LEAD GLAZES IN ANTIQUITY—METHODS OF PRODUCTION AND REASONS FOR USE*

Transparent high lead and tin-opacified lead-alkali glazes have been extensively used throughout Europe and the Near East from their first appearance in the Roman era and the tenth- to eleventh-century Islamic world, respectively, up until the present day. Using, to a large extent, information which is widely scattered through a diverse range of literature, the methods employed in the production of these two glaze types are first outlined and their merits are then compared with those of alkali glazes in terms of ease of preparation of the glaze mixture, ease of application of the glaze, ease of firing, cost of production, glaze-body fit and visual appearance. The principal advantages of transparent high lead glazes as compared to alkali glazes are shown to be ease of preparation and application of the glaze suspension, low susceptibility to glaze ‘crazing’ and ‘crawling’ and high, optical brilliance. Factors that influence the choice of tin-opacified lead-alkali glazes include ease of production of tin oxide by melting tin and lead metals together; a reduced risk of reduction of lead oxide to lead metal and consequent blackening of the glaze; and, again, low susceptibility to ‘crazing’ and ‘crawling’. Limits of current knowledge regarding these two glaze types and requirements for future research are outlined.     

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.     

A CASE STUDY OF ARTHROPODS PRESERVED ON ARCHAEOLOGICAL BRONZES—MICRO‐ARCHAEOLOGICAL INVESTIGATION HELPS RECONSTRUCTING PAST ENVIRONMENTS

This paper offers new perspectives for improving our knowledge of arthropods in wet and aerobic archaeological contexts. The very‐near environment of uncleaned buried bronze artefacts, two ronde‐bosse ornaments of a Celtic grave from the Iron Age (275 to 250 bc , La Fosse‐Cotheret, Roissy‐en‐France), was studied by means of optical and scanning electron microscopies. Taking into account recent knowledge on bronze corrosion (decuprification), this micro‐investigation (micro‐archaeology) allowed identification of two fossilized arthropods—Cryptophagus sp. (Insecta, Coleoptera, Cryptophagidae) and Coccotydaeolus sp. (Acari, Tydaeoidea, Iolinidae)—which sheds some light upon the complex taphonomic process that occurred after the burial of a Celtic chariot. These first results support the idea that the local corroded metal/soil system has to be investigated for a better understanding of archaeological microenvironments. Efficient minute investigation of soiled bronzes could be performed prior to systematic cleaning of artefacts.     

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.     

THE ISOTOPIC COMPOSITION OF TIN IN SOME ANCIENT METALS AND THE RECYCLING PROBLEM IN METAL PROVENANCING

A recent suggestion that some ancient metallurgical processes might give rise to large changes (> 0.5%) in the isotopic composition of tin gave hope that it might be possible to identify ancient bronze samples which had undergone recycling and mixing processes. This paper describes a method for the analysis of the isotopic composition of tin by thermal ionization mass spectrometry and applies it to analyse a number of ancient bronzes and tin metal objects from the Bronze Age Mediterranean. No observable isotopic fractionation of tin was found above $0.1% in the ratio¹²² Sn/¹¹⁶. Consequently, either recycling of bronze in the Late Bronze Age Mediterranean was not so common as supposed, or the isotopic composition of tin is not fractionated by anthropogenic metallurgical processes to the extent predicted by the Bradford group.     

INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY FOR THE ANALYSIS OF ANCIENT METALS*

Inductively coupled plasma-mass spectrometry (ICP-MS) is a relatively new analytical technique, growing in popularity, that offers many advantages over previously available instrumentation for the measurement of both the elemental and isotopic composition of metallic antiquities. The application of this method of analysis to archaeological metalwork is discussed and the technique compared with other methods of analysis commonly used in archaeometallurgy. Particular attention is drawn to the potential pitfalls and difficulties associated with ICP-MS and the need for extremely careful sample preparation and instrument operation.     

THE BEGINNINGS OF TIN-OPACIFICATION OF POTTERY GLAZES

A multidisciplinary programme of research on the glazed ceramics of the Islamic world has been focused on questions of their dating, provenance and technology. One particular question has been the development of tin-opacified glazes, and the nature of glaze opacification generally in the Islamic world. The findings of the various studies combine to indicate that tin was first used experimentally in Basra, Iraq, in the first half of the eighth century AD, apparently within the context of pre-Islamic opaque-glaze technology. Over the course of the next century, an opaque-glaze technology entirely reliant on tin oxide inclusions was developed in Iraq and Egypt and, subsequently, this technology spread to the rest of the Islamic world and also to Europe.     

THERMOLUMINESCENCE DATING OF A CRUCIBLE FRAGMENT FROM AN EARLY TIN PROCESSING SITE IN TURKEY

Archaeological exploration in the Taurus mountains at Göltepe in south-central Turkey has uncovered a site indicating the presence of extensive tin ore mining and smelling operations The most recent find of smelting crucible fragments allowed for a thermoluminescence-hased age determination spanning a late fifth to early third millennium BC date. This result is consistent with a number of radiocarbon dates derived for charcoal also found at the site. The importance of this site relates to the possible tin production and subsequent trade with southwestern Asia which would have provided this otherwise scarce ingredient to bronze technology in that area. This date is directly for crucible material and thus confirms the antiquity of tin smelting at Göltepe.     

MICROANALYTICAL METAL TECHNOLOGY STUDY OF ANCIENT NEAR EASTERN BRONZES FROM TELL BEYDAR*

Forty‐six bronze objects have been investigated to assess their composition and microstructure, using SEM–EDX and optical microscopy. The bronzes originate from Tell Beydar, a site in the northeastern part of Syria that was mainly occupied during the third millennium bc . The compositional results of the metals show a clear chronological sequence in the use of the alloying elements arsenic and tin. In addition, the microstructure indicates advancement in the metalworking techniques that were used.     

OPTICAL PROPERTIES OF TIN‐OPACIFIED GLAZES*

Tin glazes contain SnO2 particles, with a diameter similar to the wavelength of visible light, which are responsible for glaze opacification. In this paper a theoretical model to explain the optical behaviour of these glazes is developed. This model is tested by measurement of the reflectance and transmittance spectra for different optical paths in Spanish Islamic and mudejar glazed ceramics and it is shown to be valid by total reflectance non‐destructive measurements on a wide range of other Islamic and related glazed ceramics.