadata": {"title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "year": "2018", "chunk_index": 3, "journal": "Dyes and Pigments", "doi": "10.1016/j.dyepig.2017.10.009", "source": "pdf_reextract/雄黄", "ingest_kind": "pdf_reextract"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Small quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Therefore, the migrat uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "score": null, "metadata": {"journal": "Dyes and Pigments", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "chunk_index": 24, "ingest_kind": "pdf_reextract", "year": "2018", "doi": "10.1016/j.dyepig.2017.10.009", "source": "pdf_reextract/雄黄"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Therefore, the migrat uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "score": null, "metadata": {"journal": "Dyes and Pigments", "year": "2018", "source": "pdf_reextract/雄黄", "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "ingest_kind": "pdf_reextract", "chunk_index": 25, "doi": "10.1016/j.dyepig.2017.10.009"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Realgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].\nBefore this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].\nRadiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "score": null, "snippets": [{"text": "Realgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].", "score": null, "metadata": {"chunk_index": 7, "journal": "Heritage Science", "source_file": "s40494-024-01350-x.pdf", "ingest_kind": "pdf_direct", "doi": "10.1186/s40494-024-01350-x", "source": "pdf_direct/s40494-024-01350-x", "year": "2024", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Realgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].", "score": null, "metadata": {"source_file": "s40494-024-01350-x.pdf", "source": "pdf_direct/s40494-024-01350-x", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization", "journal": "Heritage Science", "year": "2024", "chunk_index": 9, "doi": "10.1186/s40494-024-01350-x", "ingest_kind": "pdf_direct"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Radiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "score": null, "metadata": {"source": "pdf_direct/s40494-024-01350-x", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization", "chunk_index": 19, "year": "2024", "ingest_kind": "pdf_direct", "journal": "Heritage Science", "source_file": "s40494-024-01350-x.pdf", "doi": "10.1186/s40494-024-01350-x"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical", "resolver"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "As4S5", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Radiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "alacranite", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Radiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "score": null, "snippets": [{"text": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "score": null, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "page": "16", "ingest_kind": "pdf_fulltext", "chunk_index": "53", "source_file": "On the stability of mediaeval inorganic pigments - a review", "doi": "10.1186/s40494-017-0125-6", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "journal": "Heritage Science"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The light‐induced alteration of realgar to pararealgar.", "score": null, "snippets": [{"text": "The light‐induced alteration of realgar to pararealgar.", "score": null, "metadata": {"source_file": "On the stability of mediaeval inorganic pigments - a review", "year": "2017", "chunk_index": "102", "journal": "Heritage Science", "page": "24", "source": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext", "doi": "10.1186/s40494-017-0125-6", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The light‐induced alteration of realgar to pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The light-induced alteration of realgar to pararealgar.", "score": null, "snippets": [{"text": "The light-induced alteration of realgar to pararealgar.", "score": null, "metadata": {"doi": "10.1186/s40494-016-0078-1", "chunk_index": 34, "ingest_kind": "pdf_direct", "source_file": "s40494-016-0078-1.pdf", "title": "Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues", "year": "2016", "source": "pdf_direct/s40494-016-0078-1", "journal": "Heritage Science"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The light-induced alteration of realgar to pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 8, "resolver_scanned": 2314, "resolver_candidates": 18, "resolver_kept": 7, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 3, "lexical_scanned": 2314, "lexical_candidates": 146, "lexical_kept": 25, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/d85741f3c543604f00e1dad2814a52df5b19a730.json b/rag_report_cache/d85741f3c543604f00e1dad2814a52df5b19a730.json
new file mode 100644
index 0000000000000000000000000000000000000000..16a25d1366cb630524b5675b9c038965c0e83777
--- /dev/null
+++ b/rag_report_cache/d85741f3c543604f00e1dad2814a52df5b19a730.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Chloride]--> Cu2Cl(OH)3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nMinerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.\n\n[2] Evidence classification: edge 1: direct\nThe alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "ref_list": ["PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1.", "MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "DOMÉNECH‐CARBÓ MT, EDWARDS HGM, DOMÉNECH‐CARBÓ A, et al. An authentication case study: Antonio Palomino versus Vicente Guillo paintings in the vaulted ceiling of the Sant Joan del Mercat church (Valencia, Spain) [J/OL]. Journal of Raman Spectroscopy, 2012. DOI: 10.1002/jrs.3168."], "ref_snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "metadata": {"source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "year": "2024", "doi": "10.1007/s00339-024-07954-1", "journal": "Applied Physics A", "chunk_index": 23, "license": "https://creativecommons.org/licenses/by/4.0", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "page": 12, "ingest_kind": "pdf_fulltext", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "snippets": [{"text": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "score": null, "metadata": {"journal": "Journal of Raman Spectroscopy", "title": "Raman spectroscopic analysis of azurite blackening", "year": "2008", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "doi": "10.1002/jrs.1845", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "chunk_index": 1, "ingest_kind": "pdf_reextract"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The alteration most frequently studied is the discoloration from blue to green due to the degradation of azurite into malachite 3 (a similar basic copper carbonate, (CuCO 3ÐCu(OH)2)o ri n t o any basic copper chloride 4 (into one of the three isomers atacamite, paratacamite or clinoatacamite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "clinoatacamite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 24, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 185, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
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+{"root_material": "As4S4", "path_str": "As4S4 --[Uv]--> p-As4S4 --[Uv]--> As2O3", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThis means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).\n\n[1] Evidence classification: edge 1: direct\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.\n\n[1] Evidence classification: edge 1: direct\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.\n\n[1] Evidence classification: edge 1: direct\nFigure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).\n\n[1] Evidence classification: edge 1: direct\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\n\n[1] Evidence classification: edge 1: direct\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\n\n[1] Evidence classification: edge 1: direct\nAlthough the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.\n\n[1] Evidence classification: edge 1: direct\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\n\n[1] Evidence classification: edge 1: direct\nAs it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].\n\n[1] Evidence classification: edge 1: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\n\n[1] Evidence classification: edge 1: direct\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).\n\n[2] Evidence classification: edge 2: direct, pathway endpoints As4S4 -> As2O3: direct\nArsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.\n\n[2] Evidence classification: edge 1: direct\nRealgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].\n\n[2] Evidence classification: edge 2: direct\nPararealgar can degrade further to arsenic trioxide. During the degradation also the metastable χ-phase is formed [71]. The As-containing components found in artworks are (therefore) often complex mixtures of several compounds and difficult to trace back to the original recipe. In general, when arsenic sulfides pigments are present in oil paintings, these are often simply described as “orpiment and/or realgar” , even though, as described above, many other arsenic sulfide pigments were available from the fifteenth century onwards. Typically, the identification of arsenic sulfides is often based on visual appearance, light microscopy, and elemental analysis.\n\n[2] Evidence classification: edge 1: direct\nBefore this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].\n\n[2] Evidence classification: edge 1: direct\nRadiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].\n\n[3] Evidence classification: edge 1: direct\nThe Light-Induced Alteration of Realgar to Pararealgar.\n\n[4] Evidence classification: edge 2: direct, pathway endpoints As4S4 -> As2O3: direct\nThe highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].\n\n[4] Evidence classification: edge 1: direct\nThe light-induced alteration of realgar to pararealgar.\n\n[5] Evidence classification: edge 1: direct\nSmall quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.\n\n[5] Evidence classification: edge 1: direct\nAs such, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58].\n\n[5] Evidence classification: edge 2: direct\nHowever, arsenic oxide is also an expected degradation product of pararealgar itself [58].\n\n[5] Evidence classification: edge 1: direct\nuch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.\n\n[5] Evidence classification: edge 2: direct\nHowever, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light. Therefore, if realgar would have been used to synthesized the pigment, it ought to be found in this area as it is observed for natural orpiment [8,59].\n\n[6] Evidence classification: edge 1: direct, pathway endpoints As4S4 -> As2O3: direct\nExposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].\n\n[7] Evidence classification: edge 1: direct\nThe light‐induced alteration of realgar to pararealgar.", "ref_list": ["JOVANOVSKI G, MAKRESKI P. Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization [J/OL]. ChemTexts, 2020. DOI: 10.1007/s40828-019-0100-9.", "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization [J/OL]. Heritage Science, 2024. DOI: 10.1186/s40494-024-01350-x. (bibliographic metadata partially available)", "BROERS FTH, JANSSENS K, WEKER JN, et al. Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings [J/OL]. Journal of the American Chemical Society, 2023. DOI: 10.1021/jacs.2c12271.", "KEUNE K, MASS J, MEHTA A, et al. Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues [J/OL]. Heritage Science, 2016. DOI: 10.1186/s40494-016-0078-1.", "VERMEULEN M, SAVERWYNS S, COUDRAY A, et al. Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments [J/OL]. Dyes and Pigments, 2018. DOI: 10.1016/j.dyepig.2017.10.009.", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:16. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)", "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments [J/OL]. Heritage Science, 2017:24. DOI: 10.1186/s40494-017-0125-6. (bibliographic metadata partially available)"], "ref_snippets": [{"text": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).\nIt summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.\nFigure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\n(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration\nAlthough the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.\n### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction\nAs it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in\nThe systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": 0.4454336166381836, "snippets": [{"text": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).", "score": 0.5155298709869385, "metadata": {"ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "year": "2020", "journal": "ChemTexts", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "doi": "10.1007/s40828-019-0100-9", "chunk_index": 61, "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "This means that the fragment As2As3S4As4S3 is the half-molecule fragment that survives the transformation of realgar to pararealgar as As2As3'S4As4S3' (Fig. 7c).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.", "score": 0.4454336166381836, "metadata": {"doi": "10.1007/s40828-019-0100-9", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "chunk_index": 1, "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "year": "2020", "ingest_kind": "existing_chroma", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "It summarizes the results of a detailed study of the reaction mechanism of photoinduced solid-state transformation of the mineral realgar (alpha-As4S4) to its distinct polymorph pararealgar by a combination of in situ single-crystal X-ray photodiffraction, Fourier transform infrared spectroscopy, and micro-Raman spectroscopy.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.", "score": 0.45685338973999023, "metadata": {"chunk_index": 2, "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "year": "2020", "ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "doi": "10.1007/s40828-019-0100-9", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Figure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).", "score": 0.4743976593017578, "metadata": {"doi": "10.1007/s40828-019-0100-9", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "ingest_kind": "existing_chroma", "chunk_index": 67, "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "year": "2020", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Figure 8: Temporal profiles and kinetic constants of the conversion of realgar to pararealgar induced by excitation at 1.96 eV and monitored by the reaction extent, expressed as the normalized integrated intensity of the 274 cm{}^{-1} Raman band of pararealgar (green, blue, and red marks correspond to excitation at 24.2, 10.3, and 1.5 kW/cm{}^{2}, respectively).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "score": 0.5056250691413879, "metadata": {"journal": "ChemTexts", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "ingest_kind": "existing_chroma", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "year": "2020", "chunk_index": 42, "doi": "10.1007/s40828-019-0100-9", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light ### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "score": null, "metadata": {"ingest_kind": "existing_chroma", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "doi": "10.1007/s40828-019-0100-9", "year": "2020", "journal": "ChemTexts", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 3, "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "(step 2) reacts with a molecule of realgar to produce a molecule of pararealgar (step 3), whereupon a sulfur atom is released which continues the process (step 4). The photodiffraction technique provides direct atomic resolution evidence of formation of intermediate As4S5 phase in which half of the realgar molecule retains its envelope-type conformation, while the geometry of the other half is transformed by effective switching of positions of one sulfur and one arsenic atom. The migration (hopping) of sulfur atoms between the molecules of the single crystal of realgar is observed and visualized. Polymorphs of minerals Phase transitions of polymorphs Realgar-pararealgar Photoinduced solid-state transition Single-crystal X-ray photodiffraction FTIR spectroscopy Raman spectroscopy Sulfur atom migration", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Although the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.", "score": null, "metadata": {"doi": "10.1007/s40828-019-0100-9", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "chunk_index": 34, "ingest_kind": "existing_chroma", "year": "2020", "journal": "ChemTexts", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Although the complete mechanism of the photoinduced transformation of realgar to pararealgar on the atomic scale has been unraveled, the interest to continue exploring the light-induced transformation in the scientific community (by means of FTIR [75; 76], Raman spectroscopy [75; 76; 77], and X-ray diffraction [75; 77]) remains. In addition, recently the multistage reverse transformation of pararealgar to both As4S4 phases (beta-As4S4 and realgar) was revealed and described by X-ray powder diffraction (XRPD) [78] leading to better understanding of the photoinduced solid-solid transformation among these three As4S4 phases.