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.     

TRACING THE RESOURCES OF IRON WORKING AT ANCIENT SAGALASSOS (SOUTH‐WEST TURKEY): A COMBINED LEAD AND STRONTIUM ISOTOPE STUDY ON IRON ARTEFACTS AND ORES*

Lead and strontium isotope analyses were performed by thermal ionization mass spectrometry (TIMS) on Roman to Byzantine iron artefacts and iron ores from the territory of ancient Sagalassos (south‐west Turkey), to evaluate Pb and Sr isotopes for provenance determination of ores for local iron production. It can be demonstrated that for early Roman artefacts and hematite iron ore processed in early Roman times from Sagalassos proper, as well as for magnetite placer sands and early Byzantine raw iron from the territory of the city, Sr isotopes are much less ambiguous than Pb isotopes in providing clearly coherent signatures for ore and related iron objects. Late Roman iron objects were produced from iron ores that as yet remain unidentified. Early Byzantine iron artefacts display more scatter in both their Pb and Sr isotope signatures, indicating that many different ore sources may have been used. Our study demonstrates that iron objects can be precisely analysed for their Sr isotopic composition, which, compared to Pb isotopes, appears to be a much more powerful tool for distinguishing between chronological groups and determining the provenance of raw materials.     

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.     

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.     

AN ELEMENTAL AND LEAD‐ISOTOPIC STUDY ON BRONZE HELMETS FROM ROYAL TOMB NO. 1004 IN YIN RUINS

Lead isotope and element composition analyses were performed by thermal ionization mass spectrometry (TIMS) and inductively coupled plasma optical emission spectroscopy (ICP–OES) on bronze helmets from royal tomb No. 1004 at Yin Ruins, the last capital of China's Shang Dynasty (17th to 11th centuries bc ). The data show that the copper‐based alloy helmets can be divided into two categories: tin bronze and leaded tin bronze; and the lead isotope ratios for both categories are in the range of highly radiogenic lead (HRL). This result offers some important clues to answering questions concerning the provenance of raw metal materials, as well as the chronology of this famous royal tomb.     

A GEOLOGICAL PERSPECTIVE ON THE USE OF Pb ISOTOPES IN ARCHAEOMETRY

Lead isotope ratios in ore bodies and magmatic rocks depend in a complex way on several a priori independent parameters, including the geological age of the tectonic province in which the ores and magmas formed and its U/Pb (μ) and Th/U (κ) ratios, two very sensitive parameters characteristic of metal sources. All these parameters are entangled in hard‐to‐read Pb isotopic ratios. With respect to the commonly used fingerprinting techniques, which rely on the comparison of raw isotope ratios, the main motivation for the present work is to provide a method for making geologically and geochemically educated guesses about metal provenance even in the absence of isotopic data on reference ores. It shows how to unscramble a geological model age and μ and κ information from isotopic measurements. This approach brings to light a new organization of the Pb isotope database and an untapped wealth of information that can be used for provenance studies and other archaeometric purposes. We provide expressions with which to calculate these parameters and, using literature data, demonstrate how Pb isotopes in ores and magmas define clear zones in the silver‐rich provinces of the Central Andes. We further show how the geological model age and μ and κ values fingerprint production areas in 16th–18th century silver coins minted in Mexico and South America. Finally, we use Pb isotopes to illustrate how the Reconquista of the Emirate of Granada (1482–91) and the seizure of the Betic silver mines are reflected in the silver coins of the Catholic Monarchs.     

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.     

Application of Kernel Density Estimates to Lead Isotope Compositions of Bronzes from Ningxia,North‐West China

The aim of this paper is to apply kernel density estimates (KDEs) to the visualization and interpretation of lead isotope data from bronze assemblages found along the northern border of central China, here designated as the Arc. New lead isotope analyses of 30 leaded tin–bronze artefacts from the Wangdahu cemetery (c.500–300 bc ) in the Ningxia Hui Autonomous Region, north‐west China, provide the basis for the discussion. By using multivariate KDEs and the calculated likelihood of the overlap, the present work shows that the Wangdahu objects feature a unique linear array of isotope ratios, representing an important element of overall bronzes from the Arc in the first millennium bc . This characteristic isotope signature is fundamentally different from that of Dajing ores in north‐east China, as well from that of early Qin bronzes in Shaanxi and Gansu provinces. This suggests that a variety of metal resources were utilized by peoples living in the Arc. The KDE approach thus proves effective at presenting and comparing lead isotope data.     

