何郢遗址出土青铜器铜矿料来源的初步研究

本文利用地球化学示踪的方法对何郢遗址出土青铜器的铜矿料来源进行了初步研究.采用ICP-AES测试了样品的微量元素,根据元素的地球化学亲和性,探索其在冶炼过程中的化学行为和再分配规律,从而选出对铜绿山和皖南的铜陵、南陵铜矿具有指示意义的特征元素,作为判断其铜料输出路线的综合判别标志.结合文献和地质资料,可初步认为何郢遗址青铜器的铜矿料来自滁县.     

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。     

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。     

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.     

长江中下游古铜矿及冶炼产物输出方向判别标志初步研究

根据大量野外调查和相关样品的测试分析,指出了长江中下游铜矿带古代矿冶遗址分布及冶炼遗物岩相和地球化学特征;讨论了利用铅、铜等同位素及微量元素示踪本区铜矿冶炼产物输出方向的可行性,指出利用亲铜微量元素特征组合(包括富集、贫化元素,元素对及元素组合等)作为判别标志是相对而言较好的方法,同时要定性与定量标志综合考虑。     

Early copper smelting at Itziparátzico,Mexico

Archaeological fieldwork and archaeometallurgical analysis have identified a Late Postclassic regional centre of copper production in western Mexico. The total output from a single unit of production at the site of Itziparátzico is an estimated ten tons of copper and nearly forty tons of slag over the lifetime of the installation. It is argued that this smelting was based on slag-tapping furnaces, a technology previously unknown from Mesoamerican archaeological sites. The smelting site is in dense woodland with ample fuel supply, some 125 km from the next mining area with documented contemporary ore extraction; the copper produced would have been passed on to the capital, another 60 km away, for further distribution and working. The scale of production at Itziparátzico indicates that copper smelting was done by part-time specialists embedded in a predominantly agricultural economy, and formed part of a centrally organized network of mining, smelting and processing of copper to supply the Tarascan state.     

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。     

安徽省南陵县江木冲古铜矿冶炼遗物自然科学研究及意义

本通过对江木冲冶炼遗址古铜矿、古炼渣、古铜锭及青铜器的对比研究,利用矿床学、冶金学等理论,探索利用自然科学手段解决其输出路线问题,提出了判别其产物(铜锭)的特征微量元素和其它综合判别标志,同时也为青铜器其它矿料来源(尤其锡矿)难题的解决进行了技术路线探索和方法研究。     

THE TUNGSTEN AND TIN SIGNATURE OF IRON ORES FROM ELBA ISLAND (ITALY): A TOOL FOR PROVENANCE STUDIES OF IRON PRODUCTION IN THE MEDITERRANEAN REGION

The mineralogy, petrography and major‐ and trace‐element composition of iron ores from Elba Island (Tuscany, Italy), one of the most important iron sources in the Mediterranean area since the first millennium bc , revealed that hematite‐rich ores display prominent enrichments in W and Sn (up to 4950 μg g^?1 and 8400 μg g^?1, respectively). These two elements are hosted by tiny grains of W–Sn mineral phases (ferberite, scheelite and cassiterite) that are disseminated throughout the hematite matrix. A comparison with iron ores from many Italian and European localities (most of which were exploited in ancient times) suggests the uniqueness of the geochemical pattern of Elba Island hematite‐rich ores (i.e., high W and Sn, low Mo and low Cu, Pb and Zn). We suggest that this geochemical signature may represent a new provenance marker not only for discarded ore at smelting/smithing sites, but, possibly, also for metallurgical slag and smelted metal produced in the chaîne opératoire of the iron process.     

Evaluating copper isotope fractionation in the metallurgical operational chain: An experimental approach

Until today, raw material information of copper (Cu) objects is mostly gained from impurities and trace elements and not from the Cu itself. This might be obtained using its stable isotopes. However, isotopic fingerprinting requires the absence of fractionation during the smelting process. The Cu isotope evolution during outdoor smelting experiments with Cu sulphide ore was investigated. It is shown that external materials, in particular furnace lining, clay, manure and sand, alter the isotopic composition of the smelting products. Cu isotopes are fractionated within low viscosity slag derived from matte smelting. The produced metallic Cu has a Cu isotope signature close to the ore.     

