{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,2,21]],"date-time":"2025-02-21T14:09:54Z","timestamp":1740146994541,"version":"3.37.3"},"reference-count":52,"publisher":"Public Library of Science (PLoS)","issue":"6","license":[{"start":{"date-parts":[[2024,6,13]],"date-time":"2024-06-13T00:00:00Z","timestamp":1718236800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100003977","name":"Israel Science Foundation","doi-asserted-by":"publisher","award":["371\/18"],"award-info":[{"award-number":["371\/18"]}],"id":[{"id":"10.13039\/501100003977","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["www.plosone.org"],"crossmark-restriction":false},"short-container-title":["PLoS ONE"],"abstract":"<jats:p>Tefillin are Jewish ritual artifacts consisting of leather cases, containing inscribed slips, which are affixed with leather straps to the body of the tefillin practitioner. According to current Jewish ritual law, the tefillin cases and straps are to be colored black. The present study examines seventeen ancient tefillin cases discovered among the Dead Sea Scrolls in caves in the Judean Desert. All seventeen cases display grain surfaces with a very dark, nearly black appearance. We start with a hypothesis that the cases were intentionally colored black in antiquity using either a carbon-based or iron-gall-based paint or dye. The aim of this study is to test this hypothesis by subjecting these tefillin cases to a battery of examinations to assess the presence of carbon and iron used as pigments, and of organic materials which may have been used as binding agents in a paint. The tests deployed are: (1) macroscopic and microscopic analyses; (2) multispectral imaging using infrared wavelengths; (3) Raman spectroscopy; (4) Fourier transform infrared spectroscopy (FTIR); and (5) scanning electron microscope (SEM) and energy dispersive X-ray (EDX) spectroscopy. The results of these tests found no traces of carbon-based or iron-gall-based pigments, nor of organic compounds which may have served as binders in a paint. These results suggest that our posited hypothesis is unlikely. Instead, results of the SEM examination suggest it more likely that the black color on the surfaces of the tefillin cases is the result of natural degradation of the leather through gelatinization. The Judean Desert tefillin likely represent tefillin practices prior to when the rabbinic prescription on blackening tefillin was widely practiced. Our study suggests that the kind of non-blackened tefillin which the later rabbis rejected in their own times may well have been quite common in earlier times.<\/jats:p>","DOI":"10.1371\/journal.pone.0303635","type":"journal-article","created":{"date-parts":[[2024,6,13]],"date-time":"2024-06-13T17:25:18Z","timestamp":1718299518000},"page":"e0303635","update-policy":"https:\/\/doi.org\/10.1371\/journal.pone.corrections_policy","source":"Crossref","is-referenced-by-count":0,"title":["Black surfaces on ancient leather tefillin cases and straps from the Judean Desert: Macroscopic, microscopic and spectroscopic analyses"],"prefix":"10.1371","volume":"19","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7709-5453","authenticated-orcid":true,"given":"Yonatan","family":"Adler","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ilit","family":"Cohen-Ofri","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yonah","family":"Maor","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Theresa","family":"Emmerich Kamper","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7434-9844","authenticated-orcid":true,"given":"Iddo","family":"Pinkas","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"340","published-online":{"date-parts":[[2024,6,13]]},"reference":[{"key":"pone.0303635.ref001","doi-asserted-by":"crossref","first-page":"113","DOI":"10.2307\/j.ctv2z0vv3c.9","volume-title":"The origins of Judaism: An archaeological-historical reappraisal","author":"Y. Adler","year":"2022"},{"key":"pone.0303635.ref002","doi-asserted-by":"crossref","unstructured":"Adler Y. The distribution of tefillin finds among the Judean Desert caves. In: Fidanzio M, editor. The caves of Qumran: Proceedings of the international conference, Lugano 2014. Leiden: Brill; 2016. p. 161\u2013173.","DOI":"10.1163\/9789004316508_012"},{"key":"pone.0303635.ref003","unstructured":"Adler Y, Hayes GA. The scope of scriptural passages in tefillin in light of a comprehensive palaeographic analysis of the tefillin from the Judean Desert. Forthcoming."