虢国墓地出土部分青铜器微量元素的分析

将微量元素示踪法与铅同位素比值法结合起来对青铜器矿料的溯源会起到相得益彰的效果。先前对虢国墓地青铜器的铅同位素比值测定表明,其青铜器铅同位素与山西中条山和长江中下游地区都有重合。本次微量元素分析结果显示,虢国墓地青铜器与山西中条山古矿冶遗址微量元素特征不同,而与长江中下游地区的湖北铜绿山古矿冶遗址铜锭的微量元素特征相似,推测长江中下游地区可能为虢国墓地青铜器提供了大量的铜料。此外,微量元素与铅同位素都表明虢国墓地不同墓葬的青铜器基本具有一致的矿料来源。     

广州地区出土西汉青铜器矿料来源分析

广州地区出土汉代青铜器数量众多，在考古学方面研究成果不少，但通过科技考古研究其产地的却不多。为研究广州地区出土西汉青铜器矿料来源，通过对广州出土西汉青铜器进行成分分析和铅同位素比值测试，与广西、江西、云南、贵州、安徽、湖北、河南、河北、北京等地出土同时期青铜器成分进行比较，发现西汉中晚期各地青铜器合金配比情况基本趋同。且根据含砷等微量元素这一显著特征，认为与广西合浦出土同时期青铜器矿料可能来自同一个地方。测试的铅同位素比值高度集中，其矿料应该来自同一个地方。分别与广东、贵州、云南、陕西、河南等地战国至西汉青铜器铅同位素比值进行比对，发现与广东、贵州、云南出土青铜器矿料来源同属一个大的成矿区，与河南、陕西等地明显区别。验证了学者们在考古学研究认为岭南地区出土西汉青铜器产自本地的观点。     

东周青铜器铅同位素比值的初步研究

铅同位素比值能够反映矿料的类型及其空间分布,指示矿料的流通方式,并为准确溯源提供重要的线索和判别标准。将东周时期青铜器铅同位素比值数据按时代、地域分组,可以初步构建青铜器矿料的时空框架。春秋早期青铜器的铅同位素比值高度集中,各地均使用A类矿料;春秋中期存在汉淮地区B类矿料与中原地区A类矿料的对立;春秋晚期至战国早期,中原及周边地区主要使用C类矿料。战国中晚期铅同位素比值趋于分散。     

从铅同位素比值试析商周时期青铜器的矿料来源

1．商代中原青铜器的铅同位素比值结果 在中国冶金术的起源研究中．商周时期青铜器的矿料来源问题,显得格外引人瞩目,半个多世纪以来,这一问题作为涉及商周历史的重大学术课题,一直得到人们的足够重视。郭沫若、唐兰、容庚、闻广等前辈都进行过热烈的讨论,     

秦始皇帝陵园出土彩绘青铜水禽铜矿料来源探索

关于秦始皇帝陵出土彩绘青铜水禽铜矿料来源的研究,对进一步研究秦代的物质文化、青铜器冶铸工艺、装饰工艺以及铜矿来源均具有重要意义。本研究对部分秦始皇帝陵园出土彩绘青铜水禽基体进行了铅同位素分析及微量元素分析。并在此基础之上,与甘肃东部及关中西部出土的部分早期秦文化铜器、国墓地出土的部分铜器、周原李家铸铜作坊出土的部分铜器、山西中条山、江西瑞昌、江西铜岭、安徽铜陵以及湖北大冶铜绿山古铜矿以及秦岭山区的部分现代铜矿的相关数据进行了对比研究。结果发现,秦始皇帝陵园出土的青铜水禽使用了相同的矿料,且与绝大多数早期秦文化铜器所使用的矿料基本相同,但与国墓地以及李家铸铜作坊出土西周铜器的矿料明显有别。秦人使用的铜矿与秦岭山区现代铜矿较为接近,表明秦人的铜矿来源可能与秦岭山区有关。     

