Defining the Lead Isotopic Fingerprint of Copper Ores from North‐West Spain: The El Milagro Mine (Asturias)

This study is focused on the El Milagro mine (Asturias, Spain) and is part of a large‐scale effort on the measurement of the lead isotopic composition of Spanish copper ores from prehistoric mines in the provinces of Asturias and León, from which no data were available until recently. Lead isotopic values are compared to the published lead data from the El Aramo mine in the same region. The results show that both mines have a very similar lead isotopic composition, apart from some highly radiogenic samples in the El Milagro mine, which are clearly different from those previously reported for the Iberian Peninsula.     

A Provenance Study of Early Bronze Age Artefacts Found in Asturias (Spain) by Means of Metal Impurities and Lead,Copper and Antimony Isotopic Compositions

We describe here the first combined isotopic and impurities study on 27 copper artefacts found in the north‐west of Spain. This study follows previous studies on the lead isotopic composition of copper ores in three local mines that were exploited during the Bronze Age. The levels of impurities found were clearly different from ingots and axes, with ingots having much higher levels of impurities. It was not possible to differentiate the origin of the artefacts only by the impurities present. On the other hand, the lead isotopic composition indicated that all artefacts were prepared from local ores, the ‘La Profunda’ mine being the most probable source for most artefacts that carried out a clear radiogenic lead signature. The copper isotopic composition seemed to be able to differentiate artefacts from the ‘El Aramo’ mine from those from the ‘El Milagro’ and ‘La Profunda’ mines. On the other hand, the antimony isotopic signature was not useful for source allocation.     

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 early roman imperial AES coinage II: Tracing the copper sources by analysis of lead and copper isotopes—copper coins of Augustus and Tiberius*

Lead and copper isotopes of Roman Imperial copper coins (denominations as and quadrans) were analysed by MC–ICP–MS. We concentrated on well‐dated coins minted at the official mint of Rome under the Emperors Augustus and Tiberius (between 16 bc and ad 37). The lead isotope results were compared with published lead isotope data of ore bodies from the Aegaean, Cyprus, Italy and Spain, in order to fingerprint the sources of Roman copper. During the Augustan period the main copper supply, as judged from the copper coins, is from Sardinia and south‐east Spain, with minor contributions from Tuscany. Except for Tuscany, this continued into the Tiberian period, when Cypriot copper also appears. Augustan quadrantes and late Tiberian asses came solely from the Rio Tinto area in south‐west Spain. Copper isotopes were applied here for the first time to systematic archaeometric studies. They are supplementary to lead isotopes and allow further grouping and classification of the copper coins.     

Characterisation of the raw metal sources used for the production of copper and copper-based objects with copper isotopes

Copper isotopes can be successfully used to determine the origin of copper or bronze artefacts from either primary or supergene sulphide or hydrocarbonate ores. In conjunction with lead isotopes, they provide information on the origin and type of the metal ore. We demonstrate this in this paper from the combination of literature and own data on metal ores and artefacts (coins and ingots). Low-temperature hydrocarbonates (esp. malachite and azurite) do not fractionate the copper isotopes amongst each other and have identical lead isotopes. Substantial fractionation of copper isotopes, however, occurs between copper sulphides and hydrocarbonates (malachite, azurite) such that the ⁶⁵Cu isotope is always enriched in the oxidised relative to the sulphide phase with a clear distinction between the two ore types. Expressed in the δ⁶⁵Cu notation, we assigned supergene sulphides to values less than −0.4‰ down to negative values of −2‰ and more, primary sulphides to a range between −0.4 and +0.3‰ and hydrocarbonates to positive values higher than +0.3‰. We have applied these boundaries to copper coins and ingots from the time of the Roman emperors with known ages from Augustus up to 250 AD. The deposit fields of the metal used for the production of the coins were previously identified from the lead isotope ratios to lie in the Southwest and the Central South of Spain. From the combination of the lead and copper isotopes and the exact time constrains, we could develop a picture of the change in mining activities in Spain involving continued mining sulphide ore deposits and, indicated by positive δ⁶⁵Cu values as proxies for malachite and azurite, the opening of new mines in various time slots. This first application shows that copper isotopes will become the most important tool in archaeometallurgy to distinguish between the exploitation of deeper-seated primary and supergene sulphide ores and shallower, secondary hydrocarbonate ores. This will become especially relevant for archaeometric questions regarding the distinction between occasional and intentionally produced alloys.     

