{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T03:01:38Z","timestamp":1787022098585,"version":"build-2736575974"},"reference-count":114,"publisher":"Public Library of Science (PLoS)","issue":"1","license":[{"start":{"date-parts":[[2022,1,24]],"date-time":"2022-01-24T00:00:00Z","timestamp":1642982400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006251","name":"Universit\u00e9 de Bordeaux","doi-asserted-by":"crossref","id":[{"id":"10.13039\/501100006251","id-type":"DOI","asserted-by":"crossref"}]},{"DOI":"10.13039\/501100005416","name":"Research Council of Norway","doi-asserted-by":"crossref","award":["262618"],"award-info":[{"award-number":["262618"]}],"id":[{"id":"10.13039\/501100005416","id-type":"DOI","asserted-by":"crossref"}]},{"DOI":"10.13039\/100010663","name":"h2020 european research council","doi-asserted-by":"publisher","award":["FP7\/2007\/2013"],"award-info":[{"award-number":["FP7\/2007\/2013"]}],"id":[{"id":"10.13039\/100010663","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["www.plosone.org"],"crossmark-restriction":false},"short-container-title":["PLoS ONE"],"abstract":"<jats:p>\n                    Paint technology, namely paint preparation and application procedures, is an important aspect of painting traditions. With the expansion of archaeometric studies and\n                    <jats:italic>in situ<\/jats:italic>\n                    non-destructive analytical methods, a renewal of technological studies is being observed in rock art.\n                    <jats:italic>In situ<\/jats:italic>\n                    analyses have several limitations that are widely discussed in the literature, however. It is not yet clear whether they provide accurate information on paint technology, except under certain conditions. Here, we evaluated digital microscopic and pXRF\n                    <jats:italic>in situ<\/jats:italic>\n                    analyses for the characterisation of a large set of red and yellow paintings from the El Castillo cave, Cantabria, Spain. We have set experiments and used statistical methods to identify differences between paint components and determine factors impacting pXRF measurements. We found that the compositional heterogeneity of the paintings\u2019 environment, especially variations in secondary deposits, was responsible for most of the differences observed between the pXRF signals recorded on the paintings. We concluded that the El Castillo cave environment is not suitable for non-destructive technological studies, but that more favourable contexts might exist. Following previous works and our own results, we advocate a combination of both\n                    <jats:italic>in situ<\/jats:italic>\n                    and laboratory invasive analyses for the study of paint composition and paint technology. Our research protocol, based on the comparison of rock paintings, their substrate, experimental paintings and Fe-normalisation of the signals can improve the reliability of pXRF results. We also propose to include more systematic characterisation of rock wall heterogeneity and the use of microscopic analyses in non-destructive approaches.\n                  <\/jats:p>","DOI":"10.1371\/journal.pone.0262143","type":"journal-article","created":{"date-parts":[[2022,1,24]],"date-time":"2022-01-24T13:33:55Z","timestamp":1643031235000},"page":"e0262143","update-policy":"https:\/\/doi.org\/10.1371\/journal.pone.corrections_policy","source":"Crossref","is-referenced-by-count":17,"title":["Critical evaluation of in situ analyses for the characterisation of red pigments in rock paintings: A case study from El Castillo, Spain"],"prefix":"10.1371","volume":"17","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0408-6035","authenticated-orcid":true,"given":"Laure","family":"Dayet","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Francesco","family":"d\u2019Errico","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marcos","family":"Garc\u00eda Diez","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5937-3061","authenticated-orcid":true,"given":"Jo\u00e3o","family":"Zilh\u00e3o","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"340","published-online":{"date-parts":[[2022,1,24]]},"reference":[{"key":"pone.0262143.ref001","doi-asserted-by":"crossref","first-page":"459","DOI":"10.1016\/j.talanta.2014.04.043","article-title":"First use of portable system coupling X-ray diffraction and X-ray fluorescence for in-situ analysis of prehistoric rock art","volume":"129","author":"L Beck","year":"2014","journal-title":"Talanta"},{"issue":"1","key":"pone.0262143.ref002","doi-asserted-by":"crossref","first-page":"77","DOI":"10.1111\/arcm.12073","article-title":"One Colour, (at Least) Two Minerals: A Study of Mulberry Rock Art Pigment and a Mulberry Pigment \u2018Quarry\u2019 from the Kimberley, Northern Australia","volume":"57","author":"J Huntley","year":"2015","journal-title":"Archaeometry"},{"key":"pone.0262143.ref003","doi-asserted-by":"crossref","first-page":"113","DOI":"10.2307\/j.ctvxrq0ks.11","volume-title":"Paleoart and Materiality The Scientific Study of Rock Art [Internet]","author":"RV Blanco","year":"2016"},{"key":"pone.0262143.ref004","doi-asserted-by":"crossref","first-page":"48","DOI":"10.1016\/j.jas.2016.03.007","article-title":"The technology of the earliest European cave paintings: El Castillo Cave, Spain","volume":"70","author":"F d\u2019Errico","year":"2016","journal-title":"J Archaeol Sci."},{"key":"pone.0262143.ref005","first-page":"102006","article-title":"Relative chronology of Palaeolithic drawings of the Great Ceiling, Rouffignac cave, by chemical, stylistic and superimposition studies","volume":"29","author":"M Gay","year":"2020","journal-title":"J Archaeol Sci Rep"},{"key":"pone.0262143.ref006","author":"BL MacDonald","year":"2016","journal-title":"Methodological developments for the geochemical analysis of ochre from archaeological contexts: case studies from British Columbia and Ontario, Canada [Internet] [Thesis]"},{"issue":"10","key":"pone.0262143.ref007","doi-asserted-by":"crossref","first-page":"e0163565","DOI":"10.1371\/journal.pone.0163565","article-title":"A Unique Collection of Palaeolithic Painted Portable Art: Characterization of Red and Yellow Pigments from the Parpall\u00f3 Cave (Spain)","volume":"11","author":"C Roldan Garc\u00eda","year":"2016","journal-title":"PLOS ONE"},{"key":"pone.0262143.ref008","doi-asserted-by":"crossref","first-page":"59","DOI":"10.2307\/j.ctvxrq0ks.7","volume-title":"Paleoart and Materiality The Scientific Study of Rock Art [Internet]","author":"M. 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