The Origin and Archaeometallurgy of a Mixed Sulphide Ore for Copper Production on the Island of Kea,Aegean Sea,Greece

At the hill of Agios Symeon, on the island of Kea, Aegean Sea, Greece, ancient metallurgical slags with a high Pb–Zn–Cu content have been found. Thermodynamic simulations have been carried out, using the FactSage? thermodynamic database computing system, with a view to understanding the ancient metallurgical processes that produced the observed slag compositions and morphologies. The simulations demonstrate that the slag samples resulted from Cu‐making processes. It would thus appear that mixed ores were used, containing Cu₂S–FeS–PbS with significant amounts of sphalerite (ZnS) as impurity. The roasted ores were reduced at relatively high oxygen potentials at ～1125°C to form Cu containing low levels of Pb, Fe and Zn.     

Lead isotopic analyses of copper ores in the Early Bronze Age central Hexi Corridor,north-west China

This paper explores the possible provenance of ores employed for metallurgical production during the Early Bronze Age in the central Hexi Corridor of north-west China. In total, 78 pieces of copper (Cu) ore samples were collected from five Early Bronze Age sites and one Cu deposit site (the Beishantang Cu deposit) in the Heihe River region of the central corridor. These sites were dated to the late Machang (4100–4000 bp ), Xichengyi (4000–3700 bp ), Qijia (4000–3600 bp ) and Siba (3700–3400 bp ) cultures. After comparing with published lead (Pb) isotopic data from other possible Cu deposits in north-west China, the results show that the Cu ores collected from the Early Bronze Age sites were most likely derived from the adjacent Beishan Cu deposit. More intriguingly, for the first time in Hexi Corridor, a dozen Cu ores were discovered containing highly radiogenic Pb. Though fundamentally different from those in the Central Plains, they illustrate a possible new type of Cu used in Bronze Age western China, and the first-hand materials are significant for further understanding the provenance of raw metals for metallurgical production in the prehistoric Hexi Corridor.     

Characterization of some ancient glass beads unearthed from the Kizil reservoir and Wanquan cemeteries in Xinjiang,China

A total of 33 ancient glass beads unearthed from the Kizil reservoir cemetery and Wanquan cemetery in Xinjiang are studied using Raman spectroscopy, scanning electron microscopy with energy‐dispersive spectrometry (SEM–EDS) and other methods. The detailed study of the glassy matrices, the crystalline inclusions and the microstructural heterogeneities for these glass beads has revealed some valuable information to help in the understanding of their possible manufacturing technology and provenance. At least two different types of glass were present in the two cemeteries. For the first time, antimony‐based colourant/opacifier—for example, Pb₂Sb₂O₇ or CaSb₂O₆—was systematically identified in some beads of plant‐ash type soda–lime glass dated to about 1000–500 bc . The limited number of potash glass beads from the Kizil reservoir cemetery, which were dated to about 500–300 bc , used tin oxide as an opacifier. The diverse resources of the soda–lime and potash glasses indicate the existence of a complex trade network between China and the West much earlier than the Western Han Dynasty.     

First Finding of Early Medieval Iron Slags in Sardinia (Italy): A Geochemical–Mineralogical Approach to Insights into Ore Provenance and Work Activity

At Santa Filitica, a Roman settlement in north‐western Sardinia occupied until the ninth century ad , archaeological excavations have found the remnants of a furnace consisting of a semi‐circular base made of stony slabs and tiles bound with clay. The furnace is attached to a wall of Roman age. Layers of the sixth century ad , bearing several variously oxidized slags, were found close to the furnace. These findings first testify to an ironworks in Sardinia, within a well‐defined context. XRPD and SEM–EDS mineralogical and textural analyses suggest that the slags derive from a bloomery and smithing work that was the first evidence of this type documented in Sardinia during the Early Middle Ages. Chemical analyses (performed with ICP and INAA) of rare earth elements and trace elements in two slags and in two Sardinian iron deposits allow some conclusions to be drawn on the local provenance of the ore. Our comparison of the Sardinian findings and some slags representative of archaeological smelting sites at the front of Elba island—the largest and longest lived iron‐working sites in the Mediterranean—also improves the methodology with which iron slags derived from different ores are compared.     