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "score": null, "metadata": {"chunk_index": 43, "doi": "10.1007/s40828-019-0100-9", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "ingest_kind": "existing_chroma", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "journal": "ChemTexts", "year": "2020", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "### Monitoring of the transition with Raman spectroscopy #### Irradiation by laser light Compared to the approximately 180 days required for transformation of realgar to pararealgar during sunlight irradiation, we have used the laser excitation of 632.8 nm that fits within the established 500-670 nm region [33] appropriate for the realgar-pararealgar photoconversion. By irradiation of the natural realgar, carried out by adjusting the power intensity to 10.3 kW/cm{}^{2} (although we have conducted two successful additional measurements at 1.5 and 24.2 kW/cm{}^{2}, not presented here), the photoconversion was completed in about 3 h and afforded a final Raman spectrum that fully conforms to the corresponding spectrum of pure pararealgar (Fig. 6) [47]. ### Direct observation of the transition with single-crystal X-ray photodiffraction", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "As it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].", "score": null, "metadata": {"chunk_index": 62, "journal": "ChemTexts", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "doi": "10.1007/s40828-019-0100-9", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "year": "2020", "ingest_kind": "existing_chroma", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "As it was already mentioned, once very small red crystals of realgar are exposed to direct visible light, they convert slowly to a yellow powder of pararealgar, and the process continues even after they have been stored in the dark [60].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "score": null, "metadata": {"journal": "ChemTexts", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "chunk_index": 73, "doi": "10.1007/s40828-019-0100-9", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "year": "2020", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "score": null, "metadata": {"ingest_kind": "existing_chroma", "source_file": "Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "source": "markdown_output/Intriguing minerals: photoinduced solid‑state transition of realgar to pararealgar—direct atomic scale observation and visualization.md", "year": "2020", "title": "Intriguing minerals: photoinduced solid-state transition of realgar to pararealgar—direct atomic scale observation and visualization", "doi": "10.1007/s40828-019-0100-9", "chunk_index": 75, "journal": "ChemTexts", "authors": [{"family": "Jovanovski", "given": "Gligor"}, {"family": "Makreski", "given": "Petre"}], "volume": "6", "issue": "1", "article_number": "5", "url": "https://doi.org/10.1007/s40828-019-0100-9"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The systematic knowledge gained from the photoinduced transformation of realgar to pararealgar has implications for the conservation of minerals and their optimal storage. Namely, the destruction of realgar samples should be avoided or at least slowed down by proposing safety measures to eliminate the possibility for its solid-solid photo-transformation. Having in mind that mineral photoconversion essentially needs combination of oxygen atmosphere and visible light in the 500-670 nm region, one should prevent either the presence of oxygen or the presence of light. However, because transparent exhibition box-windows are needed to constantly monitor and observe the real mineral color of the sample by naked eye, it is recommended to either keep the realgar samples in air-evacuated (vacuum) conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both). One procedure that might overcome the light problem is placing the realgar specimens in conditions or keep the samples in an inert gas atmospheric chamber (or a subsequent combination of both).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Arsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.\nRealgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].\nPararealgar can degrade further to arsenic trioxide. During the degradation also the metastable χ-phase is formed [71]. The As-containing components found in artworks are (therefore) often complex mixtures of several compounds and difficult to trace back to the original recipe. In general, when arsenic sulfides pigments are present in oil paintings, these are often simply described as “orpiment and/or realgar” , even though, as described above, many other arsenic sulfide pigments were available from the fifteenth century onwards. Typically, the identification of arsenic sulfides is often based on visual appearance, light microscopy, and elemental analysis.\nBefore this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].\nRadiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "score": 0.49438923597335815, "snippets": [{"text": "Arsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.", "score": 0.49438923597335815, "metadata": {"title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization", "source": "pdf_direct/s40494-024-01350-x", "year": "2024", "chunk_index": 22, "ingest_kind": "pdf_direct", "source_file": "s40494-024-01350-x.pdf", "doi": "10.1186/s40494-024-01350-x", "journal": "Heritage Science"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "p-As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Arsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "pararealgar", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Arsenolite is known to be a light-induced degradation product of orpiment and pararealgar, which explains why it is mainly present close to the surface and in the crack of the paint sample, where the highest levels of light exposure can be expected.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "pararealgar", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Realgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].", "score": null, "metadata": {"source": "pdf_direct/s40494-024-01350-x", "ingest_kind": "pdf_direct", "year": "2024", "doi": "10.1186/s40494-024-01350-x", "source_file": "s40494-024-01350-x.pdf", "chunk_index": 7, "journal": "Heritage Science", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Realgar on the other side, is known to degrade to pararealgar within days upon exposure to normal light levels [70].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Pararealgar can degrade further to arsenic trioxide. During the degradation also the metastable χ-phase is formed [71]. The As-containing components found in artworks are (therefore) often complex mixtures of several compounds and difficult to trace back to the original recipe. In general, when arsenic sulfides pigments are present in oil paintings, these are often simply described as “orpiment and/or realgar” , even though, as described above, many other arsenic sulfide pigments were available from the fifteenth century onwards. Typically, the identification of arsenic sulfides is often based on visual appearance, light microscopy, and elemental analysis.", "score": null, "metadata": {"source": "pdf_direct/s40494-024-01350-x", "ingest_kind": "pdf_direct", "year": "2024", "doi": "10.1186/s40494-024-01350-x", "source_file": "s40494-024-01350-x.pdf", "chunk_index": 7, "journal": "Heritage Science", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "p-As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Pararealgar can degrade further to arsenic trioxide. During the degradation also the metastable χ-phase is formed [71]. The As-containing components found in artworks are (therefore) often complex mixtures of several compounds and difficult to trace back to the original recipe. In general, when arsenic sulfides pigments are present in oil paintings, these are often simply described as “orpiment and/or realgar” , even though, as described above, many other arsenic sulfide pigments were available from the fifteenth century onwards. Typically, the identification of arsenic sulfides is often based on visual appearance, light microscopy, and elemental analysis.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "pararealgar", "product_span": "arsenic trioxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].", "score": null, "metadata": {"source": "pdf_direct/s40494-024-01350-x", "doi": "10.1186/s40494-024-01350-x", "chunk_index": 9, "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization", "ingest_kind": "pdf_direct", "journal": "Heritage Science", "source_file": "s40494-024-01350-x.pdf", "year": "2024"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Before this date, the historical sources mention that light exposed realgar forms orpiment, which led to misinterpretation and up until almost 30 years ago, the friable yellow pararealgar generally was identified as orpiment [71, 72].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Radiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "score": null, "metadata": {"chunk_index": 19, "source_file": "s40494-024-01350-x.pdf", "ingest_kind": "pdf_direct", "doi": "10.1186/s40494-024-01350-x", "journal": "Heritage Science", "year": "2024", "source": "pdf_direct/s40494-024-01350-x", "title": "Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Radiation damage Pararealgar is known to be a light-induced degradation product of realgar as well as of the minerals in the alacranite (As8S9) series, both the natural and synthetic phases [2].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The Light-Induced Alteration of Realgar to Pararealgar.", "score": 0.5079103708267212, "snippets": [{"text": "The Light-Induced Alteration of Realgar to Pararealgar.", "score": 0.5079103708267212, "metadata": {"source": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "chunk_index": 36, "year": "2023", "license": "https://creativecommons.org/licenses/by/4.0/", "fulltext_url": "https://pure.uva.nl/ws/files/168418547/broers-et-al-2023-two-pathways-for-the-degradation-of-orpiment-pigment-_as2s3_-found-in-paintings.pdf", "ingest_kind": "pdf_fulltext", "journal": "Journal of the American Chemical Society", "source_file": "Two_Pathways_for_the_Degradation_of_Orpiment_Pigment_As_sub_2_sub_S_sub_3_sub_Found_in_Pai_f17328a8a073.pdf", "doi": "10.1021/jacs.2c12271", "page": 13, "title": "Two Pathways for the Degradation of Orpiment Pigment (As2S3) Found in Paintings"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The Light-Induced Alteration of Realgar to Pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].\nThe light-induced alteration of realgar to pararealgar.", "score": null, "snippets": [{"text": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "score": null, "metadata": {"ingest_kind": "pdf_direct", "source": "pdf_direct/s40494-016-0078-1", "title": "Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues", "chunk_index": 4, "doi": "10.1186/s40494-016-0078-1", "journal": "Heritage Science", "year": "2016", "source_file": "s40494-016-0078-1.pdf", "authors": [{"family": "Keune", "given": "Katrien"}, {"family": "Mass", "given": "Jennifer"}, {"family": "Mehta", "given": "Apurva"}, {"family": "Church", "given": "Jonathan"}, {"family": "Meirer", "given": "Florian"}], "volume": "4", "issue": "1", "article_number": "10", "url": "https://doi.org/10.1186/s40494-016-0078-1"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 2, "reactant": "p-As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "pararealgar", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The highest degradation efficiency is in the green part of the visible light spectrum (530–560 nm) [6]. In the first step of light induced degradation, realgar undergoes poly - morphism and becomes friable and bright yellow, (As xSy, para-realgar) and subsequently degrades further to a white phase (As2O3, arsenolite). The photo-oxidation of orpiment, on the other hand, results directly in a white product (arsenolite), often appearing as a dirty/off white color or an ocherous material because of the presence of an overlying varnish [6, 7]. In objects painted with large fields of orpiment, the degradation is often not uniform, resulting in a mix of ivory to ochre yellow [8]. The deg - radation products of arsenic sulfide pigments have been observed and identified in painted works of art by visual observation, µRaman spectroscopy, and X-ray diffraction [9–18].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "arsenolite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The light-induced alteration of realgar to pararealgar.", "score": null, "metadata": {"doi": "10.1186/s40494-016-0078-1", "journal": "Heritage Science", "ingest_kind": "pdf_direct", "title": "Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues", "chunk_index": 33, "source": "pdf_direct/s40494-016-0078-1", "source_file": "s40494-016-0078-1.pdf", "year": "2016", "authors": [{"family": "Keune", "given": "Katrien"}, {"family": "Mass", "given": "Jennifer"}, {"family": "Mehta", "given": "Apurva"}, {"family": "Church", "given": "Jonathan"}, {"family": "Meirer", "given": "Florian"}], "volume": "4", "issue": "1", "article_number": "10", "url": "https://doi.org/10.1186/s40494-016-0078-1"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The light-induced alteration of realgar to pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Small quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.\nAs such, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58].\nHowever, arsenic oxide is also an expected degradation product of pararealgar itself [58].\nuch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.\nHowever, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light. Therefore, if realgar would have been used to synthesized the pigment, it ought to be found in this area as it is observed for natural orpiment [8,59].", "score": null, "snippets": [{"text": "Small quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.", "score": null, "metadata": {"journal": "Dyes and Pigments", "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "source": "pdf_reextract/雄黄", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "ingest_kind": "pdf_reextract", "doi": "10.1016/j.dyepig.2017.10.009", "year": "2018", "chunk_index": 3}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Small quantities of yellow crystalline pararealgar was obtained by natural light aging of natural realgar (Kremer Pigmente GmbH & Co, Aichstetten, Germany) while orange-red g-As40S60 was considered as reference for the amor- phous arsenic sul fide.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "As such, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58].", "score": null, "metadata": {"source": "pdf_reextract/雄黄", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "chunk_index": 24, "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "ingest_kind": "pdf_reextract", "year": "2018", "journal": "Dyes and Pigments", "doi": "10.1016/j.dyepig.2017.10.009"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "As such, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "However, arsenic oxide is also an expected degradation product of pararealgar itself [58].", "score": null, "metadata": {"source": "pdf_reextract/雄黄", "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "chunk_index": 24, "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments", "ingest_kind": "pdf_reextract", "year": "2018", "journal": "Dyes and Pigments", "doi": "10.1016/j.dyepig.2017.10.009"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "p-As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "However, arsenic oxide is also an expected degradation product of pararealgar itself [58].