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.     

LEAD ISOTOPE ANALYSIS OF ARCHAEOLOGICAL METALS BY MULTIPLE‐COLLECTOR INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY*

Lead isotope ratios in archaeological silver and copper were determined by MC–ICPMS using laser ablation and bulk dissolution without lead purification. Laser ablation results on high‐lead metals and bulk solution analyses on all samples agree within error of TIMS data, suggesting that problems from isobaric interferences and/or mass bias variations due to the presence of matrix elements are insignificant. Inaccurate laser ablation analyses on low‐lead copper reflect erroneous mass bias corrections from use of a non‐matrix matched standard. However, in most cases, silver and copper are analysable for lead isotopes by bulk dissolution or laser ablation MC–ICPMS with simplified sample preparation.     

CHEMICAL AND MINERALOGICAL CHARACTERIZATION OF SASANIAN AND EARLY ISLAMIC GLAZED CERAMICS FROM THE DEH LURAN PLAIN,SOUTHWESTERN IRAN*

One hundred and seventy‐five glazed ceramics from Sasanian and Early Islamic period sites located on the Deh Luran Plain in southwestern Iran were examined by instrumental neutron activation analysis for characterizing differences in ceramic pastes and by laser‐ablation inductively coupled plasma mass‐spectrometry for identifying the constituents of the ceramic glazes. The results of the analysis reveal that alkaline‐based glazed ceramics have paste compositions that are distinct from contemporary and later ceramics decorated with alkaline–low‐lead and lead‐based glazes.     

The key role of zinc,tin and lead in copper-base objects from medieval Talgar in Kazakhstan

Metallurgical examination of brass and bronze objects from the medieval (AD 9th–13th century) site at Talgar in Kazakhstan shows that they were mostly cast from the quaternary copper–zinc–tin–lead system with some exceptions that were forged from binary copper–zinc alloys. Evidence is found that brass was produced in the cementation process and that the addition of tin and lead to the parent brass was considered beneficial in casting but was strictly avoided in forging. The mutual effect of zinc, tin and lead for better casting and the advantages of the binary copper–zinc alloys in forging seem to have been the major factors driving the establishment of this unique brass tradition in a society with probably limited access to tin.     

CHEMICAL ANALYSIS OF COPPER ALLOY TRADE METAL FROM A POST-CONTACT HURON SITE IN ONTARIO,CANADA

Fifty-three copper-based metal fragments, recovered from the Robitaille site in southcentral Ontario, were analysed by neutron activation to establish their chemical make-up and to sort them by their trace elemental chemistries. Three different European copper samples, one brassy copper and 48 brass samples with five different chemistries were found. As few as eight trading actions may account for all of the recovered European metal fragments.     

THE COMPOSITION OF COPPER-BASED SMALL FINDS FROM A WEST PHOENICIAN SETTLEMENT SITE AND FROM NIMRUD COMPARED WITH THAT OF CONTEMPORARY MEDITERRANEAN SMALL FINDS

About 100 Phoenician copper alloy artefacts from Morro de Mezquitilla (Spain) have been analysed by inductively coupled plasma spectrometry and atomic unpublished analyses of contemporary material from Nimrud and with small finds of the same period from several Mediterranean areas. There are no published large-scale analyses of Phonenician metalwork and few analyses of the copper-based, very minor objects of the sort typically recovered from excavation and the comparisons show both similarities and differences in techniques and alloys of the various civilizations and classes of objects.     

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.     

APPLICATION OF LEAD ISOTOPE ANALYSIS TO A WIDE RANGE OF LATE BRONZE AGE EGYPTIAN MATERIALS*

Lead isotope analysis was applied to Egyptian materials from the Late Bronze Age in order to investigate the relationship between these different materials, many of which have lead as a significant component. The galena kohls analysed can be provenanced to Gebel Zeit, a large mining site known to have been active during the period. However, the source of lead metal is different and seems to be outside Egypt, along with the source of copper. Lead‐based pigments such as lead antimonate that were used in glass and glazes seem mostly to come from Egypt, although they may well contain a component of ‘Mesopotamian’ lead. In the Predynastic period, galena from many sources is being exploited for use as kohl. However, by the Middle Kingdom (2055–1650 bc ), extraction has concentrated on one source, Gebel Zeit, perhaps reflecting increasingly centralized control and/or the use of large‐scale exploitation. It therefore appears that a complex pattern of trade in lead‐based materials was evident, with lead metal and galena being separate commodities from separate sources and treated as such.     

