Abstract This work is focused on the chemical characterization of the organic residues preserved in ceramic fragments that are suspected to have been used by the Basque whalers in the period from 16th to 17th Century to store whale oil. The lipid profiling along with the identification of biomolecular markers, makes possible to obtain information on the contents of the vessels and on the transformations undergone by the organic substances during the burial process. To achieve this goal, two complementary analytical techniques, High-Performance Liquid Chromatography - Electrospray Ionization - Quadrupole Time-of-Flight Mass Spectrometry (HPLC-ESI-QToF) and Gas Chromatography-Mass Spectrometry (GC–MS), were used not only to study the archaeological materials but also fresh whale oil products used as reference materials with the aim to detect potential diagnostic biomarkers. HPLC-ESI-QToF was used to identify triacylglycerols (TAGs) and study their distribution in the various samples, whereas GC–MS after suitable derivatization provided the fatty acid (FA) profile together with the detection of degradation compounds (dicarboxylic and dihydroxy fatty acids) and biomarkers related to marine commodities (isoprenoid acids). Samples of blubber from 5 different whale species belonging to the genus Balaenoptera (fin, sei and minke whale), Megaptera (Humpback whale) and Phocoena (harbour porpoise) were used as reference materials together with a sample of whale oil of unknown origin. The chemical results confirm the archaeological data regarding the vessels use as containers to store whale oil and indicate the whales from Balaenoptera genus as the most probable source of the oil.

中文翻译：

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16 至 17 世纪巴斯克捕鲸者使用的陶瓷容器中有机脂质残留物的 GC-MS 和 HPLC-ESI-QToF 表征

摘要 这项工作的重点是保存在陶瓷碎片中的有机残留物的化学特征，这些碎片被怀疑在 16 至 17 世纪被巴斯克捕鲸者用来储存鲸油。脂质分析以及生物分子标记的鉴定，使得获得关于容器内容物和有机物质在埋藏过程中所经历的转变的信息成为可能。为了实现这一目标，两种互补的分析技术，高效液相色谱 - 电喷雾电离 - 四极杆飞行时间质谱 (HPLC-ESI-QToF) 和气相色谱 - 质谱 (GC-MS)，不仅用于研究考古材料，还用于研究用作参考材料的新鲜鲸油产品，目的是检测潜在的诊断生物标志物。HPLC-ESI-QToF 用于鉴定三酰甘油 (TAGs) 并研究它们在各种样品中的分布，而适当衍生化后的 GC-MS 提供脂肪酸 (FA) 谱以及降解化合物（二羧酸和二羟基脂肪酸）的检测）和与海洋商品（异戊二烯酸）相关的生物标志物。来自 5 种不同鲸鱼物种的鲸脂样本，属于 Balaenoptera（鳍鲸、sei 和小须鲸）、Megaptera（座头鲸）和 Phocoena（港湾鼠海豚）与来源不明的鲸油样本一起用作参考材料。