Unraveling a Historical Mystery: Identification of a Lichen Dye Source in a Fifteenth Century Medieval Tapestry

Heritage Pub Date : 2024-05-01 DOI:10.3390/heritage7050112
Rachel M. Lackner, S. Ferron, J. Boustie, F. Le devehat, H. Lumbsch, Nobuko Shibayama
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Abstract

As part of a long-term campaign to document, study, and conserve the Heroes tapestries from The Cloisters collection at The Metropolitan Museum of Art, organic colorant analysis of Julius Caesar (accession number 47.101.3) was performed. Analysis with liquid chromatography–quadrupole time-of-flight mass spectrometry (LC-qToF-MS) revealed the presence of several multiply chlorinated xanthones produced only by certain species of lichen. Various lichen dye sources have been documented in the literature for centuries and are classified as either ammonia fermentation method (AFM) or boiling water method (BWM) dyes based on their method of production. However, none of these known sources produce the distinctive metabolites present in the tapestry. LC-qToF-MS was also used to compare the chemical composition of the dyes in the tapestry with that of several species of crustose lichen. Lichen metabolites, including thiophanic acid and arthothelin, were definitively identified in the tapestry based on comparison with lichen xanthone standards and a reference of Lecanora sulphurata, confirming the presence of a lichen source. This finding marks the first time that lichen xanthones have been identified in a historic object and the first evidence that BWM lichen dyes may have been used prior to the eighteenth century.
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揭开历史之谜:鉴定 15 世纪中世纪挂毯中的地衣染料来源
作为记录、研究和保护大都会艺术博物馆回廊系列英雄挂毯的长期活动的一部分,对凯撒大帝(编号 47.101.3)进行了有机着色剂分析。通过液相色谱-四极杆飞行时间质谱(LC-qToF-MS)分析,发现其中存在几种仅由某些地衣物种产生的多氯化氧杂蒽酮。几个世纪以来,文献中记载了各种地衣染料来源,并根据其生产方法将其归类为氨发酵法(AFM)或沸水法(BWM)染料。然而,这些已知的染料来源都不会产生织锦中出现的独特代谢物。我们还利用 LC-qToF-MS 将挂毯中染料的化学成分与几种甲壳地衣的化学成分进行了比较。根据与地衣黄酮标准品和硫磺藻参考品的比较,确定了挂毯中的地衣代谢物,包括硫hanic 酸和 arthothelin,从而证实了挂毯中存在地衣来源。这一发现标志着首次在历史文物中鉴定出地衣氧杂蒽酮,也首次证明了 BWM 地衣染料可能在十八世纪之前就已使用。
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