Lead Isotope Study on the Source of Copper Material for Bronze Vessels in Dongdazhangzi Warring States Period Cemetery, Liaoning Province
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摘要: 东大杖子墓地作为辽宁乃至东北亚地区等级极高的战国时期墓地，自发掘以来一直受到学术界的高度关注，前期的研究工作主要集中在墓葬以及随葬品类型学、文化性质等方面，缺乏对该墓地出土青铜器矿料来源的研究。本文采用电感耦合等离子体发射光谱仪、扫描电镜能谱仪和表面电离型固体质谱仪对该墓地出土的7件青铜样品进行了成分和铅同位素比值分析。成分测试结果显示7件样品中有4件为铅锡青铜，2件为锡青铜，1件未知，器物功用和合金性能基本相匹配；铅同位素示踪结果显示部分器物的铜料不大可能来自内蒙古林西大井、辽宁红透山以及山西中条山等铜矿；5件铅含量大于2%的样品铅同位素比值206Pb/204Pb、207Pb/204Pb、208Pb/204Pb变化范围分别为17.685~17.941、15.530~15.612、38.080~38.404，其铅料来自辽宁青城子铅锌矿的可能性极大。本研究有助于探索辽宁东大杖子战国墓地出土铜器的矿料来源，同时为研究战国时期辽西与辽东半岛的金属资源贸易和流通以及辽东半岛资源开发历史提供了科学的证据。
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关键词:
- 青铜器 /
- 合金技术 /
- 矿料来源 /
- 青城子铅锌矿 /
- 电感耦合等离子体发射光谱仪 /
- 扫描电镜-能谱仪 /
- 表面电离型固体质谱仪
Abstract:BACKGROUNDAs a high-grade cemetery in Liaoning Province and Northeastern Asia in the Warring States Period, Dongdazhangzi cemetery has received a lot of attention since it was excavated. Previous studies mainly focus on the structure of the tombs, the typology of burial objects, and the cultural properties. The provenance studies for bronze objects are lacking. OBJECTIVESTo discuss the provenance of bronzes in the Dongdazhangzi cemetery. METHODSICP-OES, SEM-EDS and TIMS have been used to analyze the chemical and lead isotopic compositions of 7 bronze samples from tomb No.03JDM4. RESULTSChemical analysis revealed that there are 4 lead-tin bronzes and 2 tin bronzes out of all 7 samples, but the alloy type of the rest is yet unknown. The function of the objects is basically matched with the properties of the alloy. Lead isotope analysis indicated that the copper is unlikely to come from copper mines such as Inner Mongolia Linxi Dajing, Liaoning Hongtoushan and Shanxi Zhongtiaoshan. The lead isotope ratios of 5 samples, which contain lead exceeding 2%, range from 17.685 to 17.941 for 206Pb/204Pb, 15.530 to 15.612 for 207Pb/204Pb, 38.080 to 38.404 for 208Pb/204Pb. The lead sources are likely from the Qingchengzi lead-zinc deposit in Liaoning Province. CONCLUSIONSThis study contributes to the provenance study of bonzes in Dongdazhangzi Warring States cemetery in Liaoning Province. At the same time, scientific evidence for the research of the trade and circulation of metal sources between Western Liaoning and Liaodong Peninsula during the Warring States Period is provided, as well as the exploitation history of the metal resources of Liaodong Peninsula. -
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图 2 锡青铜器与北方部分铜矿的铅同位素比值(a)208Pb/204Pb -206Pb/204Pb和(b)207Pb/204Pb-206Pb/204Pb比较图
Figure 2.
图 3 铅锡青铜器与东北地区部分铅矿的铅同位素比值(a)208Pb/204Pb -206Pb/204Pb和(b)207Pb/204Pb-206Pb/204Pb比较图
Figure 3.
表 1 东大杖子战国墓地出土铜器的化学成分及铅同位素比值
Table 1. Chemical composition and Pb isotope ratios of the bronze samples from the Dongdazhangzi cemetery, the Warring States Period
样品编号 出土编号 器物名称 取样部位 分析方法 元素成分(%) 合金类型 铅同位素比值 Cu Sn Pb 206Pb/204Pb 207Pb/204Pb 208Pb/204Pb ZY-2136 03JDM4:40 匜 腹部 ICP-OES 80.92 9.97 8.48 铅锡青铜 17.934 15.612 38.379 ZY-2137 03JDM4:13 洗 口沿 ICP-OES 83.56 8.93 7.87 铅锡青铜 17.941 15.592 38.404 ZY-2138 03JDM4:21 盖豆 底部 SEM-EDS 70.30 10.35 - 锡青铜 17.695 15.544 38.280 ZY-2139 03JDM4 残件 残块 ICP-OES 82.15 14.85 1.37 锡青铜 17.875 15.572 38.252 ZY-2140 03JDM4 残件 残块 ICP-OES 78.87 9.66 3.73 铅锡青铜 17.685 15.530 38.233 ZY-2141 03JDM4:10 鼎 底部 SEM-EDS 19.48 20.04 20.70 铅锡青铜 17.719 15.548 38.120 ZY-2142 03JDM4:10 鼎 足部 SEM-EDS 20.06 1.27 29.41 未知 17.704 15.533 38.080 注：本表中成分数据未作归一化处理，“-”表示该元素未检出。 
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