秦始皇帝陵园出土彩绘青铜水禽铜矿料来源探索

关于秦始皇帝陵出土彩绘青铜水禽铜矿料来源的研究,对进一步研究秦代的物质文化、青铜器冶铸工艺、装饰工艺以及铜矿来源均具有重要意义。本研究对部分秦始皇帝陵园出土彩绘青铜水禽基体进行了铅同位素分析及微量元素分析。并在此基础之上,与甘肃东部及关中西部出土的部分早期秦文化铜器、国墓地出土的部分铜器、周原李家铸铜作坊出土的部分铜器、山西中条山、江西瑞昌、江西铜岭、安徽铜陵以及湖北大冶铜绿山古铜矿以及秦岭山区的部分现代铜矿的相关数据进行了对比研究。结果发现,秦始皇帝陵园出土的青铜水禽使用了相同的矿料,且与绝大多数早期秦文化铜器所使用的矿料基本相同,但与国墓地以及李家铸铜作坊出土西周铜器的矿料明显有别。秦人使用的铜矿与秦岭山区现代铜矿较为接近,表明秦人的铜矿来源可能与秦岭山区有关。     

夏家店下层文化遗址出土铜器的矿料来源分析

为进一步了解夏家店下层文化铜器的物料信息,探讨其矿料来源,采用多接收电感耦合等离子体质谱仪(MC-ICP-MS)对4处夏家店下层文化遗址和1处高台山文化遗址出土的部分铜器进行了铅同位素比值测定,并将测定结果同辽西地区几处金属矿的铅同位素数据进行了对比。结果表明:这4处夏家店下层文化遗址出土铜器的原料可能是使用辽西当地的大井多金属矿的矿石冶炼而成,而大山前遗址出土铜器的铅料有可能来自辽宁桓仁的多金属矿,二道井子遗址所出红铜器的铜料则可能另有来源。所属高台山文化的湾柳遗址铜器的铅同位素数据具有高放射性成因铅特征,表明其与同期其他考古学文化存在某种联系。     

重庆地区出土青铜器铅同位素比值研究

青铜器矿料来源和产地研究,是青铜时代至关重要的考古问题,也是考古的重点和难点之一.通过比较青铜器样品和矿床的Pb同位素分析数据,可以进行青铜金属原料来源的产地研究.为此,本工作利用MAT262固态离子源型质谱仪对重庆地区云阳李家坝遗址,涪陵小田溪墓群,万州大坪墓群,开县余家坝遗址东周时期巴地青铜器的铅同位素进行了测定和比值研究.结果显示其中合金中铅都为普通铅,而非放射性成因铅.实验数据反映出206Pb/204 Pb比值分布在17.4630 ～ 18.6960,207 Pb/204 Pb比值分布在15.5573 ～ 15.8490,208 pb/204 Pb比值分布在36.7828 ～39.3869,除了两个数据外,大部分器物铅同位素比值分布范围几乎重叠,显示了稳定铅源的存在.此外,这批数据与滇川黔铅锌多金属成矿区的底苏和大梁子矿床数据分布范围相近,局部重合,表明其铅料来源与这一地区有着一定的关系.实验结果反映了重庆地区东周青铜器群在铅料来源上具有同一性和连续性,说明了巴人在春秋时期就已经建立了独立的青铜冶铸业,一直延续到战国时期.     

郑韩故城出土青铜器的矿料来源初步分析

基于富集在铜料中而保留其母矿信息的元素可以用于示踪青铜器的矿料来源,为了解郑韩故城青铜器的矿料来源,利用ICP-AES方法对郑韩故城出土东周时期青铜器的微量元素进行了检测。结果显示,21个青铜器样品微量元素特征具有相对一致性,推测可能具有相同的原料来源。与小双桥遗址出土青铜器的微量元素特征进行对比,二者存在明显的差异,说明从商代中期到春秋战国时期,这一地区的原料来源发生了改变。研究结果可为研究东周时期这一地区铜业发展状况提供线索。     

青铜器铅同位素指示意义的范铸实验研究

铅同位素比值作为探索青铜器产地和矿料来源的指示剂而被广泛采用,为论证这种方法的可行性,进行了仿古范铸实验。测试分析表明,长江中、下游出土古铜锭含铅量大多在1％以下,样品中添加铅的含量远高于铜、锡料所带入的微量铅。结果证明,青铜器铅同位素的指示意义是不确定的,并且在冶铸过程中可能存在铅同位素的分馏。     

Provenance of Early Bronze Age metal artefacts in Western Switzerland using elemental and lead isotopic compositions and their possible relation with copper minerals of the nearby Valais

Ten Early Bronze Age (BzA1, 2200–2000 BC) copper artefacts from the central Valais region from Switzerland were studied for their elemental composition and lead isotope ratios. In order to answer the archaeological question of a local copper supply, a database for copper minerals across the Valais (Switzerland) has been established. This database contains 69 data on lead isotope ratios as well as additional information on the minerals and geochemical associations for copper minerals from 38 locations in the Valais. Comparisons of the artefacts were also made with data pertaining to minerals from various deposits from Europe and Anatolia taken from the literature. The provenance of the materials is very diverse. Some of the data are compatible with the data from the copper mineral deposits of the Valais region. Moreover, three copper lunulae were identified as possibly Tuscan, which suggests contacts between Italy and the Valais region. This pattern also establishes a multiplicity of provenances for the metal and cultural influences in the Alpine environment of the Rhone Valley of Switzerland at the beginning of the Early Bronze Age.     

