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.     

EARLY BRONZE AGE METAL TRADE IN THE EASTERN MEDITERRANEAN. NEW COMPOSITIONAL AND LEAD ISOTOPE EVIDENCE FROM CYPRUS

Summary.   This paper presents the results of chemical and lead isotope analyses of 17 Early and Middle Bronze Age artefacts from Cyprus. These suggest that a number of objects are of non-Cypriot copper and lead to the identification of several as imports, a new explanation for some artefact types as ingots and a discussion of the nature of deposits at the key Cypriot site of Vasilia. This in turn allows a reconsideration of the role of Cyprus in an Aegean/eastern Mediterranean metals trade in the early years of the second half of the third millennium BC and of the development of metalworking on the island.     

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.     

LEAD ISOTOPE ANALYSES OF BRONZE AGE COPPER‐BASE ARTEFACTS FROM AL‐MIDAMMAN,YEMEN: TOWARDS THE IDENTIFICATION OF AN INDIGENOUS METAL PRODUCTION AND EXCHANGE SYSTEM IN THE SOUTHERN RED SEA REGION*

The results of the lead isotope analysis (LIA) of 15 copper‐base artefacts from the Bronze Age site of al‐Midamman, Yemen, are reported. The LIA data suggest the existence of an indigenous Bronze Age metal production and exchange system centred on the southern Red Sea region, distinct from those in neighbouring regions of Arabia and the Levant. These preliminary results are highly significant for the archaeology of the region, suggesting that local prehistoric copper extraction sites have thus far gone unrecorded, and highlighting the need for systematic archaeometallurgical fieldwork programmes in the countries surrounding the southern Red Sea.     

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.     

PREHISTORIC COPPER PRODUCTION IN THE INN VALLEY (AUSTRIA), AND THE EARLIEST COPPER IN CENTRAL EUROPE*

In recent years archaeological finds and scientific analyses have provided increasing evidence for a very early beginning of copper production in the rich mining area of the Tyrolean Alps. The earliest findings derive from an excavation of a multi‐phase settlement on the Mariahilfbergl in Brixlegg, which revealed evidence that a small amount of fahlores, probably of local provenance, was at least heated if not even smelted there in the Late Neolithic Münchshöfen culture (the second half of the fifth millennium bc ). However, most copper finds of this horizon consist of low‐impurity copper that most probably derives from Majdanpek in Serbia. This long‐distance relationship is corroborated by typological features that link some aspects of the Münchshöfen culture with the Carpathian basin. Thus it is not yet clear if, at Brixlegg, actual copper production took place or, rather, an experimental treatment of the local ores. The typical fahlore composition, with arsenic and antimony in the per cent and silver and bismuth in the per mille ranges, appears in quantity only in the Early Bronze Age. Many thousands of Ösenringe are known from many central European Early Bronze Age sites, with a chemical composition typical of fahlores. At Buchberg near Brixlegg, a fortified settlement with slags from fahlore smelting proves that the local ores were indeed exploited. The lead isotope ratios of Ösenringe from the Gammersham hoard in Bavaria, which consist of fahlore copper, confirm this and suggest that copper mining and production in the Inn Valley reached a first climax during that period. In the Late Bronze Age, copper was produced at an almost industrial level.     

The Mineralogy of Bronze Age Copper Ores from the British Isles: Implications for the Composition of Early Metalwork

Numerous analytical studies during the latter half of this century have contributed to the compilation of a large compositional database of Early to Middle Bronze Age copper-based artefacts revealing distinctive impurity patterns which appear to change over time. However, attempts to relate these data to copper ore sources proved problematic in the absence of firm evidence for the location of prehistoric copper mines. Over the last fifteen years this situation has changed dramatically with the discovery of numerous Early and Middle Bronze Age copper mines in England and Wales. This study is the first attempt at a comprehensive mineralogical survey of the principal mines investigated to date in order to define the likely composition of the copper ores as mined in antiquity for comparison with the artefact database. The study suggests that the majority of these mines can only have produced essentially pure copper. Only one mine, Ross Island, is likely to have produced copper with a significant level of impurities. The relative purity of the known ore sources is contrasted with significant levels of various metallic impurities among the analysed artefacts, leading to the conclusion that metal circulation and mixing may have been more extensive than previously thought even during the earliest part of the Bronze Age.     