},{"key":"pone.0303635.ref004","unstructured":"Jerusalem Talmud, Megillah 4:9 (75c) (Leiden, Bibliotheek der Rijksuniversiteit\u2014Or. 4720)."},{"key":"pone.0303635.ref005","unstructured":"Babylonian Talmud, Shabbat 28b (all standard manuscripts)."},{"key":"pone.0303635.ref006","unstructured":"Babylonian Talmud Mena\u1e25ot 35a (all standard manuscripts)."},{"key":"pone.0303635.ref007","unstructured":"Karo J. Bet Yosef, \u02beOra\u1e25 \u1e25ayim 32, s.v. \u201cand black\u201d."},{"key":"pone.0303635.ref008","first-page":"7","volume-title":"Qumran Cave 1. DJD 1","author":"GL Harding","year":"1955"},{"key":"pone.0303635.ref009","first-page":"29","volume-title":"Les grottes de Murabba\u02bf\u00e2t. DJD 2","author":"R. De Vaux","year":"1961"},{"key":"pone.0303635.ref010","unstructured":"De Vaux R. Arch\u00e9ologie. In: Baillet M, Milik JT, De Vaux R, editors. Les \u2018petites grottes\u2019 de Qumr\u00e2n: Exploration de la falaise: Les grottes 2Q, 3Q, 5Q, 6Q, 7Q \u00e0 10Q: Le rouleau de cuivre. DJD 3; Oxford: Clarendon; 1962. p. 3\u201341 (esp. 31, pl 8:5\u20136)."},{"key":"pone.0303635.ref011","first-page":"178","volume-title":"Les \u2018petites grottes\u2019 de Qumr\u00e2n: Exploration de la falaise; Les grottes 2Q, 3Q, 5Q, 6Q, 7Q \u00e0 10Q; Le rouleau de cuivre. DJD 3","author":"JT Milik","year":"1962"},{"volume-title":"Tefillin from Qumran (XQ Phyl 1\u20134)","year":"1969","author":"Y. Yadin","key":"pone.0303635.ref012"},{"key":"pone.0303635.ref013","unstructured":"Milik JT. Tefillin, mezuzot et targums. In: De Vaux R, Milik JT, editors. Qumr\u00e2n grotte 4.II: I. Arch\u00e9ologie; II. Tefillin, mezuzot et targums (4Q128\u20134Q157). DJD 6; Oxford: Clarendon; 1977. p. 33\u201393 (esp. 34\u201335, pl. 6:1\u201313)."},{"key":"pone.0303635.ref014","doi-asserted-by":"crossref","first-page":"112","DOI":"10.1163\/15685179-12341413","article-title":"Remains of tefillin from Na\u1e25al \u1e62e\u02beelim (Wadi Seiyal): A leather case and two inscribed fragments (34Se 1 A\u2013B)","volume":"24","author":"Y. Adler","year":"2017","journal-title":"DSD"},{"volume-title":"Ancient skins, parchments and leathers","year":"1972","author":"R. Reed","key":"pone.0303635.ref015"},{"key":"pone.0303635.ref016","first-page":"42","volume-title":"Tefillin from Qumran (XQ Phyl 1\u20134)","author":"Y. Frankl","year":"1969"},{"volume-title":"Tangled up in text: Tefillin and the ancient world","year":"2008","author":"YB Cohn","key":"pone.0303635.ref017"},{"key":"pone.0303635.ref018","unstructured":"Zerdoun Bat-Yehouda M. Les encres noires au Moyen \u00e2ge (jusqu\u2019\u00e0 1600). Aubervilliers: Institut de Recherche et d\u2019Histoire des Textes (IRHT); 1983."},{"key":"pone.0303635.ref019","first-page":"167","article-title":"Manufacture of black ink in the ancient Mediterranean","volume":"54","author":"T. Christiansen","year":"2017","journal-title":"Bulletin of the American Society of Papyrologists"},{"key":"pone.0303635.ref020","unstructured":"Babylonian Talmud, \u0160abb. 23a (all standard manuscripts)."},{"key":"pone.0303635.ref021","unstructured":"Mishnah Gi\u1e6d\u1e6din 2:3 (all standard manuscripts)."},{"key":"pone.0303635.ref022","first-page":"77","volume-title":"Holistic Qumran: Trans-disciplinary research of Qumran and the Dead Sea Scrolls","author":"B Murphy","year":"2013"},{"key":"pone.0303635.ref023","unstructured":"Pliny, NH 34:123\u2013127. Rackham H, translator. Pliny, Natural history. Vol. 9, Books 33\u201335. Loeb Classical Library 394. Cambridge, MA: Harvard University Press; 1952."