Non-ferrous metallurgy from the Phoenician site of La Fonteta (Alicante, Spain): a study of provenance

The lead isotope composition of 22 samples from the excavation of the Phoenician site of La Fonteta (Guardamar del Segura, Alicante, Spain) has been analysed in a preliminary study of their provenance. These materials span chronologically from the first half of the 8th century BC to the middle of the 6th century BC.The samples have been selected to include materials used in lead and silver production, as well as in copper-based metallurgy. Therefore, lead droplets, galena nodules and fragments of litharge have been analysed, together with a fragment of a copper ingot, an object, a melting waste composed of a Cu–Pb alloy, and two fragments of a material that we have provisionally labelled ‘Pb–Cu cupellation debris’.All these materials have been initially analysed by X-Ray Fluorescence-Spectrometry to identify their bulk compositions. Some of them have been also analysed by SEM–EDX and ICP–OES. Subsequently, lead isotope analyses (LIA) have been performed using Thermal Ionization Mass Spectrometry (TIMS). The new LIA data obtained has been compared with published lead isotope data from the Mediterranean area. The identification of different groups suggests a significant complexity of the internal and external trade routes during the Orientalising period. For this reason, the provenance study of these materials is especially important in shedding light on the commercial dynamics that the Phoenicians established with native people to control the raw materials and to commercialise finished products.     

The Status Problem of Iberian Holocene Equids: New Data from Cueva de El Mirador (Sierra de Atapuerca,Spain)

Equid remains are scarce and very fragmented in Iberian Neolithic and Bronze Age sites. Evidence suggesting that horses were domesticated does exist, but it is often inconclusive, thus leaving the question unanswered. Today, DNA analyses have provided information about a, most likely Iberian, nucleus of horse domestication, making it crucially important to expand the database. The Holocene sequence (6^th and 3^rd millennium cal bc ) of the Cueva de El Mirador (Sierra de Atapuerca, Spain) has yielded 92 equid remains distributed in 12 Neolithic and Bronze Age levels. In this paper, we present the study of the equid remains from the Cueva de El Mirador from an archaeozoological perspective, giving indirect evidence of horse domestication. Our results vary widely and lead to open interpretations about horse domestication and how humans used these animals. This study of horse remains focuses on species identification and on determining how humans economically used these animals. Copyright © 2014 John Wiley & Sons, Ltd.     

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。     

Where Do the Lead Ingots of the Saintes‐maries‐de‐la‐mer Wreck Come From? Archaeology Compared With Physics

The lead isotope compositions of many different samples from lead ingots of Roman age from two relicts (from Cabrera, and from Saintes‐Maries‐de‐la‐Mer) of the Western Mediterranean have been measured. Other lead isotope analyses of ores, metals or lead ingots from mines of Sierra Morena and from Cartagena and Sardinia have been accomplished. All the lead isotope measurements have been performed at the Joint Research Centre of the European Union, Ispra (Va), Italy. The samples have been prepared in a class 100 clean room, using only ultrapure reagents and FEP materials. In view of the archaeological arguments, it was possible to believe that the Roman lead ingots of the Saintes‐Maries‐de‐la‐Mer 1 wreck came from Spanish lodes, as well as those of the Cabrera 5 wreck. In fact, while the comparison between the first group of ingots (Cabrera 5) and the lead from Sierra Morena is consistent, the correspondence between the second group of ingots (Saintes‐Maries‐de‐la‐Mer 1) and the Cevennes ores (southern France) gives rise to several problems concerning the archaeological and physical origins. These problems are discussed.     

Ceramic productions and human interactions during the Early Bronze Age in northern Iberia

The Early Bronze Age ceramic collection found into the caves of La Llana and El Toral III in Asturias (Spain) presents common decoration such as that found in the centre of Cantabrian Spain from the same period, which resembles others found in the Ebro Valley and Atlantic Europe. Therefore, the main objective of this study it is to identify the raw material origin and understand the pottery production process during the Early Bronze Age in the Cantabrian region. A methodological approach based on the chemical and mineralogical analysis of vessels and experimentally fired clay samples collected all over the centre of this region was developed. Furthermore, the post‐depositional processes affecting the sherds’ composition was evaluated by employing the rare earth elements as markers. The results showed that the studied assemblage has important similarities with the raw materials of the surrounding area, which supports the hypothesis of a regional mobility.     