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "pararealgar", "product_span": "arsenic oxide", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "score": null, "metadata": {"ingest_kind": "pdf_reextract", "journal": "Dyes and Pigments", "source": "pdf_reextract/雄黄", "doi": "10.1016/j.dyepig.2017.10.009", "chunk_index": 25, "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "year": "2018", "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "uch, arsenic oxide and pararealgar have been identi fied as degradation products of the amorphous arsenic sul- fide made from realgar [10]. However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light. Therefore, if realgar would have been used to synthesized the pigment, it ought to be found in this area as it is observed for natural orpiment [8,59].", "score": null, "metadata": {"ingest_kind": "pdf_reextract", "journal": "Dyes and Pigments", "source": "pdf_reextract/雄黄", "doi": "10.1016/j.dyepig.2017.10.009", "chunk_index": 25, "source_file": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments.md", "year": "2018", "title": "Identification by Raman spectroscopy of pararealgar as a starting material in the synthesis of amorphous arsenic sulfide pigments"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "p-As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "However, arsenic oxide is also an expected degradation product of pararealgar itself [58]. Therefore, the migrated arsenic species identi fied in H1 (white line indicated by an arrow in Fig. 3) could not only be due to the degradation of the realgar crys- talline phase found in the glass pigment but can also find its origin in the degradation of the pararealgar remnants found in the amorphous material after its partial sublimation. Consequently, the presence of migrated arsenic degradation products and pararealgar does not ne- cessarily indicate a degradation of natural realgar used as primary source for the amorphous pigment. The analyzed particles in H1 are big enough (ca. 10 μm) to suppose that the center of the particle (where the Raman analyses were per- formed) has not yet been in fluenced by light. Therefore, if realgar would have been used to synthesized the pigment, it ought to be found in this area as it is observed for natural orpiment [8,59].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "pararealgar", "product_span": "arsenic oxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "score": null, "snippets": [{"text": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "score": null, "metadata": {"title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "doi": "10.1186/s40494-017-0125-6", "page": "16", "year": "2017", "chunk_index": "53", "source_file": "On the stability of mediaeval inorganic pigments - a review", "ingest_kind": "pdf_fulltext"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "As4S4", "product": "As2O3", "condition": "Uv", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Exposed to (green) light, both high and low temperature realgar transform into brittle, bright yellow pararealgar [106, 177, 181], and finally to arsenic trioxide (As2O3) [106, 180, 188].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "arsenic trioxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The light‐induced alteration of realgar to pararealgar.", "score": null, "snippets": [{"text": "The light‐induced alteration of realgar to pararealgar.", "score": null, "metadata": {"source": "On the stability of mediaeval inorganic pigments - a review", "journal": "Heritage Science", "chunk_index": "102", "doi": "10.1186/s40494-017-0125-6", "page": "24", "year": "2017", "ingest_kind": "pdf_fulltext", "title": "On the stability of mediaeval inorganic pigments: a literature review of the effect of climate, material selection, biological activity, analysis and conservation treatments", "source_file": "On the stability of mediaeval inorganic pigments - a review"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "As4S4", "product": "p-As4S4", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The light‐induced alteration of realgar to pararealgar.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "realgar", "product_span": "pararealgar", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 7, "resolver_scanned": 2314, "resolver_candidates": 157, "resolver_kept": 26, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 179, "lexical_kept": 26, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/e0765af450c138d1a454925a12b70603d6661d0e.json b/rag_report_cache/e0765af450c138d1a454925a12b70603d6661d0e.json
new file mode 100644
index 0000000000000000000000000000000000000000..1519a5277185c00e1187e7d8859f9c6eb8acbb21
--- /dev/null
+++ b/rag_report_cache/e0765af450c138d1a454925a12b70603d6661d0e.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Biogenic+Sulfate]--> Cu4SO4(OH)6 --[Biogenic+Sulfate]--> Cu3SO4(OH)4 --[Biogenic+Sulfate]--> CuC2O4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: pathway endpoints CuCO3·Cu(OH)2 -> CuC2O4: direct\nComputer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.\n\n[1] Evidence classification: pathway endpoints CuCO3·Cu(OH)2 -> CuC2O4: direct\nTo the best of the authors’ knowledge, this is the first time that moolooite is described as a degradation product of copper green pigments in artwork. Moolooite has been recently found as a corrosion product in coins. 25 The additional presence of calcium oxalate dihydrate (wedd- ellite, CaC 2O4·2H2O) detected in the degraded areas (bands at 1477, 910, and 506 cm -1, see Figure 1b) suggests that the map could have suffered a biological attack. Some authors state that the origin of calcium oxalate is a consequence of the biochemical activity of lichens, fungi, algae, or bacteria that excrete oxalic acid which reacts with the calcium compounds of the surroundings (calcium sulfate in the case of Blaeu’s map). Some authors have found calcium oxalates (weddellite and whedellite) as a trace of biological activity over some artworks, especially stone-made artifacts and building stone materials.", "ref_list": ["CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w."], "ref_snippets": [{"text": "Computer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.\nTo the best of the authors’ knowledge, this is the first time that moolooite is described as a degradation product of copper green pigments in artwork. Moolooite has been recently found as a corrosion product in coins. 25 The additional presence of calcium oxalate dihydrate (wedd- ellite, CaC 2O4·2H2O) detected in the degraded areas (bands at 1477, 910, and 506 cm -1, see Figure 1b) suggests that the map could have suffered a biological attack. Some authors state that the origin of calcium oxalate is a consequence of the biochemical activity of lichens, fungi, algae, or bacteria that excrete oxalic acid which reacts with the calcium compounds of the surroundings (calcium sulfate in the case of Blaeu’s map). Some authors have found calcium oxalates (weddellite and whedellite) as a trace of biological activity over some artworks, especially stone-made artifacts and building stone materials.", "score": null, "snippets": [{"text": "Computer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.", "score": null, "metadata": {"doi": "10.1021/ac800255w", "page": "1", "chunk_index": "0", "ingest_kind": "pdf_fulltext", "year": "2008", "title": "Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence", "source_file": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "journal": "Analytical Chemistry", "source": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "authors": [{"family": "Castro", "given": "Kepa"}, {"family": "Sarmiento", "given": "Alfredo"}, {"family": "Martínez-Arkarazo", "given": "Irantzu"}, {"family": "Madariaga", "given": "Juan Manuel"}, {"family": "Fernández", "given": "Luis Angel"}], "volume": "80", "issue": "11", "pages": "4103-4110", "url": "https://doi.org/10.1021/ac800255w"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "CuCO3·Cu(OH)2", "product": "CuC2O4", "condition": "Biogenic+Sulfate", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Computer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "moolooite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "To the best of the authors’ knowledge, this is the first time that moolooite is described as a degradation product of copper green pigments in artwork. Moolooite has been recently found as a corrosion product in coins. 25 The additional presence of calcium oxalate dihydrate (wedd- ellite, CaC 2O4·2H2O) detected in the degraded areas (bands at 1477, 910, and 506 cm -1, see Figure 1b) suggests that the map could have suffered a biological attack. Some authors state that the origin of calcium oxalate is a consequence of the biochemical activity of lichens, fungi, algae, or bacteria that excrete oxalic acid which reacts with the calcium compounds of the surroundings (calcium sulfate in the case of Blaeu’s map). Some authors have found calcium oxalates (weddellite and whedellite) as a trace of biological activity over some artworks, especially stone-made artifacts and building stone materials.", "score": null, "metadata": {"source_file": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "chunk_index": "12", "year": "2008", "source": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "page": "3", "journal": "Analytical Chemistry", "title": "Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence", "ingest_kind": "pdf_fulltext", "doi": "10.1021/ac800255w", "authors": [{"family": "Castro", "given": "Kepa"}, {"family": "Sarmiento", "given": "Alfredo"}, {"family": "Martínez-Arkarazo", "given": "Irantzu"}, {"family": "Madariaga", "given": "Juan Manuel"}, {"family": "Fernández", "given": "Luis Angel"}], "volume": "80", "issue": "11", "pages": "4103-4110", "url": "https://doi.org/10.1021/ac800255w"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "CuCO3·Cu(OH)2", "product": "CuC2O4", "condition": "Biogenic+Sulfate", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "To the best of the authors’ knowledge, this is the first time that moolooite is described as a degradation product of copper green pigments in artwork. Moolooite has been recently found as a corrosion product in coins. 25 The additional presence of calcium oxalate dihydrate (wedd- ellite, CaC 2O4·2H2O) detected in the degraded areas (bands at 1477, 910, and 506 cm -1, see Figure 1b) suggests that the map could have suffered a biological attack. Some authors state that the origin of calcium oxalate is a consequence of the biochemical activity of lichens, fungi, algae, or bacteria that excrete oxalic acid which reacts with the calcium compounds of the surroundings (calcium sulfate in the case of Blaeu’s map). Some authors have found calcium oxalates (weddellite and whedellite) as a trace of biological activity over some artworks, especially stone-made artifacts and building stone materials.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "copper green", "product_span": "moolooite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 29, "dense_candidates": 580, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 22, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 189, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/e61a8c4014dba0db390b5064dc9b5cc99a2d4ef5.json b/rag_report_cache/e61a8c4014dba0db390b5064dc9b5cc99a2d4ef5.json
new file mode 100644
index 0000000000000000000000000000000000000000..e5e11f7778060e21600075804d5ddb701434efde
--- /dev/null
+++ b/rag_report_cache/e61a8c4014dba0db390b5064dc9b5cc99a2d4ef5.json
@@ -0,0 +1 @@
+{"root_material": "2PbCO3·Pb(OH)2", "path_str": "2PbCO3·Pb(OH)2 --[H2S]--> PbS", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nblack compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2}\n\n[1] Evidence classification: edge 1: direct\nblack compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2} Hydrogen sulfide concentrations were measured where the drawings were stored in 2018.", "ref_list": ["PASTORELLI G, MIRANDA ASO, CLERICI EA, et al. Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation [J/OL]. Microchemical Journal, 2024. DOI: 10.1016/j.microc.2024.109912.", "PASTORELLI G, JENSEN SW, MORETTI B, et al. Experimental investigation of environmental and material factors in darkening of historic and modern lead white [J/OL]. Journal of Cultural Heritage, 2025. DOI: 10.1016/j.culher.2024.11.011."], "ref_snippets": [{"text": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2}\nblack compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2} Hydrogen sulfide concentrations were measured where the drawings were stored in 2018.", "score": 0.43398863077163696, "snippets": [{"text": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2}", "score": 0.43398863077163696, "metadata": {"journal": "Microchemical Journal", "ingest_kind": "existing_chroma", "chunk_index": 39, "source": "markdown_output/Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation.md", "doi": "10.1016/j.microc.2024.109912", "title": "Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation", "year": "2024", "source_file": "Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation.md"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbS", "condition": "H2S", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2}", "reactant_match": "exact", "product_match": "exact", "reactant_span": "2PbCO3Pb(OH)2", "product_span": "PbS", "relation_basis": "explicit_equation", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2} Hydrogen sulfide concentrations were measured where the drawings were stored in 2018.", "score": null, "metadata": {"year": "2024", "doi": "10.1016/j.microc.2024.109912", "title": "Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation", "source": "markdown_output/Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation.md", "journal": "Microchemical Journal", "ingest_kind": "existing_chroma", "source_file": "Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation.md", "chunk_index": 40}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "PbS", "condition": "H2S", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "black compound, was identified near the surface, leading to unsightly blackening of the highlights. The formation of this black phase was attributed to improper conservation conditions that exposed the artwork to elevated levels of H2S. The reaction between lead carbonates and H2S was discussed by Smith et al. [36] and is described by the following chemical equations: 2PbCO3Pb(OH)2\\text{ (s) + 3H2S (g) \\rightarrow 3PBS (s) + 2CO2 (g) + 4H2O (l)} \\tag{1} PbCO3\\text{ (s) + H2S (g) \\rightarrow PbS (s) + CO2 (g) + H2O (l)} \\tag{2} Hydrogen sulfide concentrations were measured where the drawings were stored in 2018.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "2PbCO3Pb(OH)2", "product_span": "PbS", "relation_basis": "explicit_equation", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "contradicted"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 35, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 222, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/e85107035fb38a2f8bc7dd133d8de8f3ae87b7bc.json b/rag_report_cache/e85107035fb38a2f8bc7dd133d8de8f3ae87b7bc.json
new file mode 100644
index 0000000000000000000000000000000000000000..c0013f5e58c8085e07cf0c216796248948e49108
--- /dev/null
+++ b/rag_report_cache/e85107035fb38a2f8bc7dd133d8de8f3ae87b7bc.json
@@ -0,0 +1 @@