},{"key":"pone.0303635.ref024","doi-asserted-by":"crossref","first-page":"157","DOI":"10.1163\/156851796X00183","article-title":"The black ink of the Qumran scrolls","volume":"3","author":"Y Nir-El","year":"1996","journal-title":"DSD"},{"issue":"1","key":"pone.0303635.ref025","doi-asserted-by":"crossref","first-page":"97","DOI":"10.1163\/156851709X395722","article-title":"On the origin of the ink of the Thanksgiving Scroll (1QHodayot)","volume":"16","author":"I Rabin","year":"2009","journal-title":"DSD"},{"key":"pone.0303635.ref026","doi-asserted-by":"crossref","first-page":"208","DOI":"10.1016\/j.jasrep.2017.05.042","article-title":"Chemical characterization of black and red inks inscribed on Ancient Egyptian papyri: The Tebtunis temple library","volume":"14","author":"T Christiansen","year":"2017","journal-title":"Journal of Archaeological Science Reports"},{"key":"pone.0303635.ref027","doi-asserted-by":"crossref","first-page":"286","DOI":"10.1002\/xrs.1047","article-title":"The Vercelli Gospels laid open: An investigation into the inks used to write the oldest Gospels in Latin","volume":"37","author":"M Aceto","year":"2008","journal-title":"X-Ray Spectrom"},{"issue":"4","key":"pone.0303635.ref028","doi-asserted-by":"crossref","first-page":"314","DOI":"10.1080\/00032719.2011.644712","article-title":"A review of instrumental approaches for studying historical inks","volume":"45","author":"DM Goltz","year":"2012","journal-title":"Analytical Letters"},{"key":"pone.0303635.ref029","first-page":"221","volume-title":"Codex Sinaiticus: New perspectives on the ancient biblical manuscript","author":"G Moorhead","year":"2015"},{"key":"pone.0303635.ref030","doi-asserted-by":"crossref","first-page":"70","DOI":"10.1163\/9789004444805_006","volume-title":"Traces of ink","author":"I. Rabin","year":"2021"},{"key":"pone.0303635.ref031","doi-asserted-by":"crossref","first-page":"87","DOI":"10.1016\/j.culher.2016.09.006","article-title":"A multi-technique approach to the chemical characterization of colored inks in contemporary art: The materials of Lucio Fontana","volume":"23","author":"C Zaffino","year":"2017","journal-title":"Journal of Cultural Heritage"},{"key":"pone.0303635.ref032","doi-asserted-by":"crossref","first-page":"104370","DOI":"10.1016\/j.jprot.2021.104370","article-title":"Proteomics and metabolomics composition of the ink of a letter in a fragment of a Dead Sea Scroll from Cave 11 (P1032-Fr0)","volume":"249","author":"G Zilberstein","year":"2021","journal-title":"J Proteomics"},{"key":"pone.0303635.ref033","unstructured":"Pouchou JL, Pichoir F. Electron probe X-Ray microanalysis applied to thin surface films and stratified specimens. Scanning Microscopy. 1993; 7: Article 12."},{"issue":"8","key":"pone.0303635.ref034","doi-asserted-by":"crossref","first-page":"1079","DOI":"10.1002\/jrs.1989","article-title":"Identification of iron-gall inks with near-infrared Raman microspectroscopy","volume":"39","author":"AS Lee","year":"2008","journal-title":"Journal of Raman Spectroscopy"},{"issue":"2","key":"pone.0303635.ref035","doi-asserted-by":"crossref","first-page":"170","DOI":"10.1016\/j.vibspec.2005.11.006","article-title":"Raman analysis of iron gall inks on parchment","volume":"41","author":"AS Lee","year":"2006","journal-title":"Vibrational Spectroscopy"},{"issue":"4","key":"pone.0303635.ref036","doi-asserted-by":"crossref","first-page":"469","DOI":"10.1016\/0146-6380(92)90109-B","article-title":"High abundance of low molecular weight organic acids in hypersaline spring water associated with a salt diapir","volume":"18","author":"K Kawamura","year":"1992","journal-title":"Organic Geochemistry"},{"issue":"1","key":"pone.0303635.ref037","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1007\/s10973-007-8513-x","article-title":"Study of deterioration of historical parchments by various thermal analysis techniques complemented by SEM, FTIR, UV-Vis-NIR and unilateral NMR investigations","volume":"91","author":"E Badea","year":"2008","journal-title":"Journal of Thermal Analysis and Calorimetry"},{"key":"pone.0303635.ref038","first-page":"89","volume-title":"lmproved damage assessment of parchment (IDAP): Assessment, data collection and sharing of knowledge","author":"G Della Gatta","year":"2007"},{"key":"pone.0303635.ref039","doi-asserted-by":"crossref","first-page":"109414","DOI":"10.1016\/j.polymdegradstab.2020.109414","article-title":"Parchment browning\u2014Part II: The Dead Sea Scrolls","volume":"183","author":"Y Maor","year":"2021","journal-title":"Polymer degradation and stability"},{"issue":"8","key":"pone.0303635.ref040","doi-asserted-by":"crossref","DOI":"10.1007\/s00216-012-6681-4","article-title":"Non-destructive spectroscopic investigation on historic Yemenite scriptorial fragments: Evidence of different degradation and recipes for iron tannic inks","volume":"405","author":"M Bicchieri","year":"2013","journal-title":"Analytical and