Moving metals or indigenous mining? Provenancing Scandinavian Bronze Age artefacts by lead isotopes and trace elements

The aim of this study is to further the discussion as to whether copper was extracted locally or imported to Sweden during the Bronze Age or if both of these practices could have coexisted. For this purpose, we have carried out lead isotope and chemical analyses of 33 bronze items, dated between 1600BC and 700BC. Among these are the famous Fröslunda shields and the large scrap hoard from Bräckan and other items from three regions in southern Sweden which are also renowned for their richness in copper ores. It is obvious from a comparison that the element and lead isotope compositions of the studied bronze items diverge greatly from those of spatially associated copper ores. Nor is there any good resemblance with other ores from Scandinavia, and it is concluded that the copper in these items must have been imported from elsewhere. The results furthermore indicate that there are variations in metal supply that are related to chronology, in agreement with other artefacts from Scandinavia as well as from other parts of Europe. Altogether these circumstances open up for a discussion regarding Scandinavia’s role in the maritime networks during the Bronze Age.     

LEAD ISOTOPE CHARACTERISTICS OF THE CYPRUS COPPER ORE DEPOSITS APPLIED TO PROVENANCE STUDIES OF COPPER OXHIDE INGOTS

Nearly 200 new lead isotope analyses of sulphidic and oxidized ores from 26 copper mines on Cyprus show that the mines from different geological regions group in five distinctive isotopic groups, each with a substructure, related to the geological history of the ore formation. Comparison of lead isotope compositions of Bronze Age artefacts with these data can in many cases reveal the actual mines from which the copper for particular artefacts was obtained. The particular case of the provenance of the copper for 78 Late Bronze Age copper ‘oxhide ingots’found in Cyprus, Crete, Greece, Sardinia, Turkey and Bulgaria is discussed. The data show that all oxhide ingots so far analysed, dating to the fourteenth century BC and later, were made of copper consistent isotopically with only one mining region in the geographical north of Cyprus, and especially the Apliki mine. The study provides further evidence which supports the validity of the conventional approach to the use of lead isotope analysis for provenancing metals; this evidence is antithetical to recent suggestions of a model for the production of copper oxhide ingots which involved widespread mixing of copper from a number of ore sources throughout the Mediterranean.     

Sourcing copper ores for production of bronzes excavated at Shuangyantang,a Western Zhou (1046–771 <Emphasis Type="SmallCaps">bc</Emphasis>) site in Chongqing (Southwest China): evidence from lead isotope analysis

Energy-dispersive X-ray fluorescence (EDXRF) and lead isotope analyses were applied to 12 Western Zhou (1046–771 bc) bronzes unearthed from the Shuangyantang site in Wushan County, Chongqing (southwest China), to investigate their chemical compositions and possible mineral source(s). The results showed that (1) the investigated bronzes were mostly bronzes with low, common lead and (2) their lead isotopic values almost all fall into a relatively narrow range, suggesting possibly the use of raw materials from a common copper mine. The comparison between lead isotopic values for Shuangyantang bronzes and those already published for copper mines and other bronzes produced and used about at the same times leads us to believe that the Shuangyantang bronzes probably used the same copper ores as used in bronzes from the Peng and Jin states in Shanxi Province. However, it would not be possible at this point to come up with a clear idea of where exactly these copper ores may come from. Candidate copper mines might be the Tonglvshan mines in Hubei Province, the Zhongtiaoshan mines in Shanxi Province, or the Dajing copper mines in Inner Mongolia.     

LA–ICP–MS,SEM–EDS AND EPMA ANALYSIS OF EASTERN NORTH AMERICAN COPPER‐BASED ARTEFACTS: IMPACT OF CORROSION AND HETEROGENEITY ON THE RELIABILITY OF THE LA–ICP–MS COMPOSITIONAL RESULTS*

This study discusses the relevance of compositions obtained using laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS) for the purpose of identifying the provenance of copper‐based artefacts found in Virginia at Native American sites dated from the 16th to the 18th centuries. Ten artefacts were investigated by scanning electron microscopy – energy dispersive spectrometry (SEM–EDS) to visualize the corrosion and characterize the heterogeneities in the metal and electron probe micro‐analysis (EPMA) to determine separately the compositions of the intact metal and of the corrosion product. It is shown that the corroded surfaces are highly depleted in zinc but that representative concentrations can be determined by sampling the deeper, uncorroded metal. In contrast, lead values are highly variable because of the heterogeneous distribution of this metal within the bulk copper. Despite these problems, brass is easily identifiable and American native copper and European smelted copper can be unambiguously distinguished with LA–ICP–MS on unprepared artefacts using As, Ag, Ni and Sb trace elements.     