+{"root_material": "Pb3O4", "path_str": "Pb3O4 --[H2S]--> PbS", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nIf red lead darkening on frescoes is usually attributed to the formation of plattnerite, most of the studies related to red lead alteration on manuscripts point out its transformation into lead sulfide (galena, PbS). Such a phenomenon may occur through the interaction with atmospheric hydrogen sulfide [70].", "ref_list": ["AZE S, VALLET JM, DETALLE V, et al. Chromatic alterations of red lead pigments in artworks: a review [J/OL]. Phase Transitions, 2008. DOI: 10.1080/01411590701514326."], "ref_snippets": [{"text": "If red lead darkening on frescoes is usually attributed to the formation of plattnerite, most of the studies related to red lead alteration on manuscripts point out its transformation into lead sulfide (galena, PbS). Such a phenomenon may occur through the interaction with atmospheric hydrogen sulfide [70].", "score": 0.4733572006225586, "snippets": [{"text": "If red lead darkening on frescoes is usually attributed to the formation of plattnerite, most of the studies related to red lead alteration on manuscripts point out its transformation into lead sulfide (galena, PbS). Such a phenomenon may occur through the interaction with atmospheric hydrogen sulfide [70].", "score": 0.4733572006225586, "metadata": {"title": "Chromatic alterations of red lead pigments in artworks: a review", "doi": "10.1080/01411590701514326", "source": "markdown_output/Chromatic alterations of red lead pigments in artworks: a review.md", "year": "2008", "source_file": "Chromatic alterations of red lead pigments in artworks: a review.md", "chunk_index": 18, "journal": "Phase Transitions", "ingest_kind": "existing_chroma", "authors": [{"family": "Aze", "given": "S."}, {"family": "Vallet", "given": "J.-M."}, {"family": "Detalle", "given": "V."}, {"family": "Grauby", "given": "O."}, {"family": "Baronnet", "given": "A."}], "volume": "81", "issue": "2-3", "pages": "145-154", "url": "https://doi.org/10.1080/01411590701514326"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "Pb3O4", "product": "PbS", "condition": "H2S", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "If red lead darkening on frescoes is usually attributed to the formation of plattnerite, most of the studies related to red lead alteration on manuscripts point out its transformation into lead sulfide (galena, PbS). Such a phenomenon may occur through the interaction with atmospheric hydrogen sulfide [70].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "red lead", "product_span": "lead sulfide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 1, "resolver_scanned": 2314, "resolver_candidates": 24, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 220, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/e85f3ae83e119ba4705237ad1f77f52aa5f4e9e0.json b/rag_report_cache/e85f3ae83e119ba4705237ad1f77f52aa5f4e9e0.json
new file mode 100644
index 0000000000000000000000000000000000000000..d79fe52036c6691c86a82f58b24576ac2fb90470
--- /dev/null
+++ b/rag_report_cache/e85f3ae83e119ba4705237ad1f77f52aa5f4e9e0.json
@@ -0,0 +1 @@
+{"root_material": "2PbCO3·Pb(OH)2", "path_str": "2PbCO3·Pb(OH)2 --[Chloride]--> β-PbO2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThe same results, for the distribution of two basic copper chlorides, have been obtained in the other areas mapped of CA04. In the area around atacamite and clinonatacamite crystals, the Raman spectra show the presence of plattreite. ## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.\n\n[1] Evidence classification: edge 1: direct\n## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.\n\n[2] Evidence classification: edge 1: direct\nLead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].\n\n[3] Evidence classification: edge 1: direct\nLead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]\n\n[3] Evidence classification: edge 1: direct\nLead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14] Indeed, a previous study, carried out on blackened areas from Cimabue's mural painting samples, showed the presence of plattnerite.[15] A completely degraded layer with a thickness of about 20-40 \\upmum was reported, heavily contaminated with chlorine compounds and without any trace of calcium carbonate.\n\n[3] Evidence classification: edge 1: direct\nFurthermore, hydrocerussite is known to form a mixture of plattnerite and scrutiny, both lead (IV) oxides in chlorinated water solution at pH = 8.1 after 8 days.[31] On these bases, we tested the effect of commercial NaClO (5% aq) on lead white components. Cerussite and hydrocerussite were used as powders to verify the strength of NaClO avoiding the enhancement of a basic environment. In both cases, blackening takes place immediately, and the resultant darkened powders and their XRD are shown in Figure 5. Cerussite reaction with NaClO led to plattnerite and halite (NaCl) as observed by OM and a brown coloration for this sample was noted (Figure 6a). Reaction of hydrocerussite with NaClO led instead to corussite, scrutinyite (\\upalpha-PbO2), halite and plattnerite (\\upbeta-PbO2) showing a red-brownish hue (Figure 6b).\n\n[3] Evidence classification: edge 1: direct\nUpon application of sodium hypochlorite on both hydrocerussite and corussite powders, XRD analyses showed formation of plattnerite and scrutinyite just for hydrocerussite, confirming the higher reactivity of such component.\n\n[3] Evidence classification: edge 1: direct\nFigure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).\n\n[3] Evidence classification: edge 1: direct\nHydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "ref_list": ["VAGNINI M, VIVANI R, VISCUSO E, et al. Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi [J/OL]. Vibrational Spectroscopy, 2018. DOI: 10.1016/j.vibspec.2018.07.006.", "KOTULANOVÁ E, BEZDIČKA P, HRADIL D, et al. Degradation of lead-based pigments by salt solutions [J/OL]. Journal of Cultural Heritage, 2009. DOI: 10.1016/j.culher.2008.11.001.", "VAGNINI M, VIVANI R, SGAMELLOTTI A, et al. Blackening of lead white: Study of model paintings [J/OL]. Journal of Raman Spectroscopy, 2020. DOI: 10.1002/jrs.5879."], "ref_snippets": [{"text": "The same results, for the distribution of two basic copper chlorides, have been obtained in the other areas mapped of CA04. In the area around atacamite and clinonatacamite crystals, the Raman spectra show the presence of plattreite. ## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.\n## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.", "score": null, "snippets": [{"text": "The same results, for the distribution of two basic copper chlorides, have been obtained in the other areas mapped of CA04. In the area around atacamite and clinonatacamite crystals, the Raman spectra show the presence of plattreite. ## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.", "score": null, "metadata": {"doi": "10.1016/j.vibspec.2018.07.006", "source_file": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "title": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi", "year": "2018", "chunk_index": 36, "ingest_kind": "existing_chroma", "source": "markdown_output/Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "journal": "Vibrational Spectroscopy", "authors": [{"family": "Vagnini", "given": "M."}, {"family": "Vivani", "given": "R."}, {"family": "Viscuso", "given": "E."}, {"family": "Favazza", "given": "M."}, {"family": "Brunetti", "given": "B.G."}, {"family": "Sgamellotti", "given": "A."}, {"family": "Miliani", "given": "C."}], "volume": "98", "pages": "41-49", "url": "https://doi.org/10.1016/j.vibspec.2018.07.006"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The same results, for the distribution of two basic copper chlorides, have been obtained in the other areas mapped of CA04. In the area around atacamite and clinonatacamite crystals, the Raman spectra show the presence of plattreite. ## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "lead dioxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.", "score": null, "metadata": {"title": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi", "year": "2018", "source": "markdown_output/Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "chunk_index": 37, "source_file": "Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi.md", "journal": "Vibrational Spectroscopy", "ingest_kind": "existing_chroma", "doi": "10.1016/j.vibspec.2018.07.006", "authors": [{"family": "Vagnini", "given": "M."}, {"family": "Vivani", "given": "R."}, {"family": "Viscuso", "given": "E."}, {"family": "Favazza", "given": "M."}, {"family": "Brunetti", "given": "B.G."}, {"family": "Sgamellotti", "given": "A."}, {"family": "Miliani", "given": "C."}], "volume": "98", "pages": "41-49", "url": "https://doi.org/10.1016/j.vibspec.2018.07.006"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "## 4 Conclusions In conclusion, the study of three samples from blackened areas of a Cimabue's mural painting confirmed the secondary product of lead white darkening alteration to be lead dioxide (plattreite), whose formation implies the occurrence of a redox reaction within the painting layer.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "lead dioxide", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "score": null, "snippets": [{"text": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "score": null, "metadata": {"title": "Degradation of lead-based pigments by salt solutions", "year": "2009", "doi": "10.1016/j.culher.2008.11.001", "source_file": "Degradation of lead-based pigments by salt solutions.md", "source": "markdown_output/Degradation of lead-based pigments by salt solutions.md", "chunk_index": 42, "journal": "Journal of Cultural Heritage", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Lead white and red lead altered to plattnerite has been noted by many authors [13, 14, 34].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]\nLead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14] Indeed, a previous study, carried out on blackened areas from Cimabue's mural painting samples, showed the presence of plattnerite.[15] A completely degraded layer with a thickness of about 20-40 \\upmum was reported, heavily contaminated with chlorine compounds and without any trace of calcium carbonate.\nFurthermore, hydrocerussite is known to form a mixture of plattnerite and scrutiny, both lead (IV) oxides in chlorinated water solution at pH = 8.1 after 8 days.[31] On these bases, we tested the effect of commercial NaClO (5% aq) on lead white components. Cerussite and hydrocerussite were used as powders to verify the strength of NaClO avoiding the enhancement of a basic environment. In both cases, blackening takes place immediately, and the resultant darkened powders and their XRD are shown in Figure 5. Cerussite reaction with NaClO led to plattnerite and halite (NaCl) as observed by OM and a brown coloration for this sample was noted (Figure 6a). Reaction of hydrocerussite with NaClO led instead to corussite, scrutinyite (\\upalpha-PbO2), halite and plattnerite (\\upbeta-PbO2) showing a red-brownish hue (Figure 6b).\nUpon application of sodium hypochlorite on both hydrocerussite and corussite powders, XRD analyses showed formation of plattnerite and scrutinyite just for hydrocerussite, confirming the higher reactivity of such component.\nFigure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).\nHydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "score": null, "snippets": [{"text": "Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]", "score": null, "metadata": {"source_file": "Blackening of lead white: Study of model paintings.md", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "doi": "10.1002/jrs.5879", "chunk_index": 5, "ingest_kind": "existing_chroma", "year": "2020", "journal": "Journal of Raman Spectroscopy", "title": "Blackening of lead white: Study of model paintings"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14]", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14] Indeed, a previous study, carried out on blackened areas from Cimabue's mural painting samples, showed the presence of plattnerite.[15] A completely degraded layer with a thickness of about 20-40 \\upmum was reported, heavily contaminated with chlorine compounds and without any trace of calcium carbonate.", "score": null, "metadata": {"title": "Blackening of lead white: Study of model paintings", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "source_file": "Blackening of lead white: Study of model paintings.md", "ingest_kind": "existing_chroma", "journal": "Journal of Raman Spectroscopy", "doi": "10.1002/jrs.5879", "year": "2020", "chunk_index": 6}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Lead white blackens very quickly only in the presence of NaClO, converting itself into plattnerite, as shown by XRD measurements.[14] Indeed, a previous study, carried out on blackened areas from Cimabue's mural painting samples, showed the presence of plattnerite.[15] A completely degraded layer with a thickness of about 20-40 \\upmum was reported, heavily contaminated with chlorine compounds and without any trace of calcium carbonate.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "lead white", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Furthermore, hydrocerussite is known to form a mixture of plattnerite and scrutiny, both lead (IV) oxides in chlorinated water solution at pH = 8.1 after 8 days.[31] On these bases, we tested the effect of commercial NaClO (5% aq) on lead white components. Cerussite and hydrocerussite were used as powders to verify the strength of NaClO avoiding the enhancement of a basic environment. In both cases, blackening takes place immediately, and the resultant darkened powders and their XRD are shown in Figure 5. Cerussite reaction with NaClO led to plattnerite and halite (NaCl) as observed by OM and a brown coloration for this sample was noted (Figure 6a). Reaction of hydrocerussite with NaClO led instead to corussite, scrutinyite (\\upalpha-PbO2), halite and plattnerite (\\upbeta-PbO2) showing a red-brownish hue (Figure 6b).", "score": null, "metadata": {"ingest_kind": "existing_chroma", "journal": "Journal of Raman Spectroscopy", "year": "2020", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "title": "Blackening of lead white: Study of model paintings", "doi": "10.1002/jrs.5879", "source_file": "Blackening of lead white: Study of model paintings.md", "chunk_index": 27}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Furthermore, hydrocerussite is known to form a mixture of plattnerite and scrutiny, both lead (IV) oxides in chlorinated water solution at pH = 8.1 after 8 days.[31] On these bases, we tested the effect of commercial NaClO (5% aq) on lead white components. Cerussite and hydrocerussite were used as powders to verify the strength of NaClO avoiding the enhancement of a basic environment. In both cases, blackening takes place immediately, and the resultant darkened powders and their XRD are shown in Figure 5. Cerussite reaction with NaClO led to plattnerite and halite (NaCl) as observed by OM and a brown coloration for this sample was noted (Figure 6a). Reaction of hydrocerussite with NaClO led instead to corussite, scrutinyite (\\upalpha-PbO2), halite and plattnerite (\\upbeta-PbO2) showing a red-brownish hue (Figure 6b).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Upon application of sodium hypochlorite on both hydrocerussite and corussite powders, XRD analyses showed formation of plattnerite and scrutinyite just for hydrocerussite, confirming the higher reactivity of such component.", "score": null, "metadata": {"source": "markdown_output/Blackening of lead white: Study of model paintings.md", "source_file": "Blackening of lead white: Study of model paintings.md", "journal": "Journal of Raman Spectroscopy", "year": "2020", "doi": "10.1002/jrs.5879", "ingest_kind": "existing_chroma", "chunk_index": 28, "title": "Blackening of lead white: Study of model paintings"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Upon application of sodium hypochlorite on both hydrocerussite and corussite powders, XRD analyses showed formation of plattnerite and scrutinyite just for hydrocerussite, confirming the higher reactivity of such component.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Figure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).", "score": null, "metadata": {"doi": "10.1002/jrs.5879", "source": "markdown_output/Blackening of lead white: Study of model paintings.md", "source_file": "Blackening of lead white: Study of model paintings.md", "title": "Blackening of lead white: Study of model paintings", "chunk_index": 31, "year": "2020", "ingest_kind": "existing_chroma", "journal": "Journal of Raman Spectroscopy"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Figure 5: Diffractograms of corussite (I, black) and hydrocerussite (II, grey) after reaction with NaClO (H = halite, P=plattnerite, C=cerussite, S= scrutinyite).", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "plattnerite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Hydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "score": null, "metadata": {"source": "markdown_output/Blackening of lead white: Study of model paintings.md", "ingest_kind": "existing_chroma", "journal": "Journal of Raman Spectroscopy", "source_file": "Blackening of lead white: Study of model paintings.md", "doi": "10.1002/jrs.5879", "title": "Blackening of lead white: Study of model paintings", "year": "2020", "chunk_index": 33}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2PbCO3·Pb(OH)2", "product": "beta-PbO2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Hydrocerussite forms scrutinyite to a larger extent than plattenrite, whereas cerussite turns mainly into plattenrite with small contents of scrutinyite.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "hydrocerussite", "product_span": "scrutinyite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 42, "resolver_kept": 8, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 207, "lexical_kept": 8, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/e9e0959c06900129f65098a3ba4e32e740cf8ddc.json b/rag_report_cache/e9e0959c06900129f65098a3ba4e32e740cf8ddc.json
