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微量天然蚕丝样品的锶同位素组成高精度测定及产地溯源OA

High-Precision Strontium Isotope Analysis and Origin Tracing of Trace-Level Natural Silk Samples

中文摘要英文摘要

丝绸作为古代丝绸之路最具代表性的贸易载体,其产地溯源研究长期依赖艺术史学方法,缺乏基于自然科学的精准判别技术.放射性锶同位素(87Sr/86Sr)因具有鲜明的地域特征,被认为是最具潜力的溯源技术之一,其应用已从传统地质学领域广泛拓展至文物考古领域.蚕丝是丝绸的主要纺织材料,具有高有机质(>95%)、低锶含量(~1 μg/g)等特性.然而,现有地质样品分析方法通常需消耗整个或多个蚕茧(数百毫克),难以满足珍贵丝绸文物的微损耗分析要求.本文研究建立了一种微量蚕丝样品高精度锶同位素分析技术.通过强氧化剂(浓硝酸-双氧水)消解结合锶特效树脂柱纯化,在高效去除有机质的同时,实现高锶回收率(>99%)和超低流程本底(≤35 pg).纯化后的样品采用热电离质谱仪(TIMS)进行测定,结合"三明治"点样法和钨硅酸发射剂,将电离效率提升至 10%,对低至 0.5 ng的NBS987锶同位素标准物质进行测定,获得87Sr/86Sr比值为 0.710251±0.000033(n=31,2SD),与参考值一致.该方法仅需消耗大约 10 mg蚕丝样品,较传统方法耗样量降低 1~2个数量级.应用该技术对我国五大主产区不同品种蚕茧进行测定,发现蚕丝的锶同位素呈现地域与品种双重控制特征,其中地域因素起主导作用,证实锶同位素指纹作为丝绸产地溯源指标的可行性.本研究突破了微量蚕丝样品的锶同位素分析技术瓶颈,为丝绸文物微损溯源提供了技术支撑.

As one of the most representative trade commodities along the ancient Silk Road,silk artifacts have long been studied for provenance using art historical methodologies,yet have lacked scientifically rigorous analytical techniques grounded in the natural sciences.Radiogenic strontium(Sr)isotopes(87Sr/86Sr),known for their distinct geographical signatures,have emerged as a promising provenance tracing tool,with applications extending from geology into archaeology.Silkworm cocoons,the primary textile material for silk,exhibit high organic content(>95%)and low Sr concentrations(~1 μg/g).Conventional geological analysis methods typically require large sample sizes(entire or multiple cocoons or several hundred milligrams),making them unsuitable for minimally destructive analysis of precious silk artifacts.In this study,we developed a technique for high-precision Sr isotope analysis tailored to trace amounts of silk samples.By combining strong oxidant digestion(HNO3-H2O2)with Sr-specific resin purification,we achieved efficient organic matrix removal while maintaining high strontium recovery(>99%)and ultra-low procedural blanks(≤35 pg).Purified samples were analyzed using thermal ionization mass spectrometry(TIMS)with a"sandwich"loading technique and silicotungstic acid emitter,enhancing ionization efficiency to 10%.The method reliably measured as little as 0.5 ng of the NBS987 standard,yielding a mean 87Sr/86Sr ratio of 0.710251±0.000033(n=32,2SD),consistent with certified values.This approach reduces sample consumption to approximately 10 mg per analysis,representing a 1-2 order of magnitude improvement over conventional methods.This technique was then applied to cocoons of various silkworm breeds from China's five major silk-producing regions.The results revealed that Sr isotopic signatures of silk are influenced by both geographic origin and silkworm variety,with regional factors playing a dominant role.This confirms the viability of Sr isotopes as silk provenance indicators.Our technical breakthroughs in Sr isotope analysis of trace silk samples provide a foundational analytical framework for minimally invasive provenance studies of silk artifacts.The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202504060079.

贾丽玲;胡雅婷;胡志芳;冯兰平;周旸

中国丝绸博物馆,浙江 杭州 310002中国地质大学(武汉),地质过程与成矿预测全国重点实验室,湖北 武汉 430074赛默飞世尔科技(中国)有限公司,上海 201102中国地质大学(武汉),地质过程与成矿预测全国重点实验室,湖北 武汉 430074中国丝绸博物馆,浙江 杭州 310002

化学化工

珍贵样品蚕丝锶同位素热电离质谱法耗样量产地溯源

precious samplecocoon silkstrontium isotopeTIMSsample consumptiongeographic origin traceability

《岩矿测试》 2026 (2)

370-381,12

国家重点研发计划项目"考古有机残留物生物来源精细鉴别关键技术与应用"(2022YFF0903800)国家文物局文物科学技术研究项目"蚕丝纤维锶同位素提取方法优化研究"(2023ZCK016)浙江省文物保护科技项目"基于树脂交换分离技术对蚕丝中锶元素的分离富集方法研究"(2024003)

10.15898/j.ykcs.202504060079

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