The history of silver refining in New Spain, 16c to 18c: back to the basics

The refining of silver ores in New Spain was defined by the chemical nature of the silver ore. Argentiferous galena (lead sulphide) could only be refined by smelting (36% silver produced), irrespective of silver content, and amalgamation (64%) could only be applied to the silver sulphide ores. Both processes were transferred from Europe, but amalgamation was transformed by local expertise from a recipe of limited application to an industrial-scale solution for refining sulphidic silver ores. Its implementation shaped the environmental history of colonial silver refining in the New World. Mercury was consumed mainly through its chemical conversion into calomel, with minimal emissions of volatile mercury. Waste silt and liquid mercury in the soil and waterways were its main legacy. Smelting created a greater impact on the environment of New Spain, via lead in lead fumes as the main heavy metal issued to the air, and its depletion of woodlands. This article argues that a technical analysis of period refining practices in New Spain reorients our understanding of Spain’s imperial relations with its New World colonies, of the role of local knowledge in a global economy of silver production, and of environmental issues in colonial history. It thus speaks to the problem of unpacking the complex web of relations that composed early European imperialism, in which were enmeshed commodities such as silver, cotton and sugar.     

Rediscovering famous assemblages: A rare Bronze Age crucible from El Argar,Spain

A rare open shallow crucible from the British Museum collection, excavated at the Bronze Age site of El Argar in south-east Spain by Louis and Henri Siret, was studied using X-radiography and scanning electron microscopy. The crucible has relatively thick walls, a spout and a non-refractory fabric. It was used for melting copper alloys for various possible purposes, such as alloying, refining, recycling or before casting, at around 1100°C. Both arsenic and tin were detected in various places and concentrations in the analysed specimens. This crucible could have been used during the period of transition from arsenic-rich copper to tin bronzes in the El Argar culture, or used for the recycling of arsenic-rich copper artefacts being alloyed with tin to produce tin bronzes. This melting crucible is a rare example of its kind to have been investigated scientifically, as most crucibles from contemporary sites on the Iberian Peninsula are generally associated with smelting. This study has also crucially shed more light on the types of alloys and variety of activities undertaken during that transitional period between the use of arsenical copper and tin bronzes in this region.     

‘DE CAERIMONIAE’ TECHNOLOGICAL CHOICES IN COPPER‐SMELTING FURNACE DESIGN AT EARLY BRONZE AGE CHRYSOKAMINO,CRETE*

The excavation of a number of Early Bronze Age sites in the Aegean has recovered perforated ceramic fragments. Archaeometallurgical analysis of slag adhering to these fragments indicates that they are the remains of copper‐smelting furnaces. Despite compelling analytical data supporting this identification, no attempt has been made, thus far, to establish how these unusual furnaces may have operated. The use of perforations is poorly understood and can be considered a counter‐intuitive solution for the reduction of oxidic copper ores. The experiments reported here explore the possible technological choices made by the ancient metalworkers of Chrysokamino to ensure the effective reduction of copper minerals. Temperature data and slag samples were obtained to ascertain the technical performance of the furnace structure with, and without, perforations. Possible reasons are given for the use of a perforated design, and the implications of such technological choices are considered.     

Electrochemical Characterization and Dating of Archaeological Leaded Bronze Objects Using the Voltammetry of Immobilized Particles

The application of solid state electrochemistry techniques for the characterization and dating of leaded bronze objects is described. Characteristic voltammetric signatures of copper and lead corrosion products were used as markers of more or less prolonged corrosion periods. The proposed methodology was applied to samples from the Roman archaeological sites of Valeria (Spain) and Gadara (Jordan), Roman and medieval sites in Xàtiva (Spain), and modern statuary exhibited outdoors, on the campus of the Universitat Politècnica of Valencia, Spain, covering a time interval between the fourth to second century bc and the 20th century ad . For such samples, the ratio between the signals for copper and lead corrosion products decreased monotonically with the corrosion time. This variation was modelled on the basis of thermochemical and kinetic considerations, the experimental data being consistent with a potential rate law for the corrosion process.     

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.     

Copper supply during the Final Neolithic at the Saint-Blaise/Bains des Dames site (Neuchâtel, Switzerland)

The Saint-Blaise/Bains des Dames stratified site in Neuchâtel, Switzerland, contains several occupations that span the Late through Final Neolithic, including the Horgen, Lüscherz, and Auvernier-Cordé periods. As part of a study on prehistoric metallurgy in western Switzerland, we compare the lead isotope ratios (multicollector inductively coupled plasma mass spectrometer) and elemental compositions (instrumental neutron activation analysis) of the site’s numerous copper finds to a database of corresponding measurements for copper ores throughout Europe. The results show a considerable variation in copper compositions present at the site, suggesting complex economic relationships and multiple chaînes opératoires during the time in question. Specifically, during the Final Neolithic, we distinguished ten coherent clusters, confirmed by both the elemental compositions and lead isotope ratios. When compared to the Europe-wide database of copper ores, we observed significant changes in the provenance of the copper through time that reflect equally significant changes in social, cultural, and economic interactions.