ENERGY DISPERSIVE X-RAY FLUORESCENCE ANALYSIS OF ANCIENT COPPER ALLOYS: EMPIRICAL VALUES FOR PRECISION AND ACCURACY

Energy dispersive X-ray fluorescence (EDXRF) analyses are compared with neutron activation as well as atomic absorption analyses of ancient copper-based alloys in order to examine their accuracy and to estimate realistic values for precision and sensitivity of EDXRF. The results show that it is possible to obtain reliable data of the surface composition of objects non-destructively. Better results for bulk composition are usually obtained with drill samples where the sensitivity of the method is at least competitive with atomic absorption spectroscopy with flame atomization.     

TIN ISOTOPY—A NEW METHOD FOR SOLVING OLD QUESTIONS

Tin was a vital commodity in times past. In central Europe, the earliest finds of tin‐bronze date to about 2200 bc , while in Greece they are c. 400–500 years earlier. While there is evidence for prehistoric copper mining—for example, in the Alps or mainland Greece, among other places—the provenance of the contemporary tin is still an unsolved problem. This work deals with a new approach for tracing the ancient tin via tin isotope signatures. The tin isotope ratios of 50 tin ores from the Erzgebirge region (D) and 30 tin ores from Cornwall (GB) were measured by MC–ICP–MS. Most ore deposits were found to be quite homogeneous regarding their tin isotope composition, but significant differences were observed between several deposits. This fact may be used to distinguish different tin deposits and thus form the basis for the investigation of the provenance of ancient tin that has been sought for more than a century. Furthermore, the tin‐isotope ratio of the ‘Himmelsscheibe von Nebra’ will be presented: the value fits well with the bulk of investigated tin ores from Cornwall.     

IDENTIFICATION OF FORGERIES BY MEASURING TIN ISOTOPES IN CORRODED BRONZE OBJECTS*

The reliable identification of fakes consisting of bronze often presents problems, because traditional methods such as stylistic studies, optical microscopy, chemical analysis or X‐ray diffraction of the corrosion may not be conclusive. We present a method that is based on the comparison of the tin isotope ratios ¹²²Sn/¹¹⁶Sn and ¹¹⁷Sn/¹¹⁹Sn in the metal and in the adherent corrosion layer. An artificial patina is usually generated within a short time period. It has been observed that such a procedure leads to a depletion of the light tin isotopes in the corrosion layer, while in naturally corroded authentic archaeological objects no isotopic fractionation has been detected. The method has also been applied to archaeological objects and it could be confirmed, among other examples, that the famous ‘Sky Disc of Nebra’ is authentic.     

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 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.     

COINS,ARTEFACTS AND ISOTOPES—ARCHAEOMETALLURGY AND ARCHAEOMETRY*

Archaeometallurgy is one of the earliest manifestations of archaeometric research, using science‐based approaches to address cultural–historical questions. This review first outlines the extent of the field, defining in some detail the main branches of archaeometallurgy, and their specific methodological approaches. It then looks at some of the early publications pioneering archaeometallurgical research, to set the scene for the publication pattern of archaeometallurgy in general, and the role that Archaeometry played in publishing archaeometallurgical research. The analysis of archaeometallurgy‐themed publications in Archaeometry, their change over time and their relationship to the total range of work done in the field indicates that there is a rather narrowly defined and specific type of archaeometallurgy that gets published in Archaeometry, initially with a strong focus on coin and object analysis, often combined with method developments. The more recent developments in isotope‐based studies in archaeometallurgy find only a limited representation in the journal, despite the leading role that the Isotrace Laboratory played in this discipline, for some considerable length of time. More recently, this Archaeometry‐specific ‘flavour’ of archaeometallurgy seems to weaken, with an increase of papers on iron and on primary production in general, subjects still much under‐represented.     

THERMI ON LESBOS: A CASE STUDY OF CHANGING TRADE PATTERNS

Summary Provenance studies on archaeological metal objects rely on their trace element abundance pattern and lead isotopic composition. A comparison of these features in artifacts from different archaeological sites often requires a comparison of results reported by different laboratories. In this case reasonable conclusions can only be expected if it is assured that the respective laboratories produce compatible results. A comparison of some twenty copper-based artifacts from Thermi I and II shows this compatibility still to be less than perfect between Oxford and Heidelberg — Mainz. We find the lead isotopic compositions reported by the two laboratories to agree within the stated uncertainties of the abundance ratios of 0.1 percent. The same is also true, to within 50 percent or better, for the contents of As, Sb, Ag, Au and possibly Ni. Serious discrepancies exist, however, for Co, Pb and Zn that we argue to be due to analytical problems at Oxford. Discriminant analysis of the data from all metal-bearing occupational levels at Thermi reveals a remarkably good correspondence between trace element signature and occupational level which suggests that at the beginning of the third millennium BC intercourse between Lesbians and Aegean metal traders was rare. Lead isotope data show that the change in metal, at least that upon the transition from Towns I + II to Towns III–IV, was indeed due to a change in source region of the metal and not one caused by a change in technology.     

SOUTHEAST ASIA'S FIRST ISOTOPICALLY DEFINED PREHISTORIC COPPER PRODUCTION SYSTEM: WHEN DID EXTRACTIVE METALLURGY BEGIN IN THE KHAO WONG PRACHAN VALLEY OF CENTRAL THAILAND?

Southeast Asian metallurgical developments have been a focus of international academic interest since Solheim (1968 ) and Bayard (1972 ) first published bronze artefacts in claimed early/middle third millennium bce contexts from northeastern Thailand, igniting a regional ‘origins’ of metallurgy debate that has smouldered for 40 years (e.g., White and Hamilton 2009 , Higham in press ). In this paper, we present the results of a lead isotope pilot study centred on the Khao Wong Prachan Valley of central Thailand—currently Southeast Asia's only documented prehistoric copper smelting locale. These preliminary data indicate that our ongoing regional metal exchange research programme may be able to elucidate interaction networks between copper‐producing and ‐consuming societies within and beyond Southeast Asia from c. 2000 bce to c. 500 ce . Furthermore, we are able to offer tentative evidence relevant to White and Hamilton's (2009 ) ‘Rapid Eurasian Technological Expansion Model’ for the Sino‐Siberian derivation of regional metal technologies around the turn of the third/second millennium bce .     

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.