Bioanalytical Chemistry"},{"key":"pone.0303635.ref041","doi-asserted-by":"crossref","first-page":"109109","DOI":"10.1016\/j.polymdegradstab.2020.109109","article-title":"Parchment browning and the Dead Sea Scrolls\u2014Part I: Artificial aging","volume":"176","author":"Y Maor","year":"2020","journal-title":"Polymer Degradation and Stability"},{"issue":"1","key":"pone.0303635.ref042","first-page":"1","article-title":"A study of the deterioration of aged parchment marked with laboratory iron gall inks using FTIR-ATR spectroscopy and micro hot table","volume":"4","author":"SC Boyatzis","year":"2016","journal-title":"Heritage Science"},{"issue":"1","key":"pone.0303635.ref043","doi-asserted-by":"crossref","first-page":"23","DOI":"10.1179\/sic.2005.50.1.23","article-title":"X-Ray fluorescence analysis of iron gall inks, pencils and coloured crayons","volume":"50","author":"O Hahn","year":"2005","journal-title":"Studies in Conservation"},{"key":"pone.0303635.ref044","article-title":"Study of discoloured iron-gall ink inscriptions\u2014case of the Gradual of Lviv Benedictines from Krzeszow","author":"A. Surmak","year":"2016","journal-title":"EEG 5"},{"key":"pone.0303635.ref045","first-page":"104","article-title":"The basics of fast-scanning XRF element mapping for iron-gall ink palimpsests","volume":"7","author":"L Glaser","year":"2014","journal-title":"Manuscript Cultures"},{"key":"pone.0303635.ref046","doi-asserted-by":"crossref","first-page":"234","DOI":"10.1002\/xrs.677","article-title":"Characterization of iron-gall inks in historical manuscripts and music compositions using X-ray fluorescence spectrometry","volume":"33","author":"O Hahn","year":"2004","journal-title":"X-Ray Spectrometry"},{"issue":"6","key":"pone.0303635.ref047","doi-asserted-by":"crossref","first-page":"1915","DOI":"10.1002\/jsfa.7297","article-title":"Effects of Maillard reaction on flavor and safety of Chinese traditional food: Roast duck","volume":"96","author":"Y Zhou","year":"2016","journal-title":"J. Sci. Food Agric"},{"issue":"C","key":"pone.0303635.ref048","doi-asserted-by":"crossref","first-page":"791","DOI":"10.1016\/0146-6380(84)90101-3","article-title":"Investigations on the structural units of melanoidins","volume":"6","author":"Y Rubinsztain","year":"1984","journal-title":"Org. Geochem"},{"issue":"4481","key":"pone.0303635.ref049","doi-asserted-by":"crossref","first-page":"491","DOI":"10.1126\/science.6779377","article-title":"Nonenzymatic browning in vivo: Possible process for aging of long-lived proteins","volume":"211","author":"VM Monnier","year":"1981","journal-title":"Science"},{"issue":"SUPPL. 2","key":"pone.0303635.ref050","doi-asserted-by":"crossref","first-page":"36","DOI":"10.2337\/diab.41.2.S36","article-title":"Maillard reaction-mediated molecular damage to extracellular matrix and other tissue proteins in diabetes, aging, and uremia","volume":"41","author":"VM Monnier","year":"1992","journal-title":"Diabetes"},{"issue":"2","key":"pone.0303635.ref051","doi-asserted-by":"crossref","first-page":"158","DOI":"10.1366\/12-06739","article-title":"Using attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) to study the molecular conformation of parchment artifacts in different macroscopic states","volume":"67","author":"L Gonzalez","year":"2013","journal-title":"Appl. Spectrosc"},{"key":"pone.0303635.ref052","first-page":"61","volume-title":"The synoptic problem in rabbinic literature","author":"C. Hayes","year":"2000"}],"container-title":["PLOS ONE"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/dx.plos.org\/10.1371\/journal.pone.0303635","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,6,13]],"date-time":"2024-06-13T17:25:47Z","timestamp":1718299547000},"score":1,"resource":{"primary":{"URL":"https:\/\/dx.plos.org\/10.1371\/journal.pone.0303635"}},"subtitle":[],"editor":[{"given":"Carlos P.","family":"Odriozola","sequence":"first","affiliation":[],"role":[{"role":"editor","vocabulary":"crossref"}]}],"short-title":[],"issued":{"date-parts":[[2024,6,13]]},"references-count":52,"journal-issue":{"issue":"6","published-online":{"date-parts":[[2024,6,13]]}},"URL":"https:\/\/doi.org\/10.1371\/journal.pone.0303635","relation":{},"ISSN":["1932-6203"],"issn-type":[{"type":"electronic","value":"1932-6203"}],"subject":[],"published":{"date-parts":[[2024,6,13]]}}}