Metallurgical traditions and metal exchange networks in late prehistoric central Myanmar,c. 1000 BC to c. AD 500

Myanmar has been notably underrepresented in recent studies of archaeometallurgy in Southeast Asia, despite its richness in both mineral and cultural resources and its potentially central role in long-distance exchange networks linking India, China and peninsular neighbours. Here, we present original analytical data on copper-base artefacts from several Bronze Age and Iron Age sites in Myanmar. Observed microstructures range from as-cast, worked, to fully annealed; compositions include leaded copper, low-tin to high-tin bronzes, and arsenical copper/bronze. Lead isotope analyses indicate that the metal originates from different geological sources, including several that match the lead isotope signatures of known prehistoric copper mines in Thailand and Laos. These archaeometallurgical data, including evidence for secondary copper-base production, more than double those currently available for Myanmar and document the presence of multiple local alloying and working traditions, perhaps chronologically differentiated, as well as identifying possible links to primary mineral sources across the region. Overall, this adds significant new information to the emerging picture of Southeast Asian prehistoric metallurgy at the crossroads of several major ancient cultures.     

A Late Bronze Age Shipwreck with a Metal Cargo from Hishuley Carmel,Israel

A 13th‐century‐BC shipwreck site, Hishuley Carmel, is described and discussed. It provides direct evidence for marine transport of copper and tin along the Israeli coast and may indicate inland and maritime trade‐routes of metals in the Mediterranean. The shipwreck represents a supply‐system providing the demand for bronze in the Levant. Trace‐elements and lead‐isotope analysis suggest that the copper came from Cyprus, similarly to bun and oxhide ingots from Uluburun. The source of the tin cannot yet be ascertained. The medium‐size ship was probably grounded and wrecked during a storm. Some of the cargo may have been salvaged in Antiquity. © 2012 The Authors     

ON THE COMPOSITION AND PROVENANCE OF METAL ARTEFACTS FROM POLIOCHNI ON LEMNOS

Summary. The majority of the well-stratified Early Bronze Age metal objects from Poliochni, with the exclusion of one hoard find, was analyzed for their chemical and lead isotope composition. The results show that a major change occurred in the metal used at Poliochni during periods contemporary with Troy I and Troy II. Unalloyed or arsenical copper with relatively high lead contents during the earliest two periods 'azzurro' and 'verde' is gradually replaced and supplemented by tin bronze which, during period 'giallo', i.e., by the end of Troy II, becomes the dominant metal type. Lead isotope abundance ratios in the earlier artefacts are consistent with a derivation of the metal from regional ore sources but the trace element abundance pattern is not. Concurrent with the appearance of tin bronzes is an increase in the diversity of ore deposits exploited; for about one third of the artefacts from period 'giallo' there is as yet no matching ore source in all Anatolia and the Eastern Mediterranean. It is argued that the tin bronzes have been imported as such but that the lead isotope signature does not provide any direct clues to the origin of the tin.     

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.     

Late Bronze Age Oxhide and oxhide‐like ingots from areas other than the Mediterranean: problems and challenges

Oxhide ingots are probably one of the most remarkable metal artefacts that ever circulated throughout the Mediterranean during the second millennium BC. From the Levantine coast to Sardinia, oxhide ingots were produced, exchanged, used and transformed for almost six centuries (c.1600–1100/1000 BC). They are generally regarded as a class of material that is found only in the Mediterranean area. However, there are a number of oxhide ingots that have been encountered far beyond the coasts of the Mediterranean. The aim of this paper is to throw some light on these items and their significance in order to increase our understanding of the complex and far‐reaching Bronze Age metal supply networks in Europe. The application of a commodity branding model also allows the possibility of achieving a deeper understanding of these items as tokens of the long‐lasting links between Continental Europe and the Mediterranean.     