古代含砷麻江型铜鼓研究

为研究古代麻江型铜鼓的成分、工艺和矿料来源及麻江型铜鼓与遵义型铜鼓的发展源流关系,本研究采用扫描电镜能谱分析、金相显微镜分析和铅同位素比值分析等方法,对所取4面含砷麻江型铜鼓进行分析研究。结果表明其为Cu-Sn-As-Pb四元合金。同时结合文献研究可知,古代麻江型铜鼓中含砷的情况较为普遍,且含量较高。将该4面麻江型铜鼓与含砷遵义型铜鼓进行成分及铅同位素比值对比及地缘、矿产进行相关研究可知,含砷的两种类型铜鼓存在着一定的源流关系,并且含砷的两种类型铜鼓的矿料可能来源于云南文山地区与广西百色地区一带。     

Isotopic Composition of Lead in Copper Ores and a Copper Artefact from the La Profunda Mine (León,Spain)

This paper continues the characterization of the lead isotopic fingerprint of ancient copper mines in the north‐west of Spain. In this work, the lead isotopic compositions found in copper ores from the La Profunda mine are presented. Azurites and malachites sampled from this deposit were subjected to lead isotope analysis by multicollector ICP–MS. The results showed a clear radiogenic lead signature compatible with the presence of uranium‐rich minerals (such as zeunerite) in the same mining complex. Moreover, a rare copper artefact, found in the galleries of the mine during its modern exploitation, was also analysed and showed that local mineral was used for its manufacturing.     

THE ORIGIN of METAL OBJECTS FROM the EARLY BRONZE AGE SITE of THERMI ON the ISLAND of LESBOS

Summary: Lead isotope analysis of metal are deposits in the Mediterranean provides an important database for provenance studies of ancient metal artefacts. the Isotrace laboratory at Oxford has accumulated during the past decade well over 2000 lead isotope data on copper and lead ores and these data (in addition to analyses published by other groups) can be used for comparisons with lead isotope compositions of ancient metal objects. In a search for the roots of Early Bronze Age metallurgy in Europe we have analysed 34 copper-based objects from the Early Bronze Age strata of the town of Thermi on the Aegean island of Lesbos. the results of lead isotope analysis show that the metal objects on this site have a quite varied origin. Some of the objects are made of copper consistent with an origin from the mineral deposits of the Troad whilst others might be made of copper from the Cyclades. However, there are also some objects which are not made of copper from any of the Aegean deposits. These imports have later parallels on the site of Kastri on Syros and amongst the objects excavated by Schliemann at Troy.     

朝鲜半岛及日本细形青铜武器的原料产地

对朝鲜半岛及日本出土细形青铜武器的原料产地问题作了尝试性探讨,以了解朝、日及中国大陆古代青铜原料的流通状况。利用青铜器及铅矿物中所含铅的四种稳定同位素的比值,在三维坐标系中观察其分布规律,并结合统计学方法探讨青铜器所含铅与铅矿地域特征的关联。通过比较分析中国大陆、朝鲜半岛及日本列岛出土的部分青铜器及铅矿物标本的铅同位素比值,指出上述三地某些青铜器原料中的铅可能有共同的产地,而朝、日当地铅矿的开采似不早于公元7世纪,故朝、日细形青铜武器的铅原料可能来自中国大陆。     

NEW APPROACHES ON THE ARCHAIC TRADE IN THE NORTH‐EASTERN IBERIAN PENINSULA: EXPLOITATION AND CIRCULATION OF LEAD AND SILVER

A wide‐ranging study based on compositional and isotopic analyses of minerals and manufactured objects from the north‐eastern Iberian Peninsula and their respective archaeological and cultural contexts demonstrates significant lead mineral exploitation in the El Priorat area (Tarragona province) linked to Phoenician trade (seventh–sixth centuries BC). This exploitation continued, despite losing intensity, until the Romanization of the territory. Our project also aims to determine the nature and origin of the lead and silver supply in the northern Iberian territory surrounding the Phocaean enclave of Emporion, especially with regard to the demands of the colonial mint. The behaviour pattern of the circulation of lead, silver and copper in Catalonia in the period studied indicates a plurality of contemporary supply sources, although, at least from the fifth century BC onward, minerals and metals from the south‐eastern Iberian Peninsula take on considerable importance.     

