古骨胶原硫含量和同位素比值的测定及其考古学意义  

Determination of sulfur content and isotope ratio of archaeological bone collagenusing EA-IRMS with temperature-ramped GC

作　　者：蔡慧娉 薛轶宁 杨刘杨 胡耀武 CAI Huiping;XUE Yining;YANG Liuyang;HU Yaowu(Department of Cultural Heritage and Museology,Fudan University,Shanghai 200433,China;Institute of Archaeological Science,Fudan University,Shanghai 200433,China;Thermo Fisher Scientific(China)Co.,Ltd.,Shanghai 201206,China)

机构地区：[1]复旦大学文物与博物馆学系,上海200433 [2]复旦大学科技考古研究院,上海200433 [3]赛默飞世尔科技(中国)有限公司,上海201206

出　　处：《文物保护与考古科学》2025年第2期8-16,共9页Sciences of Conservation and Archaeology

基　　金：国家自然科学基金(42172007)资助。

摘　　要：人(动物)骨胶原蛋白的硫稳定同位素比值,不仅可区分个体食物来源的差异,也可判断其迁徙行为。然而,受限于硫元素在骨胶原蛋白中的低含量(约0.2%),硫元素含量和其同位素比值的准确测定,一直是制约同位素生物考古研究的瓶颈。近些年来,国际学界新出现的质谱分析技术,虽已可实现对低样品量骨胶原S同位素比值的测定,但因缺乏低含量硫标准物质造成硫元素含量测定困难的问题依然存在。目前,我国尚未见到专门用于古骨胶原S含量和同位素测试方法的相关报道。为此,本研究利用基于具有程序升温气相色谱(GC)的元素分析-稳定同位素比值质谱仪(EA-IRMS)联机系统以磺胺和面团参考物质(pasta reference material,S含量为0.14%)为S元素含量测定的标准物质;以国际稳定同位素参考物质USGS42和USGS89为同位素标准物质,对2例古骨胶原中S含量和碳氮硫稳定同位素比值进行了多次测定;并以国际稳定同位素标样IAEA-S-1和IAEA-S-2对骨胶原数据校正,首次建立了骨胶原S含量和同位素比值的分析技术。该技术以低S含量参考物质为元素含量标准物质实现了古骨胶原S含量的准确测定(标准偏差约为0.02%);在保证硫稳定同位素测试精度、准度(<0.4‰)和仪器稳定的情况下,古骨胶原的用量(5.2~5.8 mg)较常用量(10 mg)大幅降低。该分析技术的建立,对于在我国重建先民(动物)的食谱和生存环境、探讨其迁徙行为具有重要的应用价值。The stable sulfur isotope ratio of human(animal)bone collagen can be used not only to distinguish differences in individual food sources,but also to judge their migratory behaviors.Stable sulfur isotopic analysis has become more and more important with the development of bioarchaeology.Previously,its application was not common because the extremely low content of sulfur in collagen(there was no suitable standard material with low sulfur content for accurate testing),requirement of a large sample size for testing,and memory effects made the test more complicated.Failure of the accurate determination of sulfur content and its isotope ratio has been a limitation for the research on isotopic bioarchaeology.In recent years,a newly developed mass spectrometry(MS)technology has been able to determine the sulfur isotope ratio of bone collagen with a small sample size,but the difficulty in determining the sulfur content due to the lack of a low-sulfur content standard substance still exists.At present,we have not yet seen any reports on the methods specific to sulfur content and isotopic testing for archaeological bone collagen.In this study,we used an elemental analysis-isotope ratio mass spectrometry(EA-IRMS)with programmed ramping gas chromatograph(GC)for the determination of sulfur content and isotope values of collagen.Our instrumental parameter settings and testing procedure are provided in the text.Firstly,we used sulfanilamide and pasta reference material(PRM,0.14%sulfur content)as standard substances for sulfur content determination.The standard curve established by PRM with different gradient masses was used to calibrate the international standard samples(USGS89 and USGS42)with a margin of error of lower than 0.1%,and a standard deviation of the sulfur content of the archaeological collagen samples within 0.02%.Then,we used the sulfur isotope values of the international standard samples(IAEA-S-1 and IAEA-S-2)to establish a linear regression curve by the two-point method,and corrected USGS42,whoseδ34 S was avail

关 键 词：元素分析-稳定同位素比值质谱仪 考古骨胶原 硫稳定同位素 元素含量 低样品量 

分 类 号：K854[历史地理—考古学及博物馆学]