{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T08:57:53Z","timestamp":1790931473148,"version":"4.1.0"},"reference-count":71,"publisher":"MDPI AG","issue":"10","license":[{"start":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T00:00:00Z","timestamp":1790899200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000780","name":"iPhotoCult","doi-asserted-by":"publisher","award":["101132448"],"award-info":[{"award-number":["101132448"]}],"id":[{"id":"10.13039\/501100000780","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Heritage"],"abstract":"<jats:p>The present work reports the results of a multianalytical study on a renowned Etruscan large bronze masterpiece from Florence\u2019s National Museum of Archaeology known as the Arringatore of Pila. Thorough microstratigraphic characterization, metallotechnical examination, and measurement of the alloy compositions using the LIBS depth profile approach were carried out. This allowed us to collect new information on the execution processes of the present bronze sculpture and, more in general, on the materials and methods of the art foundry during the late Etruscan period, which is still little known. Furthermore, we provide the first compositional and microstructural demonstration of an intentional blackish patina based on thermally induced surface oxidation to form a cuprite\u2013tenorite bilayer on the present bronze surface. The discrimination between ancient or modern production of such a bilayer is discussed in some detail along with microstructural clues supporting the intentionality of the tenorite-based blackish appearance. To achieve this goal, \u03bcRaman spectroscopy compositional mapping was successfully associated with the results of optical and SEM microscopy and XRD to achieve an exhaustive material characterization. With respect to the general objective of delving into issues of the art foundry of the past, seeking to uncover its unknown aspects, the results reported here offer various points for discussion and make a concrete contribution to advancing knowledge on the technological aspects of ancient large bronze statuary.<\/jats:p>","DOI":"10.3390\/heritage9100402","type":"journal-article","created":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T08:15:18Z","timestamp":1790928918000},"page":"402","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["New Material Clues on Execution Processes and Appearance of Ancient Large Bronzes Unveiled by Imaging, Microstructural, and Laser Spectroscopy Characterization of the Arringatore of Pila"],"prefix":"10.3390","volume":"9","author":[{"given":"Salvatore","family":"Siano","sequence":"first","affiliation":[{"name":"Istituto di Fisica Applicata \u201cNello Carrara\u201d-Consiglio Nazionale delle Ricerche, 50019 Sesto Fiorentino, Florence, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sonia","family":"Mugnaini","sequence":"additional","affiliation":[{"name":"Department of Physical Sciences, Earth and Environment, University of Siena, 53100 Siena, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5357-8346","authenticated-orcid":false,"given":"Iacopo","family":"Osticioli","sequence":"additional","affiliation":[{"name":"Istituto di Fisica Applicata \u201cNello Carrara\u201d-Consiglio Nazionale delle Ricerche, 50019 Sesto Fiorentino, Florence, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7217-8663","authenticated-orcid":false,"given":"Daniele","family":"Ciofini","sequence":"additional","affiliation":[{"name":"Istituto di Fisica Applicata \u201cNello Carrara\u201d-Consiglio Nazionale delle Ricerche, 50019 Sesto Fiorentino, Florence, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0372-7614","authenticated-orcid":false,"given":"Andrea A.","family":"Mencaglia","sequence":"additional","affiliation":[{"name":"Istituto di Fisica Applicata \u201cNello Carrara\u201d-Consiglio Nazionale delle Ricerche, 50019 Sesto Fiorentino, Florence, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1531-4750","authenticated-orcid":false,"given":"Lorenzo","family":"Marzini","sequence":"additional","affiliation":[{"name":"Istituto di Fisica Applicata \u201cNello Carrara\u201d-Consiglio Nazionale delle Ricerche, 50019 Sesto Fiorentino, Florence, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marco","family":"Giamello","sequence":"additional","affiliation":[{"name":"Department of Physical Sciences, Earth and Environment, University of Siena, 53100 Siena, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6119-2470","authenticated-orcid":false,"given":"Juri","family":"Agresti","sequence":"additional","affiliation":[{"name":"Istituto di Fisica Applicata \u201cNello Carrara\u201d-Consiglio Nazionale delle Ricerche, 50019 Sesto Fiorentino, Florence, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,10,2]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"120","DOI":"10.1021\/ed044p120","article-title":"The Early History of Chemistry in the Service of Archaeology","volume":"44","author":"Caley","year":"1967","journal-title":"J. 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