new file mode 100644
index 0000000000000000000000000000000000000000..7f45c0ac39c2e8bf58a272a5a0e72553598eba4c
--- /dev/null
+++ b/rag_report_cache/e9e0959c06900129f65098a3ba4e32e740cf8ddc.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Chloride]--> Hg", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nThe residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.\n\n[2] Evidence classification: edge 1: direct\nAdditionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "ref_list": ["KEUNE K, BOON JJ. Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings [J/OL]. Analytical Chemistry, 2005. DOI: 10.1021/ac048158f.", "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "COTTE M, SUSINI J, METRICH N, et al. Blackening of Pompeian Cinnabar Paintings: X-ray Microspectroscopy Analysis [J/OL]. Analytical Chemistry, 2006. DOI: 10.1021/ac0612224."], "ref_snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.4839329719543457, "snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.4839329719543457, "metadata": {"doi": "10.1021/ac048158f", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "year": "2005", "ingest_kind": "existing_chroma", "journal": "Analytical Chemistry", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "chunk_index": 46}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "Hg", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": 0.4224860668182373, "snippets": [{"text": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": 0.4224860668182373, "metadata": {"year": "2021", "journal": "Communications Chemistry", "doi": "10.1038/s42004-021-00610-2", "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "chunk_index": 4, "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "ingest_kind": "existing_chroma"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "Hg", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 8, "dense_candidates": 160, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 112, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 212, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/ec11b104e88d3bafcdf1c8d146e99b2d67700174.json b/rag_report_cache/ec11b104e88d3bafcdf1c8d146e99b2d67700174.json
new file mode 100644
index 0000000000000000000000000000000000000000..5aaa122ab896bf0b78c88bad43c8d38ab2ef59d7
--- /dev/null
+++ b/rag_report_cache/ec11b104e88d3bafcdf1c8d146e99b2d67700174.json
@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Chloride]--> α-Hg3S2Cl2 --[Chloride]--> Hg2Cl2 --[Chloride]--> Hg", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct, edge 2: direct, pathway endpoints alpha-HgS -> Hg: direct\nThe residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.\n\n[2] Evidence classification: pathway endpoints alpha-HgS -> Hg: direct\nAdditionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "ref_list": ["KEUNE K, BOON JJ. Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings [J/OL]. Analytical Chemistry, 2005. DOI: 10.1021/ac048158f.", "ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "COTTE M, SUSINI J, METRICH N, et al. Blackening of Pompeian Cinnabar Paintings: X-ray Microspectroscopy Analysis [J/OL]. Analytical Chemistry, 2006. DOI: 10.1021/ac0612224."], "ref_snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.5111522674560547, "snippets": [{"text": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "score": 0.5111522674560547, "metadata": {"year": "2005", "ingest_kind": "existing_chroma", "title": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings", "source_file": "Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md", "journal": "Analytical Chemistry", "chunk_index": 46, "doi": "10.1021/ac048158f", "source": "markdown_output/Analytical Imaging Studies Clarifying the Process of the Darkening of Vermilion in Paintings.md"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "resolver", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "alpha-Hg3S2Cl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "corderoite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 2, "reactant": "alpha-Hg3S2Cl2", "product": "Hg2Cl2", "condition": "Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "corderoite", "product_span": "calomel", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}, {"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "The residual vermilion reacts with this external chloride to the light-sensitive mineral corderoite, which degrades under the influence of light into calomel, metallic mercury, and sulfur.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "vermilion", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": 0.47456979751586914, "snippets": [{"text": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "score": 0.47456979751586914, "metadata": {"ingest_kind": "existing_chroma", "chunk_index": 5, "journal": "Communications Chemistry", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "year": "2021", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "doi": "10.1038/s42004-021-00610-2", "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 0, "reactant": "alpha-HgS", "product": "Hg", "condition": "Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Additionally, the imperative role played by chlorides has been recognized, either as a catalyst in the redox reaction of cinnabar or as intermediate reaction products that are subsequently photochemically reduced to metallic mercury[6, 10].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "metallic mercury", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "qualified"}], "related_context": [], "retrieval_trace": {"query_count": 29, "dense_candidates": 580, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 27, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 2, "lexical_scanned": 2314, "lexical_candidates": 201, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/ec582c9b09f00a075dfbdf69d132a871f77a9b14.json b/rag_report_cache/ec582c9b09f00a075dfbdf69d132a871f77a9b14.json
new file mode 100644
index 0000000000000000000000000000000000000000..ec36a8c2653c9389eff7466a855b0badf4bf6278
--- /dev/null
+++ b/rag_report_cache/ec582c9b09f00a075dfbdf69d132a871f77a9b14.json
@@ -0,0 +1 @@
+{"root_material": "Na8[Al6Si6O24]S3", "path_str": "Na8[Al6Si6O24]S3 --[Acids]--> SiO2", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["DEL FEDERICO E, SHÖFBERGER W, SCHELVIS J, et al. Insight into Framework Destruction in Ultramarine Pigments [J/OL]. Inorganic Chemistry, 2006, 45(3):1270-1276. DOI: 10.1021/ic050903z."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [{"source": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 1: Accelerated Aging of Smalt and Lapis Lazuli-Based Paints. DOI: 10.3390/min10050427.", "snippet": "Although we cannot confirm the dissolution of calcite in LAP-paints, the formation of pentahydrite can be considered to occur at the expense of the diopside due to the fact that the Mg\\({}^{2+}\\) content of the water used was very low. The contribution of the impurities in the lapis lazuli pigment to the aging susceptibility of tempera model paints has not yet been fully examined in the specialist literature, even though impurities affect the final color of the natural pigment, the chemical-physical properties, and, therefore, its resistance to alteration, as found in the present study and elsewhere [22; 26; 27]. Hence, the use of impurity-free synthetic ultramarine instead of (natural) lapis lazuli could be a satisfactory preventive conservation strategy in restoration campaigns. In the literature, previous efforts aimed to obtain acidic-resisting ultramarine pigments by means of a novel two-step silica coating process [70] or by incorporating white lead or amine compounds as light", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "Na8[Al6Si6O24]S3", "product": "SiO2", "condition": "Acids", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "Although we cannot confirm the dissolution of calcite in LAP-paints, the formation of pentahydrite can be considered to occur at the expense of the diopside due to the fact that the Mg{}^{2+} content of the water used was very low. The contribution of the impurities in the lapis lazuli pigment to the aging susceptibility of tempera model paints has not yet been fully examined in the specialist literature, even though impurities affect the final color of the natural pigment, the chemical-physical properties, and, therefore, its resistance to alteration, as found in the present study and elsewhere [22; 26; 27]. Hence, the use of impurity-free synthetic ultramarine instead of (natural) lapis lazuli could be a satisfactory preventive conservation strategy in restoration campaigns. In the literature, previous efforts aimed to obtain acidic-resisting ultramarine pigments by means of a novel two-step silica coating process [70] or by incorporating white lead or amine compounds as light", "reactant_match": "alias", "product_match": "alias", "reactant_span": "ultramarine", "product_span": "silica", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "CATO E, BORCA C, HUTHWELKER T, et al. Aluminium X-ray absorption near-edge spectroscopy analysis of discoloured ultramarine blue in 20th century oil paintings [J/OL]. Microchemical Journal, 2016. DOI: 10.1016/j.microc.2015.11.021.", "snippet": "s from the surface. This penetration depth was estimated using the x-ray attenuation depth calculator provided by the Centre for X-ray Op- tics (Cxro) which takes into account factors in fluencing penetration depth including beam angle, sample composition and beam energy. The spectra were processed accordingly using Athena software (Ravel and Newville 2005). The Al K- fluorescence line was first normalised against incident intensity (I0), then normalised to a post-edge value of 1. No time dependent changes in the XANES spectra were detected for the different locations on the sample, indicating that the sample was not degrading due to radiation exposure. 3. Results 3.1. Pigment characterisation The FTIR spectrum of a sample taken from a discoloured area is shown in Fig. 3. Peaks were observed in the FTIR spectra at 1002, 722, 697, and 656 cm −1 (corresponding to Al \\\\Oa n dS i \\\\Os t r e t c h i n g vibrations of the ultramarine pigment) and at 2918, 2850 and 1735 cm−1 (corresponding to an oil binding medium). There is also a small quantity of quartz, with signals at 1090, 798, and 777 cm−1. BSE images of the cross section showed that the paint consisted of two layers, identi fied by EDX as a calcium carbonate ground (Ca, C and O) and an ultramarine paint layer (Si, Al, Na, S, O) (Fig. 4). Environ- mental SEM images of the non-embedded sample were compared with LM images of the same area ( Fig. 5). From the images it was observed that the ultramarine particles within the white line had lost their blue colour. 3.2. Reference materials The Al K-edge spectra of the reference ultram", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "Na8[Al6Si6O24]S3", "product": "SiO2", "condition": "Acids", "evidence_scope": "edge", "verdict": "qualified", "score": 0.67, "window": "Peaks were observed in the FTIR spectra at 1002, 722, 697, and 656 cm −1 (corresponding to Al \\\\Oa n dS i \\\\Os t r e t c h i n g vibrations of the ultramarine pigment) and at 2918, 2850 and 1735 cm−1 (corresponding to an oil binding medium). There is also a small quantity of quartz, with signals at 1090, 798, and 777 cm−1.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "ultramarine", "product_span": "quartz", "relation_basis": "product_identification", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["relation_product_identification", "condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "Research on the Preparation of Ultramarine Pigments from Palygorskite [J/OL]. Molecules, 2025:4. DOI: 10.3390/molecules30040870. (bibliographic metadata partially available)", "snippet": "of the ultramarine pigments. Notably, the blueness parameter (b*) exhibits a non-monotonic relationship with a reagent concentration, initially increasing before decreasing, reaching its maximum value at an anhydrous sodium carbonate dosage of 1.5 g. This optimal concentration point corre- sponds precisely with the visual observations presented in Figure 2. Furthermore, the color difference metric (∆E*) reaches its minimum value of 1.15 at this optimal concentration, demonstrating remarkable proximity to the standard ultramarine blue reference. Table 1. Influence of anhydrous sodium carbonate dosage on ultramarine pigment color. Number Palygorskite/g Na2CO3/g Rosin/g Quartz Sand/g S/g L* a* b* ∆E* 1 0.50 1.0 0.10 0.0717 0.75 ̸= ̸= ̸= ̸= 2 0.50 1.1 0.10 0.0717 0.75 11.86 −5.09 −18.32 26.22 3 0.50 1.2 0.10 0.0717 0.75 17.67 −5.71 −20.63 20.32 4 0.50 1.3 0.10 0.0717 0.75 24.71 −4.66 −22.29 14.68 5 0.50 1.4 0.10 0.0717 0.75 26.02 −5.00 −28.66 8.81 6 0.50 1.5 0.10 0.0717 0.75 31.93 −6.31 −33.71 1.15 7 0.50 1.6 0.10 0.0717 0.75 33.30 −5.10 −30.87 4.24 8 0.50 1.7 0.10 0.0717 0.75 36.78 −5.64 −25.62 10.29 9 0.50 1.8 0.10 0.0717 0.75 39.91 −9.81 −23.90 13.84", "retrieval_origin": "resolver", "match": {"edge_index": 1, "reactant": "Na8[Al6Si6O24]S3", "product": "SiO2", "condition": "Acids", "evidence_scope": "edge", "verdict": "qualified", "score": 0.67, "window": "This optimal concentration point corre- sponds precisely with the visual observations presented in Figure 2. Furthermore, the color difference metric (∆E*) reaches its minimum value of 1.15 at this optimal concentration, demonstrating remarkable proximity to the standard ultramarine blue reference. Table 1. Influence of anhydrous sodium carbonate dosage on ultramarine pigment color. Number Palygorskite/g Na2CO3/g Rosin/g Quartz Sand/g S/g L* a* b* ∆E* 1 0.50 1.0 0.10 0.0717 0.75 ̸= ̸= ̸= ̸= 2 0.50 1.1 0.10 0.0717 0.75 11.86 −5.09 −18.32 26.22 3 0.50 1.2 0.10 0.0717 0.75 17.67 −5.71 −20.63 20.32 4 0.50 1.3 0.10 0.0717 0.75 24.71 −4.66 −22.29 14.68 5 0.50 1.4 0.10 0.0717 0.75 26.02 −5.00 −28.66 8.81 6 0.50 1.5 0.10 0.0717 0.75 31.93 −6.31 −33.71 1.15 7 0.50 1.6 0.10 0.0717 0.75 33.30 −5.10 −30.87 4.24 8 0.50 1.7 0.10 0.0717 0.75 36.78 −5.64 −25.62 10.29 9 0.50 1.8 0.10 0.0717 0.75 39.91 −9.81 −23.90 13.84", "reactant_match": "alias", "product_match": "alias", "reactant_span": "ultramarine", "product_span": "quartz", "relation_basis": "product_identification", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 24, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 98, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/f142766d53691ac4ec5fbda4e77ead4ea2251baf.json b/rag_report_cache/f142766d53691ac4ec5fbda4e77ead4ea2251baf.json
new file mode 100644
index 0000000000000000000000000000000000000000..d2c5059dbe22eef013ec9a1316a40518f0056a99
--- /dev/null
+++ b/rag_report_cache/f142766d53691ac4ec5fbda4e77ead4ea2251baf.json
@@ -0,0 +1 @@
+{"root_material": "C16H10N2O2", "path_str": "C16H10N2O2 --[Uv]--> C16H8N2O2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nSCHEME 1: Interconversion between the Neutral Indigo and Its Oxidized Form: Dehydroindigo Figure 1.", "ref_list": ["RONDÃO R, SEIXAS DE MELO JS, BONIFÁCIO VDB, et al. Dehydroindigo, the Forgotten Indigo and Its Contribution to the Color of Maya Blue [J/OL]. Journal of Physical Chemistry A, 2010, 114(4):1699-1708. DOI: 10.1021/jp907718k.", "RONDÃO R, SEIXAS DE MELO JS, BONIFÁCIO VDB, et al. Dehydroindigo, the Forgotten Indigo and Its Contribution to the Color of Maya Blue [J/OL]. The Journal of Physical Chemistry A, 2010, 114(4):1699-1708. DOI: 10.1021/jp907718k."], "ref_snippets": [{"text": "SCHEME 1: Interconversion between the Neutral Indigo and Its Oxidized Form: Dehydroindigo Figure 1.", "score": null, "snippets": [{"text": "SCHEME 1: Interconversion between the Neutral Indigo and Its Oxidized Form: Dehydroindigo Figure 1.", "score": null, "metadata": {"page": "3", "source": "Dehydroindigo the Forgotten Indigo and Maya Blue", "chunk_index": "13", "doi": "10.1021/jp907718k", "journal": "Journal of Physical Chemistry A", "ingest_kind": "pdf_fulltext", "title": "Dehydroindigo, the Forgotten Indigo and Its Contribution to the Color of Maya Blue", "year": "2010", "source_file": "Dehydroindigo the Forgotten Indigo and Maya Blue", "authors": [{"family": "Rondão", "given": "Raquel"}, {"family": "Seixas de Melo", "given": "J. Sérgio"}, {"family": "Bonifácio", "given": "Vasco D. B."}, {"family": "Melo", "given": "Maria J."}], "volume": "114", "issue": "4", "pages": "1699-1708", "url": "https://doi.org/10.1021/jp907718k"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C16H8N2O2", "condition": "Uv", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "SCHEME 1: Interconversion between the Neutral Indigo and Its Oxidized Form: Dehydroindigo Figure 1.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "dehydroindigo", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 28, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 171, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/f193b31eb1c33b863bcfcddf7d9cdc75f3dd611a.json b/rag_report_cache/f193b31eb1c33b863bcfcddf7d9cdc75f3dd611a.json