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.     

NEUTRON RESONANCE CAPTURE ANALYSIS OF SOME GENUINE AND FAKE ETRUSCAN COPPER ALLOY STATUETTES*

The probability of nuclei capturing neutrons reveals sharp peaks, so‐called ‘resonances’, which occur at neutron energies that are specific for each element. These resonances are very suitable for analysing the elemental composition of objects. They are the basis of a new analytical method, ‘neutron resonance capture analysis’ (NRCA). This is a fully non‐destructive method, which is applicable to almost all stable isotopes, determines the bulk elemental composition, does not require any sample preparation and results in a negligible residual activity. Recently, NRCA has been applied in a study of a series of bronze statuettes, obtained from the National Museum of Antiquity in Leiden (NL).     

COPPER AND COPPER ALLOYS IN ANCIENT IRAQ,SYRIA AND PALESTINE: SOME NEW ANALYSES

In a pilot-programme to increase evidence for the history of copper-alloying in ancient Iraq, Syria and Palestine 128 objects in the Ashmolean Museum, Oxford, were tested with a point-source linear X-ray spectrometer for tin, arsenic and antimony. These analyses showed the gradual introduction of tin-copper alloys into Iraq after ca. 2750 b.c. (Early Dynastic IIIA), into Syria a little later and into Palestine by the end of the third millennium b.c. , though numerous artefacts continue to be of copper or arsenical-copper until well into the second millennium b.c. at least. With the appearance of tin-copper alloys the percentage of arsenic in the copper objects noticeably declines indicating that the earlier arsenical-coppers were deliberately produced under controlled conditions.     

DISCOVERY,PRODUCTION AND USE OF TIN‐BASED OPACIFIERS IN GLASSES,ENAMELS AND GLAZES FROM THE LATE IRON AGE ONWARDS: A REASSESSMENT*

Tin‐based opacifiers (lead stannate yellow and tin oxide white) were first used in glass production for a short period in Europe from the second to the first centuries bc , and then again throughout the Roman and Byzantine Empires from the fourth century ad onwards. Tin oxide was also used in the production of Islamic opaque glazes from the ninth century ad , and subsequently in enamels applied to Islamic and Venetian glasses from the 12th century ad onwards. A selection of published analytical data for the tin‐opacified glasses, enamels and glazes is summarized, and the methods used in their production are reassessed. The phase transformations occurring when mixtures of lead oxide, tin oxide and silica are fired are investigated with high temperature X‐ray diffraction (XRD) using a synchrotron radiation source, and these results are used to explain the observed differences in the glass, enamel and glaze compositions. Possible reasons for the use of tin‐based opacifiers in the second to first centuries bc , and for the switch from antimony‐ to tin‐based opacifiers in the fourth century ad are suggested, and the possible contexts in which tin‐based opacifiers might have been discovered are considered. The introduction of tin‐opacified glazes by Islamic potters in the ninth century ad is discussed in terms of technological transfer or independent invention.     

Late medieval copper alloying practices: a view from a Parisian workshop of the 14th century AD

161 late medieval copper-based day-to-day items have been analysed, mostly consisting of small artefacts such as dress fittings. The items were all recently excavated from a 14th century AD metallurgical workshop located in Paris. Eight well-defined copper alloys have been identified that refer to various constraints, the most important one being economics. According to the model proposed, most of the alloys were obtained by dilution of a fresh brass master alloy by scrap metal containing small amounts of zinc, tin and lead. Pure lead was added separately in relatively large quantities, with a limit of 6 wt% Pb marking the boundary between leaded and unleaded alloys. It has been found that the less the cost of the artefact, the more the fresh brass is diluted. For the medium-size castings such as cast vessels, alloys containing large quantities of lead or alloys rich in antimony were used. Such complex alloying strategy pertains more to a small industrial-like plant organisation rather than to craftsman activity, as further supported by a variety of archaeological and historical evidence.     

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.     

GILDINGS AND FALSE GILDINGS OF THE BAROQUE AGE: CHARACTERIZATION AND CONSERVATION PROBLEMS

This work investigates the decayed decoration of the ‘Vergine del Carmelo’ chapel, with a particular interest in the residual gildings. Samples of the finishing layers were examined by VIS‐UV optical microscopy and scanning electron microscopy coupled with EDX spectrometry, in order to evaluate the unusual degradation phenomena. Mineralogical composition of the stucco substrate was characterized by X‐ray diffraction (XRD) and FTIR spectroscopy. The results showed the unexpected presence of a thick layer of brass flakes, applied without any binder, used as a substitute for the damaged original gold leaf, and highlighting a very uncommon selective corrosion process of the brass.     

