文物保护与考古科学2025，Vol.37Issue(2)：8-16,9.DOI:10.16334/j.cnki.cn31-1652/k.20240503266
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 collagen using EA-IRMS with temperature-ramped GC
摘要
Abstract
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,whose δ34 S was available.The accuracy of the corrected δ34 S obtained was better than 0.3‰.Finally,we tested archaeological bone collagen samples and combined various factors,such as signal strength,sample mass,and instrument stability,and determined that stable isotope values obtained could be more accurate and stable when using a mass of 5 200-5 800 μg of collagen samples,with a standard deviation of δ34 S of lower than 0.4‰. Compared with the existing stable sulfur isotopic testing methods for collagen from various institutions around the world,the analytical method we established for the sulfur content and isotope ratio of bone collagen is also in the leading position.The application of this method in China will greatly promote the development of stable isotopic bioarchaeology,making sulfur isotopic analysis become one of the routine methods for isotopic analysis in the field of archaeology.This method is expected to better reveal the food structure and migratory behavior of ancient humans(animals)in China,and to explore important scientific and archaeological issues.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Key words
EA-IRMS/Archaeological bone collagen/Stable sulfur isotope/Element content/Small sample size分类
历史学引用本文复制引用
蔡慧娉,薛轶宁,杨刘杨,胡耀武..古骨胶原硫含量和同位素比值的测定及其考古学意义[J].文物保护与考古科学,2025,37(2):8-16,9.基金项目
国家自然科学基金(42172007)资助 （42172007）