Metal provenancing using isotopes and the Oxford archaeological lead isotope database (OXALID)

This paper reviews the research into the methodology of lead isotope provenance studies carried out at the University of Oxford between 1975 and 2002, at first in the Department of Geology (Geological Age and Isotope Research Laboratory), later in the Isotrace Laboratory based in the Department of Nuclear Physics, and eventually part of the Research Laboratory of Archaeology and the History of Art. These 27 years of intensive work, funded initially by the Stiftung Volkswagenwerk, and later from numerous UK Government and Charitable funds and finally by the Institute of Aegean Prehistory laid the foundations of the lead isotope provenance methodology and resulted in a large database of analytical isotope and elemental results. In spite of the efforts of the authors, this database is still not comprehensively published or easily accessible in a digital format by all researchers interested in using this method for their projects. The possibilities of advancing this situation are discussed. The authors discuss in detail the basic restrictions and advantages of using the lead isotope compositions of ores in mineral deposits for finding the origin of the raw materials used for making ancient artefacts. Methods for the scientific interpretation of the data are discussed, including attempts to use statistical methods. The methodology of creating the Oxford lead isotope database (OXALID) is outlined and a summary is given of the lead isotope resource provided by OXALID.     

A New Method For Combining Lead Isotope and Lead Abundance Data to Characterize Archaeological Copper Alloys*

We present a new methodology for interpreting lead isotope data from archaeological copper alloy objects. It is not based on the conventional isotope ratio biplots, which were originally devised to allow the calculation of the geological age of the lead mineralization, but is derived from isotope mixing models, more often used for presenting strontium isotope data. We illustrate the method by reworking published data on Sardinian Nuragic oxhide ingots and copper alloy artefacts. While we confirm the consensus assumption that the oxhide ingot fragments found on Sardinia are isotopically consistent with Cypriot copper ores (although we see no isotopic reason to favour only Apliki, as originally suggested), we also show that there is evidence for mixing between local and ingot copper in some objects, which was previously not detected. More broadly, we suspect that the apparent mismatch between some source allocations for copper drawn from isotope geochemistry and the rest of the archaeological data in some cases might be due to mixed isotopic signals being incorrectly assigned to a specific source, and suggest that the method presented here will reduce the chances of this happening.     

The potential of stable Cu isotopes for the identification of Bronze Age ore mineral sources from Cyprus and Faynan: results from Uluburun and Khirbat Hamra Ifdan

Copper isotope ratios differ between hypogene sulfidic, supergene sulfidic and oxidized ore sources. Traditional lead isotope signatures of ancient metals are specific to deposits, while Cu isotope signatures are specific to the types of ore minerals used for metal production in ancient times. Two methodological case studies are presented: First, the mining district of Faynan (Jordan) was investigated. Here, mainly oxidized copper ores occur in the deposits. The production of copper from Fayan’s ore sources is confirmed by the measurement of the Cu isotope signature of ingots from the Early Bronze Age metal workshop from Khirbat Hamra Ifdan. Based on our results illustrating differences in the Cu isotope composition between the ore mineralizations from Timna (Israel) and Faynan, it is now possible to determine these prehistoric mining districts from which copper artifacts originated by combining trace elements and Pb isotopes with Cu isotopes. The second case study presents data on Late Bronze Age copper production in Cyprus. Oxhide ingots from the shipwreck of Uluburun (Turkey) were tested for their lead isotope signatures and assigned to Cypriot deposits in the recent decades. The oxhide ingots from Uluburun show a Cu isotope signature which we also found for oxidized copper ores from Cyprus, while younger oxhide ingots as well as metallurgical slag from the Cypriot settlements Kition and Enkomi show a different signature which might be due to the use of sulfidic ore sources from a greater depth of deposits. We assert that there could be a chronological shift from oxidized to sulfidic ore sources for the copper production in Cyprus, requiring different technologies. Therefore, Cu isotopes can be used as a proxy to reconstruct mining and induced smelting activities in ancient times.