SERIPHOS SURFACES: A STUDY OF COPPER SLAG HEAPS AND COPPER SOURCES IN THE CONTEXT OF EARLY BRONZE AGE AEGEAN METAL PRODUCTION

Kephala and Phournoi, on the island of Seriphos, add to a growing number of EBA metal production sites identified in the south‐central Aegean. Analytical examination of samples from the two sites addressed the technological parameters of the copper smelting process, indicating the use of mixed oxidic and sulphidic copper–iron ores to produce unalloyed copper with minute copper sulphide inclusions. A preliminary geological reconnaissance of the island identified several small copper mineralizations, one of them close to the site of Kephala. Nevertheless, the ore sources used remain unclear. Comparisons are made with other contemporaneous neighbouring smelting sites.     

Ancient Mining and Smelting Activities in the Wadi Abu Gerida Area,Central Eastern Desert,Egypt: Preliminary Results

Old mining and smelting features in the Abu Gerida area have been studied using field observations, microscopy and SEM–EDS to detect the ores that were exploited in antiquity. There are two groups of shafts in the area. The first group encloses secondary copper minerals and is associated with glassy slags containing copper prills. The other group is associated with hematite that was extracted and transferred to a smelting station to the west of the mining site, where iron slags and charcoal fragments are found. These slags are composed mainly of wüstite, fayalite–kirschsteinite and traces of metallic iron. Pottery fragments from this area were dated to the Ptolemaic Period, which may be the age of iron exploitation. Copper might have been exploited earlier.     

THE PROVENANCE OF IRON ARTEFACTS FROM MANCHING: A MULTI‐TECHNIQUE APPROACH*

Iron finds from the Celtic oppidum of Manching in southern Bavaria (Germany) are analysed in view of their possible provenance. The exceptional size and the location of Manching are usually attributed to the presence of abundant iron ores in its vicinity. After a review of previous approaches for source determination of iron artefacts, we introduce lead isotope analysis as a new approach. However, only by combining the trace element patterns of slag inclusions and iron metal with lead isotope ratios in the metal is it possible to distinguish various iron ore formations near Manching. As a result, it turns out that, indeed, the most obvious ones—namely, bog ores near the Danube—constituted the main resources for iron production at Manching. It was even possible to select one occurrence as the most likely ore source.     

MINERALOGICAL AND PETROLOGICAL INVESTIGATIONS OF EARLY BRONZE AGE COPPER‐SMELTING REMAINS FROM THE KIECHLBERG (TYROL,AUSTRIA)

The prehistoric settlement on the Kiechlberg hilltop is located a few kilometres to the north‐east of Innsbruck, in the Tyrolean Inn Valley. Despite its rather isolated location, a multiphase settlement between the fifth and the second millennium bc was confirmed by archaeological investigations in 2007 and 2008. Metallurgical artefacts, such as copper ore fragments, copper slag and raw copper, as well as finished copper and bronze artefacts, are concentrated mainly in Late Copper Age to Middle Bronze Age layers. The chemical compositions of the slag and raw metals confirm Fe—Zn tetrahedrite–tennantite (fahlore) smelting. The ore was most probably imported from the 30–50 km distant copper ore deposits (mainly fahlore) of Schwaz–Brixlegg, in the Lower Inn Valley. The small amount of slag and the presence of slagged and thermally altered ceramic fragments suggest copper production in small‐scale workshops. Most probably, sulphide‐rich ores were smelted in crucibles in a hearth fire. The process was relatively reducing below the 2Sb + 1.5O₂ → Sb₂O₃ reaction (?8.5 log fO₂ at 1100°C), producing Sb‐rich (>10 wt% Sb in metal) raw copper. Inhomogeneous slag remains containing high amounts of sulphide and metal inclusions suggest a poor separation of the metal, matte (copper sulphide) and silicate/oxide melt during the smelting process.     

The history of the United States cent revealed through copper isotope fractionation

Copper isotope fractionation in United States cents traces changes in the source of copper and identifies historical events. Application of copper isotopes as a geochemical tracer requires consistent isotopic signatures of the ores and refined metals. Overlapping isotopic signatures of crushed ores, chalcocite and refined metal extracted from Morenci, Arizona indicate modern mining processes that produce distinguishable single ore deposit geochemical signatures. The coincidence of copper isotope ratios in metals and ore deposits also exists within the United States cents analyzed here. Specifically, historical records confirm two different sources for copper in cents from 1800 through 1867. The copper isotope composition of the 1828, 1830, 1836, 1838 and 1843 cents coincides with the Cornwall ores of England, and cents post 1850 (1859, 1862) correspond with the Michigan ores of the United States. Three of the thirty-six post 1867 cents measured possess fractionated copper isotope ratios and indicate the change in source of copper for the United States cent.     