new file mode 100644
index 0000000000000000000000000000000000000000..e67591673dcdd7c33c16a6887ad6d5394ea66acc
--- /dev/null
+++ b/rag_report_cache/f193b31eb1c33b863bcfcddf7d9cdc75f3dd611a.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Biogenic+Chloride]--> Cu2Cl(OH)3 --[Biogenic+Chloride]--> CuC2O4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: pathway endpoints CuCO3·Cu(OH)2 -> CuC2O4: direct\nComputer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.\n\n[2] Evidence classification: edge 1: direct\nMinerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "ref_list": ["CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w.", "PURDY EH, CRITCHLEY S, HOLÉ C, et al. Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy [J/OL]. Applied Physics A, 2024. DOI: 10.1007/s00339-024-07954-1."], "ref_snippets": [{"text": "Computer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.", "score": null, "snippets": [{"text": "Computer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.", "score": null, "metadata": {"year": "2008", "doi": "10.1021/ac800255w", "ingest_kind": "pdf_fulltext", "page": "1", "chunk_index": "0", "source": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "title": "Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence", "source_file": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "journal": "Analytical Chemistry", "authors": [{"family": "Castro", "given": "Kepa"}, {"family": "Sarmiento", "given": "Alfredo"}, {"family": "Martínez-Arkarazo", "given": "Irantzu"}, {"family": "Madariaga", "given": "Juan Manuel"}, {"family": "Fernández", "given": "Luis Angel"}], "volume": "80", "issue": "11", "pages": "4103-4110", "url": "https://doi.org/10.1021/ac800255w"}, "evidence_level": "pathway_endpoint", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 0, "reactant": "CuCO3·Cu(OH)2", "product": "CuC2O4", "condition": "Biogenic+Chloride", "evidence_scope": "pathway_endpoint", "verdict": "direct", "score": 1.0, "window": "Computer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "moolooite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "snippets": [{"text": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "score": null, "metadata": {"source_file": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf", "title": "Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy", "year": "2024", "doi": "10.1007/s00339-024-07954-1", "journal": "Applied Physics A", "chunk_index": 23, "license": "https://creativecommons.org/licenses/by/4.0", "fulltext_url": "https://cnrs.hal.science/hal-05105620/document", "page": 12, "ingest_kind": "pdf_fulltext", "source": "Characterisation_of_rouaite_an_unusual_copper-containing_pigment_in_early_modern_English_w_92a10740da0a.pdf"}, "evidence_level": "edge_direct", "retrieval_origin": "resolver", "retrieval_routes": ["resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "Cu2Cl(OH)3", "condition": "Biogenic+Chloride", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "Minerals from the atacamite family are common alteration or degradation products of azurite and malachite, especially in wall paintings and murals [64, 65]. Medieval synthetic recipes producing purely atacamite have also been documented [18] The specific identity of the basic copper chloride is therefore of interest, since it could provide information about the origin and mechanism of formation in the sample. Further analysis by /u1D707XANES was therefore carried out on sample T1 to characterise its composition.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "atacamite", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 31, "resolver_kept": 1, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 1, "lexical_scanned": 2314, "lexical_candidates": 201, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/f3d2ed4f683ff5f447dbf90b18a5ca2b7367ec05.json b/rag_report_cache/f3d2ed4f683ff5f447dbf90b18a5ca2b7367ec05.json
new file mode 100644
index 0000000000000000000000000000000000000000..d3d1c70208766a6a48478b4db8f91c036d12411d
--- /dev/null
+++ b/rag_report_cache/f3d2ed4f683ff5f447dbf90b18a5ca2b7367ec05.json
@@ -0,0 +1 @@
+{"root_material": "CaCO3", "path_str": "CaCO3 --[Biogenic]--> CaC2O4·nH2O", "signature": "docs=2314", "evidence": {"context_str": "No relevant literature evidence was retrieved from the vector database.", "ref_list": ["ROSADO T, GIL M, MIRÃO J, et al. Oxalate biofilm formation in mural paintings due to microorganisms – A comprehensive study [J/OL]. International Biodeterioration & Biodegradation, 2013. DOI: 10.1016/j.ibiod.2013.06.013."], "ref_snippets": [{"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": null}], "related_context": [{"source": "ROSADO T, GIL M, MIRÃO J, et al. Oxalate biofilm formation in mural paintings due to microorganisms eA comprehensive study [J/OL]. International Biodeterioration & Biodegradation, 2013, 85:1-7. DOI: 10.1016/j.ibiod.2013.06.013.", "snippet": "calcium oxalate compounds. The presence of the 455 cm\\({}^{-1}\\), 909 cm\\({}^{-1}\\) (Fig. 3A\\(-\\)F) and 1440 cm\\({}^{-1}\\) (Fig. 3D) bands are characteristic of weddellite, however, in Fig. 3C it is also present a band of 945 cm\\({}^{-1}\\), characteristic of whewellite (Perez-Alonso et al., 2004; Villar et al., 2004). In all analysed samples it is observed a peak of 1080 cm\\({}^{-1}\\), characteristic of calcite (CaCO\\({}_{3}\\)) (Danilila et al., 2008), the substrate medium of the painting. This compound may be an available source of calcium to react with oxalic acid produced by metabolic activity of bacteria and fungi, providing the calcium oxalates compounds founded in these paintings.", "retrieval_origin": "crn_provenance", "match": {"edge_index": 1, "reactant": "CaCO3", "product": "CaC2O4·nH2O", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "In all analysed samples it is observed a peak of 1080 cm{}^{-1}, characteristic of calcite (CaCO3) (Danilila et al., 2008), the substrate medium of the painting. This compound may be an available source of calcium to react with oxalic acid produced by metabolic activity of bacteria and fungi, providing the calcium oxalates compounds founded in these paintings.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "calcite", "product_span": "calcium oxalates", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w.", "snippet": "weak band located around 989 cm -1 was present. This band could be consistent with the presence of antlerite (Cu 3SO4(OH)4). However, the high levels of noise and the weakness of the band make it difficult to ascertain the presence of this compound. Antlerite would be an intermediate degradation product between the original green pigment and the copper oxalate (moolooite), and its formation could be due to the presence of calcium sulfate as the filler of the paper. Chemical System 2: Degraded Artwork on Stone Support, Lemoniz Wallpaintings. The important findings reported above made reconsider recent analysis carried out on a wall painting. 16 In that artwork, several green areas presented high levels of degradation. Moreover, the first results obtained from the wall painting 16 revealed the presence of calcium oxalate (weddellite, CaC2O4·2H2O) as in the case of the map described above. In fact, it was possible to demonstrate the degradation of malachite to green copper sulfates (posnjakite Cu4SO4(OH)6·H2O and antlerite Cu3SO4(OH)4) in presence of calcite and gypsum coming from the mortar (a reservoir of sulfate anions) due to the attack of oxalic acid. Moreover, some lichen species live on the gypsum substrata promoting the in situ formation of calcium oxalate as a conse- quence of the reaction between the excreted oxalic acid and the gypsum. 37 Thus, the decaying phenomena observed in the wall painting could be due to an old lichen colony.", "retrieval_origin": "lexical", "match": {"edge_index": 1, "reactant": "CaCO3", "product": "CaC2O4·nH2O", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "qualified", "score": 0.87, "window": "In fact, it was possible to demonstrate the degradation of malachite to green copper sulfates (posnjakite Cu4SO4(OH)6·H2O and antlerite Cu3SO4(OH)4) in presence of calcite and gypsum coming from the mortar (a reservoir of sulfate anions) due to the attack of oxalic acid. Moreover, some lichen species live on the gypsum substrata promoting the in situ formation of calcium oxalate as a conse- quence of the reaction between the excreted oxalic acid and the gypsum. 37 Thus, the decaying phenomena observed in the wall painting could be due to an old lichen colony.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "calcite", "product_span": "calcium oxalate", "relation_basis": "product_identification", "condition_status": "exact", "provenance_level": "unspecified", "reasons": ["relation_product_identification"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}, {"source": "VAGNINI M, VIVANI R, VISCUSO E, et al. Investigation on the process of lead white blackening by Raman spectroscopy, XRD and other methods: Study of Cimabue’s paintings in Assisi [J/OL]. Vibrational Spectroscopy, 2018. DOI: 10.1016/j.vibspec.2018.07.006.", "snippet": "measurements (Fig. 3), carried out non-destructively and directly on different areas of the fragments, it has been possible to reveal the presence of gypsum and calcium oxalate, that in the CA03 sample has been identify as wheeulellite (calcium oxalate monohydrated), besides the minerals ascribable to the plaster, namely calcite and quartz. In the black-brownish area of the CA03 sample, XRD analysis proved the presence of plattnerite (PbO\\({}_{2}\\)), besides azurite (2CaO\\({}_{3}\\)Cu(OH)\\({}_{2}\\), most probably the original blue pigment) and atacamite, a basic copper(II) chloride of stoichiometry Cu\\({}_{2}\\)Cl(OH)\\({}_{3}\\)[29]. In the sample CA04 (diffraction pattern of Fig. 3b), atacamite has been found along with its polymorph clinoatacamite [29] and with a minor amount of basic iron oxide (FeO(OH)). Plattnerite has been detected by XRD also on fragment CA15 (Fig. 3c), along with hematite (Fe\\({}_{2}\\)O\\({}_{3}\\)) and iron oxide chloride (FeOCI).", "retrieval_origin": "lexical", "match": {"edge_index": 1, "reactant": "CaCO3", "product": "CaC2O4·nH2O", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "qualified", "score": 0.67, "window": "measurements (Fig. 3), carried out non-destructively and directly on different areas of the fragments, it has been possible to reveal the presence of gypsum and calcium oxalate, that in the CA03 sample has been identify as wheeulellite (calcium oxalate monohydrated), besides the minerals ascribable to the plaster, namely calcite and quartz.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "calcite", "product_span": "calcium oxalate", "relation_basis": "product_identification", "condition_status": "unstated", "provenance_level": "unspecified", "reasons": ["relation_product_identification", "condition_unstated"]}, "reason": "Retrieved as chemically related context, but it does not directly establish this graph edge."}], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 0, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 92, "lexical_kept": 0, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/f3e719c62fff402197c3d116a82d4f458dd312ad.json b/rag_report_cache/f3e719c62fff402197c3d116a82d4f458dd312ad.json
new file mode 100644
index 0000000000000000000000000000000000000000..3f482b2b1d16ba56d036905781fdf0d6725c3bf9
--- /dev/null
+++ b/rag_report_cache/f3e719c62fff402197c3d116a82d4f458dd312ad.json
@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Biogenic]--> CuC2O4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nComputer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.\n\n[1] Evidence classification: edge 1: direct\nTo the best of the authors’ knowledge, this is the first time that moolooite is described as a degradation product of copper green pigments in artwork. Moolooite has been recently found as a corrosion product in coins. 25 The additional presence of calcium oxalate dihydrate (wedd- ellite, CaC 2O4·2H2O) detected in the degraded areas (bands at 1477, 910, and 506 cm -1, see Figure 1b) suggests that the map could have suffered a biological attack.", "ref_list": ["CASTRO K, SARMIENTO A, MARTÍNEZ-ARKARAZO I, et al. Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence [J/OL]. Analytical Chemistry, 2008. DOI: 10.1021/ac800255w."], "ref_snippets": [{"text": "Computer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.\nTo the best of the authors’ knowledge, this is the first time that moolooite is described as a degradation product of copper green pigments in artwork. Moolooite has been recently found as a corrosion product in coins. 25 The additional presence of calcium oxalate dihydrate (wedd- ellite, CaC 2O4·2H2O) detected in the degraded areas (bands at 1477, 910, and 506 cm -1, see Figure 1b) suggests that the map could have suffered a biological attack.", "score": null, "snippets": [{"text": "Computer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.", "score": null, "metadata": {"doi": "10.1021/ac800255w", "source_file": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "chunk_index": "0", "source": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "journal": "Analytical Chemistry", "title": "Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence", "year": "2008", "ingest_kind": "pdf_fulltext", "page": "1", "authors": [{"family": "Castro", "given": "Kepa"}, {"family": "Sarmiento", "given": "Alfredo"}, {"family": "Martínez-Arkarazo", "given": "Irantzu"}, {"family": "Madariaga", "given": "Juan Manuel"}, {"family": "Fernández", "given": "Luis Angel"}], "volume": "80", "issue": "11", "pages": "4103-4110", "url": "https://doi.org/10.1021/ac800255w"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuC2O4", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Computer simulations, based on heterogeneous chemical equilibria, support the transformation of malachite to moolooite through the intermediate copper basic sulfates or copper basic chlorides, depending on the presence of available free sulfate or chloride anions in the chemical system. Raman and X-ray fluorescence spectral evidence found during the analysis of the three case studies investigated supported the model predictions. According to the study, the presence of lichens and other microor- ganisms might be responsible for the decay phenomena.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "malachite", "product_span": "moolooite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "To the best of the authors’ knowledge, this is the first time that moolooite is described as a degradation product of copper green pigments in artwork. Moolooite has been recently found as a corrosion product in coins. 25 The additional presence of calcium oxalate dihydrate (wedd- ellite, CaC 2O4·2H2O) detected in the degraded areas (bands at 1477, 910, and 506 cm -1, see Figure 1b) suggests that the map could have suffered a biological attack.", "score": null, "metadata": {"chunk_index": "12", "journal": "Analytical Chemistry", "source": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "ingest_kind": "pdf_fulltext", "source_file": "Green Copper Pigments Biodegradation - Malachite to Moolooite", "year": "2008", "page": "3", "doi": "10.1021/ac800255w", "title": "Green Copper Pigments Biodegradation in Cultural Heritage: From Malachite to Moolooite, Thermodynamic Modeling, X-ray Fluorescence, and Raman Evidence", "authors": [{"family": "Castro", "given": "Kepa"}, {"family": "Sarmiento", "given": "Alfredo"}, {"family": "Martínez-Arkarazo", "given": "Irantzu"}, {"family": "Madariaga", "given": "Juan Manuel"}, {"family": "Fernández", "given": "Luis Angel"}], "volume": "80", "issue": "11", "pages": "4103-4110", "url": "https://doi.org/10.1021/ac800255w"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "resolver", "lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "CuC2O4", "condition": "Biogenic", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "To the best of the authors’ knowledge, this is the first time that moolooite is described as a degradation product of copper green pigments in artwork. Moolooite has been recently found as a corrosion product in coins. 25 The additional presence of calcium oxalate dihydrate (wedd- ellite, CaC 2O4·2H2O) detected in the degraded areas (bands at 1477, 910, and 506 cm -1, see Figure 1b) suggests that the map could have suffered a biological attack.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "copper green", "product_span": "moolooite", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 14, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 169, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/f563a0e3aedf36ed3e5e54d33c90706d5c8e2d36.json b/rag_report_cache/f563a0e3aedf36ed3e5e54d33c90706d5c8e2d36.json