STATISTICAL EVALUATION OF THE PRESENTLY ACCUMULATED LEAD ISOTOPE DATA FROM ANATOLIA AND SURROUNDING REGIONS

Several hundred new stable lead isotope ratio determinations of ore and slag specimens from ancient mining sites throughout Anatolia and of samples of artefacts of the Chalcolithic, Bronze Age and Early Iron Age from museum collections in Turkey and the United States have been combined with the accumulated published isotope determinations of such specimens from throughout the eastern Mediterranean and Aegean regions to form a data base of nearly 1000 analyses. It is the purpose of this paper to evaluate the practical effectiveness of using this now extensive data base to discriminate between the many sources of metals throughout this region and to propose methods to enhance this discrimination. By using the full three-dimensional isotopic data in multivariate statistical treatments and by separating isotopically resolvable source groups within some of the source areas and isolating statistically outlying specimens from them, it has been possible to characterize some ore sources more precisely and compactly and thereby achieve better resolution between ore sources. It has also been possible to isolate isotopically compatible artefact groups which possibly relate to ore sources that, as yet, have not been well defined by isotopic analysis.     

CHEMICAL AND LEAD ISOTOPE ANALYSES OF GREEK LATE NEOLITHIC AND EARLY BRONZE AGE METALS

Results of a combined archaeological and analytical project of Late Neolithic/Early Bronze Age copper, bronze and lead artefacts from four distinct areas of mainland Greece are presented. The aim of the study is to understand better the stages of technological development of each region, their possible ore sources and also to assess any external contribution to or internal evolution of their metallurgy. Interesting results which could challenge the established view of Late Neolithic/Early Bronze Age metallurgy in the Greek mainland are presented.     

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.     

The Determination of Lead Isotope Ratios by Multiple Collector Icp‐Ms: A Case Study of Early Bronze Age Artefacts and their Possible Relation With Ore Deposits of the Erzgebirge*

Lead isotope analyses of Early Bronze Age metal artefacts from the Aunjetitz (Ún?tice) culture in central Germany and Bohemia were determined in order to find out whether they could be related to ore sources of the Erzgebirge. Historical mining began only in the 12th century ad , but despite the lack of convincing field evidence it has frequently been suspected that this region was already being exploited in prehistoric times. For the determination of the lead isotope ratios, the new technique of multiple collector inductively coupled plasma mass spectrometry (MC‐ICP‐MS) was employed, which combines relatively easy sample preparation with highly precise and accurate measurements. The results show that there is still no evidence for prehistoric mining in the Erzgebirge, but the Rammelsberg deposit in the Harz Mountains might have supplied some of the copper. Mining of stream tin in the Erzgebirge remains a possibility, but no positive evidence can be extracted from the data.     

COPPER AND BRONZE DURING THE ENEOLITHIC AND EARLY BRONZE AGE: A METALLOGRAPHIC EXAMINATION OF AXES FROM THE NORTHALPINE REGION*

This paper presents the results of a metallographic examination of Eneolithic and Early Bronze Age axes from the Northalpine region of central Europe. During this period, different types of copper were in use: arsenical copper, Fahlerz copper and tin bronze. We examine if and to what extent the different properties of the metals used were known to prehistoric metalworkers and actively manipulated in the production of the axes. The development of methods of casting and smithing is discussed. Both aspects contribute to our understanding of the nature of prehistoric technological change. During the Early Bronze Age of the Northalpine region, different traditions of early metallurgy can be identified, which differ in their use of Fahlerz copper, their attitude towards tin alloying and the use made of tin bronze in the production of the axes. These traditions can only be adequately described by reference to both composition—that is, access to different types of copper as well as tin—and knowledge of the production techniques provided by metallographic data.     

TECHNOLOGY AND PROVENANCE OF A COLLECTION OF ISLAMIC COPPER‐BASED OBJECTS AS FOUND BY CHEMICAL AND LEAD ISOTOPE ANALYSIS*

Chemical and lead isotope analyses were utilized to determine the composition, technology and origin of a collection of Islamic copper‐based objects found in Jordan. The atomic absorption spectrometry results show that the objects were made of different types of copper‐base alloys that contain various amounts of zinc, tin and lead. The use of brass, highly leaded brass and quaternary alloys of Cu‐Zn‐Sn‐Pb in the manufacture of everyday, household objects strongly points to Islamic traditions. The lead isotope compositions of the objects match very well that of the copper ore mined from the Dolomite‐Limestone‐Shale unit of the Arabah copper mines.     

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.     

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.