Does it come from the Pays de Bray? Examination of an origin hypothesis for the ferrous reinforcements used in French medieval churches using major and trace element analyses

A new methodology based on major and trace element analyses of slag inclusions is proposed to determine (or exclude) the provenance of iron artefacts. It is applied to verify if the Pays de Bray, a French area between Rouen and Beauvais, could have been an important supplier for the ferrous reinforcements used in the Middle Ages for the building of churches and cathedrals in these two towns. To this purpose, the behaviour of trace elements during both direct and indirect operating chains is studied combining experimental smelting and different analytical methods, such as SEM–EDS, ICP–MS, LA–ICP–MS and INAA, performed on archaeological samples. The chemical signature of the Pays de Bray iron ore and slag is determined considering MnO and P₂O₅ contents as a first rough filter and seven couples of trace elements. Then, the major and trace elements are analysed using the same methods in the slag inclusions of 32 artefacts from the Beauvais and Rouen churches, made by the bloomery process. The trace element signature of the inclusions from each artefact is compared with the ore from the Pays de Bray area. The iron used in the Rouen and Beauvais churches seems not to come mainly from the Pays de Bray.     

商周时期南北方铜矿开采技术比较研究--以鄂赣交界地带和辽西地区为例

本文选取了鄂赣交界地带和辽西地区的4座晚商至西周早中期的古铜矿遗址,分别从探矿技术、开采技术、开采工具、相关配套设施和选矿技术等方面对南北两区域古铜矿的开采技术进行全面比较,并试图从两地的自然环境、矿物品质以及生产组织方式等不同方面来解释出现这种差异的原因。     

微量元素示踪古代青铜器铜矿料来源的可行性

目前,微量元素示踪法在青铜器矿料来源研究中的应用不尽人意。为此,模拟熔铸青铜器,对它们的微量元素作多元统计分析,旨在探讨利用微量元素探索古代青铜器铜矿料来源的可行性。分析表明：若舍弃冶炼后富集亍炉渣中的亲石亲铁元素,而仅选取富集于铜料中的亲铜元素及一些凡具有亲铜性,又具有亲铁性元素的成分数据,则通过多元统计分析,能较好地区别不同产地的铜矿料。     

Local mining or lead importation in the Roman province of Africa Proconsularis? Lead isotope analysis of curse tablets from Roman Carthage,Tunisia

This study attempts to determine if there was Roman lead mining in Africa Proconsularis, approximately the area of modern day Tunisia, using lead isotope analysis. Another important aspect of the study is the innovative use of electron microprobe analysis (EMPA) as a screening tool to greatly reduce the number of expensive lead isotope analyses needed for the study. The EMPA X-ray mapping for arsenic, antimony, copper, and silver narrowed the sample of curse tablets to those most likely produced from Tunisian ores; these tablets were then tested using thermal ionization mass spectrometry (TIMS) analysis. A total of 96 Roman lead curse tablets from Carthage, Tunisia were screened with EMPA and twenty selected for TIMS to determine the ore sources of the lead used to manufacture the tablets. Comparing the lead isotope ratios of twelve of the sixteen tablets most likely to be made of Tunisian lead to samples of Tunisian ores suggests that the Romans were mining lead in Africa Proconsularis and were not relying solely on imports.     

COMPOSITIONAL VARIATION IN ROMAN COLOURLESS GLASS OBJECTS FROM THE BOCHOLTZ BURIAL (THE NETHERLANDS)*

We investigated the major and trace element composition and Pb and Sr isotope characteristics of a series of about 20 colourless glass objects from a single high‐status Roman burial from the Netherlands (Bocholtz). The major elements show a relatively homogeneous group, with one outlier. This is corroborated by the Sr isotopes. Based on the Sb and Pb content, three major groups can be discerned, with two other outliers. This grouping is corroborated by the contents of the trace elements Bi, Sn, Ag, As and Mo, and by variations in lead isotopic ratios. On the basis of these results, we conclude that the glass of all objects was probably made with sand and lime from the same source. The variation in trace elements and lead isotope composition is most likely the result of variations in the composition of the sulphidic antimony ore(s) that were used to decolourize the glass. The composition of the Bocholtz glass is compared with that of other Roman glass, and implications for production models, trade and use of colourless glass objects are discussed. On the basis of isotopic and major element variation, we conclude that the antimony ore presumably originated from different mines.