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@@ -0,0 +1 @@
+{"root_material": "CuCO3·Cu(OH)2", "path_str": "CuCO3·Cu(OH)2 --[Sulfate]--> 2CuSO4·Cu(OH)2·4H2O", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite. Phases identified after SO2 exposure: Quartz, Malachite, 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4.\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Azurite, Quartz, Malachite. Phases identified after SO2 exposure: Azurite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O.\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite.\n\n[1] Evidence classification: edge 1: direct\nThe SO 2 aged rabbit glue-based mock-ups showed microscopically important crack formation and binder loss and fewer sulfated salts precipitated on the surface of the paints. Keywords: tempera paint; azurite; malachite; artificial aging; Sulfur dioxide; cultural heritage XRD phase comparison for AZ-C. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O.\n\n[1] Evidence classification: edge 1: direct\nDespite the fact that the concentration of SO 2 gas in the atmosphere has been reduced in some regions Minerals 2020, 10, 424 2 of 24 XRD phase comparison for AZ-M. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O. size and the type and amount of binder present in the paints, as all these factors influenced the color of the paint and the roughness of its surface [19–22]. Other recent research has reported that the impurities found in the historic mineral pigments used in tempera paints might significantly alter their optical, chem ical, and physical properties [22–24].\n\n[1] Evidence classification: edge 1: direct\nPhases identified before SO2 exposure: Quartz, Malachite. Phases identified after SO2 exposure: Quartz, Malachite, 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4. Phases present after SO2 exposure but absent before: 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4. mpurities of other minerals such as calcite, haematite (Fe2O3), goethite alpha-FeO(OH), quartz (SiO 2), cuprite (Cu2O), rutile/anatase (TiO 2), and chrysocolle ((Cu,Al)2H2Si2O5(OH)4·nH2O, found with malachite), as well as trace elements including arsenic (As), zirconium (Zr), antimony (Sb), barium (Ba), zinc (Zn), and bismuth (Bi) [28–30]. In fact, the particular mineral composition of natural azurite and malachite varies significantly between artworks produced at different times and places, and may be related to provenance [30].", "ref_list": ["POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424."], "ref_snippets": [{"text": "Phases identified before SO2 exposure: Quartz, Malachite. Phases identified after SO2 exposure: Quartz, Malachite, 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4.\nPhases identified before SO2 exposure: Azurite, Quartz, Malachite. Phases identified after SO2 exposure: Azurite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O.\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite.\nThe SO 2 aged rabbit glue-based mock-ups showed microscopically important crack formation and binder loss and fewer sulfated salts precipitated on the surface of the paints. Keywords: tempera paint; azurite; malachite; artificial aging; Sulfur dioxide; cultural heritage XRD phase comparison for AZ-C. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O.\nDespite the fact that the concentration of SO 2 gas in the atmosphere has been reduced in some regions Minerals 2020, 10, 424 2 of 24 XRD phase comparison for AZ-M. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.\nPhases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O. size and the type and amount of binder present in the paints, as all these factors influenced the color of the paint and the roughness of its surface [19–22]. Other recent research has reported that the impurities found in the historic mineral pigments used in tempera paints might significantly alter their optical, chem ical, and physical properties [22–24].\nPhases identified before SO2 exposure: Quartz, Malachite. Phases identified after SO2 exposure: Quartz, Malachite, 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4. Phases present after SO2 exposure but absent before: 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4. mpurities of other minerals such as calcite, haematite (Fe2O3), goethite alpha-FeO(OH), quartz (SiO 2), cuprite (Cu2O), rutile/anatase (TiO 2), and chrysocolle ((Cu,Al)2H2Si2O5(OH)4·nH2O, found with malachite), as well as trace elements including arsenic (As), zirconium (Zr), antimony (Sb), barium (Ba), zinc (Zn), and bismuth (Bi) [28–30]. In fact, the particular mineral composition of natural azurite and malachite varies significantly between artworks produced at different times and places, and may be related to provenance [30].", "score": 0.3878737688064575, "snippets": [{"text": "Phases identified before SO2 exposure: Quartz, Malachite. Phases identified after SO2 exposure: Quartz, Malachite, 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4.", "score": 0.3878737688064575, "metadata": {"table_sample": "AZ-ST", "ingest_kind": "xrd_phase_table", "year": "2020", "source": "xrd_phase_table/min10050424_part2", "chunk_index": 4, "source_file": "min10050424_part2_table1.pdf", "journal": "Minerals", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "table_page": 5, "doi": "10.3390/min10050424", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite. Phases identified after SO2 exposure: Quartz, Malachite, 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Azurite, Quartz, Malachite. Phases identified after SO2 exposure: Azurite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O.", "score": 0.39142435789108276, "metadata": {"journal": "Minerals", "year": "2020", "chunk_index": 0, "source_file": "min10050424_part2_table1.pdf", "ingest_kind": "xrd_phase_table", "doi": "10.3390/min10050424", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "table_page": 5, "table_sample": "AZ-EC", "source": "xrd_phase_table/min10050424_part2", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Azurite, Quartz, Malachite. Phases identified after SO2 exposure: Azurite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "score": 0.3921933174133301, "metadata": {"table_sample": "AZ-EF", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "table_page": 5, "journal": "Minerals", "source": "xrd_phase_table/min10050424_part2", "doi": "10.3390/min10050424", "source_file": "min10050424_part2_table1.pdf", "ingest_kind": "xrd_phase_table", "chunk_index": 3, "year": "2020", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "score": 0.3961526155471802, "metadata": {"source_file": "min10050424_part2_table1.pdf", "journal": "Minerals", "doi": "10.3390/min10050424", "table_sample": "AZ-M", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "table_page": 5, "source": "xrd_phase_table/min10050424_part2", "year": "2020", "chunk_index": 2, "ingest_kind": "xrd_phase_table", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite.", "score": 0.3989757299423218, "metadata": {"ingest_kind": "xrd_phase_table", "source_file": "min10050424_part2_table1.pdf", "table_page": 5, "chunk_index": 1, "doi": "10.3390/min10050424", "journal": "Minerals", "source": "xrd_phase_table/min10050424_part2", "year": "2020", "table_sample": "AZ-C", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "The SO 2 aged rabbit glue-based mock-ups showed microscopically important crack formation and binder loss and fewer sulfated salts precipitated on the surface of the paints. Keywords: tempera paint; azurite; malachite; artificial aging; Sulfur dioxide; cultural heritage XRD phase comparison for AZ-C. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O.", "score": null, "metadata": {"title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "doi": "10.3390/min10050424", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "source": "pdf_direct/min10050424_part2.pdf", "year": "2020", "journal": "Minerals", "chunk_index": 0, "ingest_kind": "pdf_direct", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The SO 2 aged rabbit glue-based mock-ups showed microscopically important crack formation and binder loss and fewer sulfated salts precipitated on the surface of the paints. Keywords: tempera paint; azurite; malachite; artificial aging; Sulfur dioxide; cultural heritage XRD phase comparison for AZ-C. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: MgSO4·3Mg(OH)2·8H2O, 2CuSO4·Cu(OH)2·4H2O.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Despite the fact that the concentration of SO 2 gas in the atmosphere has been reduced in some regions Minerals 2020, 10, 424 2 of 24 XRD phase comparison for AZ-M. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "score": null, "metadata": {"doi": "10.3390/min10050424", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "chunk_index": 1, "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "year": "2020", "source": "pdf_direct/min10050424_part2.pdf", "ingest_kind": "pdf_direct", "journal": "Minerals", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Despite the fact that the concentration of SO 2 gas in the atmosphere has been reduced in some regions Minerals 2020, 10, 424 2 of 24 XRD phase comparison for AZ-M. Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Quartz, Malachite, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite.", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O. size and the type and amount of binder present in the paints, as all these factors influenced the color of the paint and the roughness of its surface [19–22]. Other recent research has reported that the impurities found in the historic mineral pigments used in tempera paints might significantly alter their optical, chem ical, and physical properties [22–24].", "score": null, "metadata": {"ingest_kind": "pdf_direct", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "chunk_index": 4, "source": "pdf_direct/min10050424_part2.pdf", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "doi": "10.3390/min10050424", "year": "2020", "journal": "Minerals", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite, Azurite. Phases identified after SO2 exposure: Malachite, Quartz, Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O, Azurite. Phases present after SO2 exposure but absent before: Cu2O·(SO4), 2CuSO4·Cu(OH)2·4H2O. size and the type and amount of binder present in the paints, as all these factors influenced the color of the paint and the roughness of its surface [19–22]. Other recent research has reported that the impurities found in the historic mineral pigments used in tempera paints might significantly alter their optical, chem ical, and physical properties [22–24].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "Phases identified before SO2 exposure: Quartz, Malachite. Phases identified after SO2 exposure: Quartz, Malachite, 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4. Phases present after SO2 exposure but absent before: 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4. mpurities of other minerals such as calcite, haematite (Fe2O3), goethite alpha-FeO(OH), quartz (SiO 2), cuprite (Cu2O), rutile/anatase (TiO 2), and chrysocolle ((Cu,Al)2H2Si2O5(OH)4·nH2O, found with malachite), as well as trace elements including arsenic (As), zirconium (Zr), antimony (Sb), barium (Ba), zinc (Zn), and bismuth (Bi) [28–30]. In fact, the particular mineral composition of natural azurite and malachite varies significantly between artworks produced at different times and places, and may be related to provenance [30].", "score": null, "metadata": {"year": "2020", "source": "pdf_direct/min10050424_part2.pdf", "ingest_kind": "pdf_direct", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "chunk_index": 5, "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "journal": "Minerals", "doi": "10.3390/min10050424", "authors": [{"family": "Pozo-Antonio", "given": "Jose Santiago"}, {"family": "Cardell", "given": "Carolina"}, {"family": "Barral", "given": "Diana"}, {"family": "Dionisio", "given": "Amelia"}, {"family": "Rivas", "given": "Teresa"}], "volume": "10", "issue": "5", "pages": "424", "url": "https://doi.org/10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "crn_provenance", "retrieval_routes": ["crn_provenance", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "CuCO3·Cu(OH)2", "product": "2CuSO4·Cu(OH)2·4H2O", "condition": "Sulfate", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "Phases identified before SO2 exposure: Quartz, Malachite. Phases identified after SO2 exposure: Quartz, Malachite, 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4. Phases present after SO2 exposure but absent before: 2CuSO4·Cu(OH)2·4H2O, Pseudomalachite, Bassanite, Na2Cu(SO4)2, Cu5(PO4)2(OH)4. mpurities of other minerals such as calcite, haematite (Fe2O3), goethite alpha-FeO(OH), quartz (SiO 2), cuprite (Cu2O), rutile/anatase (TiO 2), and chrysocolle ((Cu,Al)2H2Si2O5(OH)4·nH2O, found with malachite), as well as trace elements including arsenic (As), zirconium (Zr), antimony (Sb), barium (Ba), zinc (Zn), and bismuth (Bi) [28–30]. In fact, the particular mineral composition of natural azurite and malachite varies significantly between artworks produced at different times and places, and may be related to provenance [30].", "reactant_match": "alias", "product_match": "exact", "reactant_span": "malachite", "product_span": "2CuSO4·Cu(OH)2·4H2O", "relation_basis": "phase_table_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 5, "resolver_scanned": 2314, "resolver_candidates": 7, "resolver_kept": 5, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 5, "lexical_scanned": 2314, "lexical_candidates": 177, "lexical_kept": 9, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/f6448654744bdf08d721d0a3ec82759987de8320.json b/rag_report_cache/f6448654744bdf08d721d0a3ec82759987de8320.json
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@@ -0,0 +1 @@