LEAD ISOTOPE AND TRACE ELEMENT ANALYSIS IN THE STUDY OF OVER A HUNDRED SOUTH INDIAN METAL ICONS*

Technical investigations were made on 130 South Indian statuary images and a few miscellaneous artefacts mostly sampled from the Government Museum, Madras, India, and from the Victoria and Albert Museum and the British Museum, UK. Lead isotope investigations were attempted on 60 of these, and compositional analysis for 18 elements on 115, using inductively coupled plasma optical emission spectroscopy; thus, for 40 objects both lead isotope and trace element analysis was done. From the isotopic and elemental framework, insights are obtained into some art-historical problems of images and artefacts of the Pre-Pallava, Pallava, Chola (i.e., Vijayalaya Chola), Later Chola (i.e., Chalukya-Chola and Later Pandya), Vijayanagara (and Early Nayaka) and Later Nayaka (and Maratha) dynasties, spanning the Early Christian era to the nineteenth century, along with a few other regional styles. Inferences are also made regarding provenance of the lead and the early use of zinc and brass in the early historic period (c. fourth century BC—fourth century AD).     

The production and technology of glazed ceramics from the middle ages,found in the saepinum territory (Italy): a multimethodic approach*

A collection of ceramics from the Middle Ages found in Altilia and Terravecchia (the Saepinum area, Campobasso, Italy) were characterized by using different mineralogical analyses to investigate their provenance and production techniques. The body ceramic was investigated using Rietveld phase analysis of X‐ray powder diffraction patterns, X‐ray fluorescence spectrometry and scanning electron microscopy. The chemical compositions of the coatings were measured by scanning electron microscopy and their mineralogical compositions were determined using a particular technique of X‐ray small‐angle scattering (SAS) optimized for studies of thin films. Moreover, the material used for decoration was studied using micro‐Raman spectroscopy. The archaeometric results confirmed the distinction into two different ceramic classes, already individuated from archaeological analysis: the Altilia objects belong to the protomajolica class, whereas the objects from Terravecchia are RMR (ramina‐manganese‐red) ceramics. A comparison between the chemical and mineralogical compositions of good‐quality ceramic objects and those of waste products indicated local production of the ceramics. A sharp distinction was found in the chemical composition of the coatings: the Altilia products have tin‐opacified lead glazes, while the Terravecchia ones have transparent high‐lead glazes. Among the Altilia products, the unsuccessful process that produced a large quantity of discarded materials was attributed to the high lead content of the glazes. In fact, the principal advantage of the high lead content was to make the preparation and application of the glaze suspension easier, but the risk of reduction of lead oxide to metallic lead was greatly increased. Using micro‐Raman spectroscopy, the following minerals were identified as pigments: pyrolusite for the dark colour, malachite for green, lepidocrocite for yellow and hematite for red.     

THE ELEMENTAL COMPOSITION OF BENIN MEMORIAL HEADS*

Among the Nigerian cast copper‐alloy artefacts, the chronology of the Benin memorial heads has been the most fully worked out. Therefore, a study focused upon their elemental compositions is particularly likely to be interpretable in terms of development of the alloys used in their making. The elemental analyses, both published and unpublished, of 66 Benin heads, supplemented with seven analyses of some artefacts excavated from a well‐dated, very early Benin site, have been collected, analysed statistically and computed to the elemental analyses of 11 heads and figures from Udo. All but a very few of the Benin heads and artefacts separate into five compositional groups, indicating a chronological sequence of different alloying traditions. All but one of the Udo objects fall into a distinctly separate compositional group, together with two Medicine heads. The compositional groups correlate remarkably well with the stylistic types proposed by Dark.     

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.     

CHARACTERIZATION OF RED‐COLOURED SLIPS (ALMAGRA) ON ISLAMIC CERAMICS IN MUSLIM SPAIN*

Small objects found in Islamic (eleventh‐century) kilns excavated in Zaragoza (Spain) were studied to determine the nature of the red coating of almagra pottery. Ceramics with almagra decoration were completely coated with a glossy deep‐red layer, a slip, applied to the body before firing. Chemical and mineralogical studies were carried out, together with analysis of a surface treatment with organic compounds. The results of this study confirm that almagra ceramics were produced by means of a specific and elaborate process (slip preparation, firing and wax application), demonstrating the introduction of this slip into local production during the Islamic period.