A study of the glazing techniques and provenances of Tang sancai glazes using elemental and lead isotope analyses

This study discusses the elemental compositions and lead isotope ratios of Tang sancai glazes unearthed from the Huangpu kiln, Huangye kiln and two Tang sancai tomb sites. The various glazes feature distinct lead isotope ratios and trace element characteristics, which can be interpreted as evidence for the use of different lead ore deposits and siliceous raw materials in the glazes. This is a strong indication that lead isotopes combined with trace element analysis could be used as a viable approach for identifying the provenance of Tang sancai of unknown origin by linking them to kiln sites, This provenance technique could be significant in the interpretation of ancient ceramic trade and communication patterns. In this study, the provenance of several Tang sancai glazes of uncertain origin were determined using this method: some Tang sancai wares unearthed in Xi'an City were produced in the kiln near Luoyang City and then traded to Xi'an City, providing an idea of ancient Tang sancai ceramic trade routes.     

Turquoise Mine and Artefact Correlation for Some Bronze Age Archaeological Sites in Hubei Province,China

In China, there are places that are rich in gem‐quality turquoise resources, including north‐west Hubei Province and the nearby Baihe County in Shaanxi Province, and many ancient mining sites, although the mining history remains a mystery. Based on the compositional data from reference samples of known deposits, a comparison of the major and trace element contents of archaeological turquoise may help with determination of artefact provenance. This paper discusses new evidence of provenance‐tracking of turquoise in this area, obtained from geochemical analyses using REE and other trace elements of 22 turquoises and their surrounding rock samples from six ancient mines and three archaeological sites. The results indicate that the three archaeological turquoises from the tomb of the Middle Spring and Autumn Period (580–560 bc ) and the Warring States Period (476–221 bc ) in Hubei Province were made of raw material from north‐west Hubei Province and the nearby Baihe County in Shaanxi Province. [Correction added on 29 October 2014, after first online publication: In the preceding sentence, the correct dates for the Middle Spring and Autumn Period, and the Warring States Period have been added]     

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.     

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 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.     

PROVENANCE OF ANCIENT TEXTILES—A PILOT STUDY EVALUATING THE STRONTIUM ISOTOPE SYSTEM IN WOOL*

Strontium isotopes are used in archaeology to reconstruct human and animal migration routes. We present results of a pilot study applying strontium isotope analyses to modern sheep hair as a basis for its potential use as a provenance tracer for ancient woollen textiles. Our hydrofluoric acid‐based, lipid soluble analytical protocol, also tested on a number of ancient textile fibres, allows for contamination‐free, low blank strontium isotope analysis of minimal amounts of archaeological material. ⁸⁷Sr/⁸⁶Sr ratios of decontaminated sheep hair agree well with the compositions of biologically available (soluble) strontium fractions from the respective feeding ground soils, a translatable requirement for any potentially successful provenance tracing applied to wool textiles.     

Black limestones used in antiquity: the petrographic,isotopic and EPR database for provenance determination

We compiled a database of some of the most important black limestone quarries used in Roman times to be able to determine the provenance of ancient artifacts. For this purpose, we adopted a multimethod approach using the techniques commonly applied to study the provenance of white marbles: petrographic observations, carbon and oxygen isotope composition, electron paramagnetic resonance (EPR) spectra characteristics. Few black limestones were quarried and traded in ancient times; indeed, the importance of most of these quarries was restricted to the areas in which they were located. In this work, we selected a limited number of quarries that produced material believed to have been exported and used throughout the Mediterranean area; most of the quarries selected are found in northern Tunisia, i.e. the Roman proconsular Africa: Djebel Oust, Djebel Azeiz, Ain al Ksir and (presumably) Thala. The “Nero Chiota” limestone quarried on the Aegean island of Chios (Greece) was also included in the database.