+{"root_material": "α-HgS", "path_str": "α-HgS --[Uv+Moisture]--> HgSO4 --[Uv+Oxidant]--> Hg2SO4", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.\n\n[1] Evidence classification: edge 1: direct\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "ref_list": ["ELERT K, MENDOZA MP, CARDELL C. Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints [J/OL]. Communications Chemistry, 2021. DOI: 10.1038/s42004-021-00610-2.", "CHAPPÉ M, HILDENHAGEN J, DICKMANN K, et al. Laser irradiation of medieval pigments at IR, VIS and UV wavelengths [J/OL]. Journal of Cultural Heritage, 2003. DOI: 10.1016/s1296-2074(02)01206-2.", "ELERT K, CARDELL C. Weathering behavior of cinnabar-based tempera paints upon natural and accelerated aging [J/OL]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, 216:236-248. DOI: 10.1016/j.saa.2019.03.027."], "ref_snippets": [{"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.\nwould explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "score": 0.40642261505126953, "snippets": [{"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.", "score": 0.49485206604003906, "metadata": {"ingest_kind": "existing_chroma", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "year": "2021", "doi": "10.1038/s42004-021-00610-2", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "journal": "Communications Chemistry", "chunk_index": 43, "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "authors": [{"family": "Elert", "given": "Kerstin"}, {"family": "Pérez Mendoza", "given": "Manuel"}, {"family": "Cardell", "given": "Carolina"}], "volume": "4", "issue": "1", "article_number": "174", "url": "https://doi.org/10.1038/s42004-021-00610-2"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52]. \\begin{split} 2\\mathrm{HgSO4(aq)+2e^{-}\\leftrightarrow Hg2^{2+}+ 2SO4^{2-}\\ is\\ 0.83\\ V\\ vs.\\ SHE}\\\\ (standard\\ hydrogen\\ electrode)\\end{split} \\tag{2} \\mathrm{Hg2^{2+}+2e^{-}\\leftrightarrow 2Hg\\ is\\ 0.80\\ V\\ vs.\\ SHE} \\tag{3} This implies that mercury sulfate could be reduced to metallic mercury in sequential reactions via photo-induced electron transfer. Indeed, part of the cinnabar pigment grains suffered darkening upon UV exposure, and a few nano-sized droplets, presumably metallic mercury, were observed on the pigment surface. However, massive amounts of yellow schuetteite (with a 3/1 Hg/S ratio), which covered large parts of the UV-aged pigment grains acted as a sink for mercury ions and limited the formation of metallic mercury.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "mercury sulfate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}, {"text": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "score": 0.40642261505126953, "metadata": {"journal": "Communications Chemistry", "year": "2021", "doi": "10.1038/s42004-021-00610-2", "title": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints", "ingest_kind": "existing_chroma", "chunk_index": 42, "source": "markdown_output/Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "source_file": "Direct evidence for metallic mercury causing photo-induced darkening of red cinnabar tempera paints.md", "authors": [{"family": "Elert", "given": "Kerstin"}, {"family": "Pérez Mendoza", "given": "Manuel"}, {"family": "Cardell", "given": "Carolina"}], "volume": "4", "issue": "1", "article_number": "174", "url": "https://doi.org/10.1038/s42004-021-00610-2"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "alpha-HgS", "product": "HgSO4", "condition": "Uv+Moisture", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "would explain the presence of schuetteite and mercury sulfate hydrate on UV-exposed cinnabar pigment grains in our study. They form according to the following overall reaction for the photoconversion process at high RH (adapted from Meissner et al.[49], h{}^{+}= hole): \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} \\mathrm{HgS+4h^{+}+2H2O+O2\\to Hg^{2+}+SO4^{2-}+4H^{+}} \\tag{1} Considering the potential of redox reactions for mercury sulfate and mercury ions (reactions 2 and 3), it becomes obvious that both fall within the band gap of cinnabar[52].", "reactant_match": "alias", "product_match": "alias", "reactant_span": "cinnabar", "product_span": "mercury sulfate", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 20, "dense_candidates": 400, "dense_kept": 2, "resolver_scanned": 2314, "resolver_candidates": 15, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 203, "lexical_kept": 2, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/f6a688a09ba2578c595c972a2bc1cfeb47a9e0a6.json b/rag_report_cache/f6a688a09ba2578c595c972a2bc1cfeb47a9e0a6.json
new file mode 100644
index 0000000000000000000000000000000000000000..528405ae35b1ce1274811e5e86e92c23777e240f
--- /dev/null
+++ b/rag_report_cache/f6a688a09ba2578c595c972a2bc1cfeb47a9e0a6.json
@@ -0,0 +1 @@
+{"root_material": "C16H10N2O2", "path_str": "C16H10N2O2 --[Reductant]--> C16H12N2O2", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 1: direct\nIn marked contrast to what has been found for keto-indigo, where the internal conversion channel dominates>99% of the excited state deactivation, or with the fully reduced leuco-indigo, where fluorescence, internal conversion, and singlet-to-triplet intersystem crossing coexist, in the case of DHI in toluene and benzene, the dominant excited state deactivation channel involves the triplet state. Triplet state yields ( φ T)o f7 0 -80%, with negligible fluorescence ( e0.01%) are observed in these solvents.", "ref_list": ["Dehydroindigo, the Forgotten Indigo and Its Contribution to the Color of Maya Blue [J/OL]. Journal of Physical Chemistry A, 2010:1. DOI: 10.1021/jp907718k. (bibliographic metadata partially available)", "DELGADO MC. El índigo en la pintura de caballete novohispana: mecanismos de deterioro [J/OL]. Intervención, Revista Internacional de Conservación, Restauración y Museología, 2019. DOI: 10.30763/intervencion.2019.19.206."], "ref_snippets": [{"text": "In marked contrast to what has been found for keto-indigo, where the internal conversion channel dominates>99% of the excited state deactivation, or with the fully reduced leuco-indigo, where fluorescence, internal conversion, and singlet-to-triplet intersystem crossing coexist, in the case of DHI in toluene and benzene, the dominant excited state deactivation channel involves the triplet state. Triplet state yields ( φ T)o f7 0 -80%, with negligible fluorescence ( e0.01%) are observed in these solvents.", "score": null, "snippets": [{"text": "In marked contrast to what has been found for keto-indigo, where the internal conversion channel dominates>99% of the excited state deactivation, or with the fully reduced leuco-indigo, where fluorescence, internal conversion, and singlet-to-triplet intersystem crossing coexist, in the case of DHI in toluene and benzene, the dominant excited state deactivation channel involves the triplet state. Triplet state yields ( φ T)o f7 0 -80%, with negligible fluorescence ( e0.01%) are observed in these solvents.", "score": null, "metadata": {"year": "2010", "source": "Dehydroindigo the Forgotten Indigo and Maya Blue", "chunk_index": "0", "page": "1", "journal": "Journal of Physical Chemistry A", "title": "Dehydroindigo, the Forgotten Indigo and Its Contribution to the Color of Maya Blue", "source_file": "Dehydroindigo the Forgotten Indigo and Maya Blue", "ingest_kind": "pdf_fulltext", "doi": "10.1021/jp907718k"}, "evidence_level": "edge_direct", "retrieval_origin": "lexical", "retrieval_routes": ["lexical"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "C16H10N2O2", "product": "C16H12N2O2", "condition": "Reductant", "evidence_scope": "edge", "verdict": "direct", "score": 0.8, "window": "In marked contrast to what has been found for keto-indigo, where the internal conversion channel dominates>99% of the excited state deactivation, or with the fully reduced leuco-indigo, where fluorescence, internal conversion, and singlet-to-triplet intersystem crossing coexist, in the case of DHI in toluene and benzene, the dominant excited state deactivation channel involves the triplet state. Triplet state yields ( φ T)o f7 0 -80%, with negligible fluorescence ( e0.01%) are observed in these solvents.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "indigo", "product_span": "leucoindigo", "relation_basis": "observed_conversion", "condition_status": "exact_document", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "", "score": null, "snippets": [], "provenance_only": true, "best_verdict": "unsupported"}], "related_context": [], "retrieval_trace": {"query_count": 12, "dense_candidates": 240, "dense_kept": 0, "resolver_scanned": 2314, "resolver_candidates": 2, "resolver_kept": 0, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 0, "lexical_scanned": 2314, "lexical_candidates": 155, "lexical_kept": 1, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file
diff --git a/rag_report_cache/f6dfdccea84ac68dc3693ec95043107d6e26abd9.json b/rag_report_cache/f6dfdccea84ac68dc3693ec95043107d6e26abd9.json
new file mode 100644
index 0000000000000000000000000000000000000000..47e169d856209dd815abc3f6af87aab746c67c46
--- /dev/null
+++ b/rag_report_cache/f6dfdccea84ac68dc3693ec95043107d6e26abd9.json
@@ -0,0 +1 @@
+{"root_material": "2CuCO3·Cu(OH)2", "path_str": "2CuCO3·Cu(OH)2 --[Alkaline]--> Cu(OH)2 --[Alkaline]--> [Cu(OH)4]2-", "signature": "docs=2314", "evidence": {"context_str": "[1] Evidence classification: edge 2: direct\nmetastable phases that are difficult to isolate in pure crystalline form 23,43. Consequently, at room temperature and under high pH conditions, Cu(OH)2 forms a complex anion (Cu(OH)4 2−)t h a ta c t sa sap r e c u r s o ri nt h e formation of black Cu-oxides43. Although Cu-hydroxides were not identi- fied by μXRD in our samples, their formation as an intermediate phase cannot be excluded, particularly given the strongly alkaline and humid environment of frescoes. Importantly, copper hydroxides are thermodynamically unstable under ambient conditions and tend to dehy- drate or transform into copper oxides 44. In the mock-ups here evaluated, tenorite (CuO) and cuprite (Cu2O) were identified only in some samples, suggesting that hydroxides and other intermediates may evolve towards CuO over time.\n\n[2] Evidence classification: edge 1: direct\ndesantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.\n\n[3] Evidence classification: edge 1: direct\nThe treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "ref_list": ["Blackening of copper pigments in wall paintings: impact of the fresco technique and the chemical composition of the pigments [J/OL]. Heritage Science, 2026:10. DOI: 10.1038/s40494-026-02461-3. (bibliographic metadata partially available)", "MATTEI E, VIVO GD, SANTIS AD, et al. Raman spectroscopic analysis of azurite blackening [J/OL]. Journal of Raman Spectroscopy, 2008. DOI: 10.1002/jrs.1845.", "POZO-ANTONIO JS, CARDELL C, BARRAL D, et al. Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints [J/OL]. Minerals, 2020. DOI: 10.3390/min10050424."], "ref_snippets": [{"text": "metastable phases that are difficult to isolate in pure crystalline form 23,43. Consequently, at room temperature and under high pH conditions, Cu(OH)2 forms a complex anion (Cu(OH)4 2−)t h a ta c t sa sap r e c u r s o ri nt h e formation of black Cu-oxides43. Although Cu-hydroxides were not identi- fied by μXRD in our samples, their formation as an intermediate phase cannot be excluded, particularly given the strongly alkaline and humid environment of frescoes. Importantly, copper hydroxides are thermodynamically unstable under ambient conditions and tend to dehy- drate or transform into copper oxides 44. In the mock-ups here evaluated, tenorite (CuO) and cuprite (Cu2O) were identified only in some samples, suggesting that hydroxides and other intermediates may evolve towards CuO over time.", "score": 0.46558117866516113, "snippets": [{"text": "metastable phases that are difficult to isolate in pure crystalline form 23,43. Consequently, at room temperature and under high pH conditions, Cu(OH)2 forms a complex anion (Cu(OH)4 2−)t h a ta c t sa sap r e c u r s o ri nt h e formation of black Cu-oxides43. Although Cu-hydroxides were not identi- fied by μXRD in our samples, their formation as an intermediate phase cannot be excluded, particularly given the strongly alkaline and humid environment of frescoes. Importantly, copper hydroxides are thermodynamically unstable under ambient conditions and tend to dehy- drate or transform into copper oxides 44. In the mock-ups here evaluated, tenorite (CuO) and cuprite (Cu2O) were identified only in some samples, suggesting that hydroxides and other intermediates may evolve towards CuO over time.", "score": 0.46558117866516113, "metadata": {"source_file": "Blackening of copper pigments in wall paintings", "title": "Blackening of copper pigments in wall paintings: impact of the fresco technique and the chemical composition of the pigments", "page": "10", "doi": "10.1038/s40494-026-02461-3", "chunk_index": "33", "source": "Blackening of copper pigments in wall paintings", "journal": "Heritage Science", "year": "2026", "ingest_kind": "pdf_fulltext"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 2, "reactant": "Cu(OH)2", "product": "[Cu(OH)4]2-", "condition": "Alkaline", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "metastable phases that are difficult to isolate in pure crystalline form 23,43. Consequently, at room temperature and under high pH conditions, Cu(OH)2 forms a complex anion (Cu(OH)4 2−)t h a ta c t sa sap r e c u r s o ri nt h e formation of black Cu-oxides43. Although Cu-hydroxides were not identi- fied by μXRD in our samples, their formation as an intermediate phase cannot be excluded, particularly given the strongly alkaline and humid environment of frescoes. Importantly, copper hydroxides are thermodynamically unstable under ambient conditions and tend to dehy- drate or transform into copper oxides 44. In the mock-ups here evaluated, tenorite (CuO) and cuprite (Cu2O) were identified only in some samples, suggesting that hydroxides and other intermediates may evolve towards CuO over time.", "reactant_match": "exact", "product_match": "exact", "reactant_span": "Cu(OH)2", "product_span": "Cu(OH)4", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "desantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.", "score": 0.4565846920013428, "snippets": [{"text": "desantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.", "score": 0.4565846920013428, "metadata": {"chunk_index": 2, "ingest_kind": "pdf_reextract", "title": "Raman spectroscopic analysis of azurite blackening", "source_file": "Raman spectroscopic analysis of azurite blackening.md", "year": "2008", "journal": "Journal of Raman Spectroscopy", "source": "pdf_reextract/蓝铜矿黑化的拉曼光谱分析", "doi": "10.1002/jrs.1845", "authors": [{"family": "Mattei", "given": "E."}, {"family": "de Vivo", "given": "G."}, {"family": "De Santis", "given": "A."}, {"family": "Gaetani", "given": "C."}, {"family": "Pelosi", "given": "C."}, {"family": "Santamaria", "given": "U."}], "volume": "39", "issue": "2", "pages": "302-306", "url": "https://doi.org/10.1002/jrs.1845"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "crn_provenance", "resolver", "lexical", "bm25"], "evidence_aggregation": "single_fragment", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu(OH)2", "condition": "Alkaline", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "desantis@unitus.it in 1950 by Liberti, 7 who ascribed the formation of the oxide to an altered alkalinity of the plaster. The OH- ions it releases react with the copper atoms present in the azurite molecules and form copper hydroxide, which in turn transforms into water and copper oxide.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "copper hydroxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}, {"text": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "score": 0.43921196460723877, "snippets": [{"text": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "score": 0.43921196460723877, "metadata": {"journal": "Minerals", "source": "pdf_direct/min10050424_part2.pdf", "source_file": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints.pdf", "ingest_kind": "pdf_direct", "year": "2020", "title": "Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints", "chunk_index": 7, "doi": "10.3390/min10050424"}, "evidence_level": "edge_direct", "retrieval_origin": "bge_m3", "retrieval_routes": ["bge_m3", "lexical", "resolver", "bm25"], "evidence_aggregation": "adjacent_chunks_same_doi", "edge_matches": [{"edge_index": 1, "reactant": "2CuCO3·Cu(OH)2", "product": "Cu(OH)2", "condition": "Alkaline", "evidence_scope": "edge", "verdict": "direct", "score": 1.0, "window": "The treatment of such damaged azurite tempera paints with ammonium carbonate and barium hydroxide (both well- known chemical reagents used in the restoration of mural paintings) can also yield the precipitation Minerals 2020, 10, 424 3 of 24 of black copper species such as copper hydroxide or basic copper chloride [33]. Black colored tenorite (CuO) was the final product of the reaction between malachite and azurite with alkaline solutions in laboratory conditions [34]. As regards artificial aging of azurite due to SO 2 exposure, to the knowledge of the authors, only one research study has so far been carried out. In the cited study, the effect on egg yolk-based azurite paint mock-ups of exposure to a mixture of 10.2 ppm SO 2, 11.4 ppm NO, and 5.2 ppm NO 2 was evaluated over 4 days (23 °C and 55% RH) [7]: the authors detected the formation of inorganic compounds such as nitrates (NO3−), nitrites (NO2−), and sulfates (SO42−). This work is part of a two-part research series entitled Effect of a SO 2 rich atmosphere on tempera paint mock-ups.", "reactant_match": "alias", "product_match": "alias", "reactant_span": "azurite", "product_span": "copper hydroxide", "relation_basis": "observed_conversion", "condition_status": "exact", "provenance_level": "unspecified", "reasons": []}]}]}], "related_context": [], "retrieval_trace": {"query_count": 21, "dense_candidates": 420, "dense_kept": 3, "resolver_scanned": 2314, "resolver_candidates": 30, "resolver_kept": 2, "bm25_scanned": 2314, "bm25_candidates": 100, "bm25_kept": 3, "lexical_scanned": 2314, "lexical_candidates": 234, "lexical_kept": 3, "strategy": "four-route retrieval (resolver + BM25 + lexical + BGE-M3) with chemical evidence gating"}}}
\ No newline at end of file