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.     

NEUTRON ACTIVATION ANALYSIS OF ARCHAEOLOGICAL MATERIALS: AN OVERVIEW OF THE ITN NAA LABORATORY,PORTUGAL

Instrumental neutron activation analysis (INAA) has been applied to archaeological samples at the Portuguese Research Reactor (RPI) since 1973, and the number of samples analysed has increased steadily since the mid‐1990s. Archaeometric applications of INAA at RPI include the analysis of archaeological ceramics and the stones used in monumental architecture (menhirs) and other historical monuments. A programme of analysis also exists for measuring the precision of and contributing to the certified values of geochemical reference samples. In addition, the study of interference factors is performed to obtain better accuracy in the determination of concentrations of some elements (e.g., corrections for spectral interferences from uranium fission products in the determination of barium, rare earth elements and zirconium).     

BUILDING A BRIDGE TO THE PAST: ARCHAEOMETRY AT THE IPEN REACTOR

Neutron activation analysis has contributed to research in Peru in different scientific fields, particularly in archaeometry. In archaeometry, applications include the characterization of copper alloy artefacts from the tomb of El Señor de Sican to determine production methods, ceramics from the Wari Culture to study production, and distribution of Middle Horizon pottery in Cuzco, ceramics from Villa El Salvador to determine production groups, and obsidian source analysis.     

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.     

DETERMINING POTTERY PROVENANCE: APPLICATION OF A NEW HIGH-PRECISION X-RAY FLUORESCENCE METHOD AND COMPARISON WITH INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS*

A recently developed high-precision X-ray fluorescence (XRF) method, applied for the first time to the study of archaeological pottery, determines the abundances of 13 trace and four major elements from one X-ray spectrum acquired over a 1000 second counting interval. For replicate archaeological samples, the short-term and long-term measurement precisions were close to 1% for the ten elements measured with highest precision. These are comparable to the best results achieved on replicates of clay and pottery standards, and obsidian, using instrumental neutron activation analysis (INAA). High-precision XRF analysis, however, does not require a nuclear facility, and is markedly preferable to INAA in terms of the ease of both sample preparation and analytical procedure. Consequently, element abundance data can usually be provided by a single analyst within a few hours after the start of sample preparation. The accuracy of the method, determined by comparison with data of other workers on eight standard reference materials, averaged 2.4% for the ten best-agreeing elements. The effectiveness of the method for determining pottery provenance is demonstrated for a difficult problem, in which high-precision XRF analysis successfully distinguished the products of two nearby pottery manufacturers in Roman Galilee (Shikhin and Nahif) that had not been clearly differentiated by INAA. The greater effectiveness of high-precision XRF than INAA in this provenance study is a result of the different array of elements measured, and the higher precision obtained for certain elements, by XRF. These results suggest that high precision XRF has potential broad applicability for pottery provenance studies.     

Advances in Polychrome Ceramics in the Islamic World of the 12th Century AD

As part of a multidisciplinary programme of research on Islamic glazed pottery, the development of polychrome decoration during the 12th century AD has been investigated by examining polished sections through glazed pottery in an analytical scanning electron microscope. The two main decorative techniques used were underglaze and overglaze painting. The results suggest that true underglaze decoration, involving the application of pigment without any associated slip, was first developed in Syria, from where it spread to Iran, on to China and ultimately across wide areas of the world. In contrast, the overglaze technique used on mina'i ware was both very short‐lived and confined to Iran. The analytical results suggest that the probable explanation for this was the technical problems associated with maturing the overglaze paint and the consequent risk of unsatisfactory products.     

Traces of Fatty Acids from a Byzantine Sounding Lead Recovered off the Israeli Coast

Fatty acids, typical to large herbivores, were isolated from a 7th century Byzantine sounding lead recovered from a shipwreck off Dor, an ancient anchorage in Northern Israel. The fatty acids survived by being sheltered in an anaerobic environment provided through a site formation process induced by the disintegrating wreck. Previously established identification criteria for fatty acids, absorbed in ceramics, were used to show that tallow was used in this navigational instrument in the Eastern Mediterranean during late antiquity.     

A PRELIMINARY PETROGRAPHIC ANALYSIS OF CYPRIOT WHITE SLIP II WARE*

Samples of Late Bronze Age White Slip II ware from Cyprus were analysed using optical and scanning electron microscopy in conjunction with energy and wavelength dispersive analyse The slip has a novel granular nature and the coarser aggregates are impressed into the outer surface of the body, indicating that it was applied to a moist surface before the vessels were fired. It has a consistent mineral assemblage (Mg‐chlorite + illite‐smectite + sphene + anatase/rutile ± albite) which is very similar to that of hydrothermally altered zones associated with copper orebodies in the Troodos Massif which were mined in antiquity Our analysis suggests that the raw material for the slip was not found at the ground surface, because the alteration assemblage is unaffected by oxidation and copper carbonate or iron staining. It may, therefore, be a by‐product of sub‐surface ore extraction     

ARCHAEOMETRICAL INVESTIGATION OF SICILIAN EARLY BYZANTINE GLASS: CHEMICAL AND SPECTROSCOPIC DATA*

A series of early Byzantine glasses, recovered in Ganzirri (Sicily, Italy), was analysed for major, minor and trace elements. All the analysed fragments were found to be natron-based silica–lime glass. Concerning minor and trace elements, the samples can be divided into two groups: glass with high Fe, Ti and Mn contents ( HIMT glass) and glass with low levels of Fe, Ti and Mn. These results, strictly in agreement with literature data for glass of the Mediterranean region, can be interpreted as a consequence of the wide trade network established in this region and of the intense circulation of raw glass and artefacts from different Mediterranean areas. X-ray absorption spectroscopy studies at Fe and Mn K-edges, performed on HIMT glass, indicate that Fe is in the oxidized form while Mn is in the reduced form.     

THE DISCOVERY OF ANOMALOUSLY HIGH SILVER ABUNDANCES IN POTTERY FROM EARLY ROMAN EXCAVATION CONTEXTS IN JERUSALEM*

This is the first study on the differential distribution and concentrations of silver in ceramics recovered from archaeological excavations. The chemical compositions of 1174 pottery vessels from 38 Roman‐period sites in Israel have been determined. Unusually high and variable abundances of silver were discovered in pottery samples of all vessel types and chemical compositions from four distinct archaeological contexts dating to late first century bce to 70 ce Jerusalem. The large majority of the Jerusalem vessels could be distinguished by their silver abundances from all analysed pottery pieces recovered at rural sites outside Jerusalem, even when the pottery types and chemical compositions, except for silver, of pottery found within and outside Jerusalem were indistinguishable. The evidence is suggestive of a human origin for the high and variable silver abundances, and dispersion of the silver by aqueous transport. The differential silver concentrations found in excavated pottery from Jerusalem and other urban and rural sites suggest that attention to the distribution of silver in pottery from excavated contexts may be helpful for evaluating the nature and function of archaeological remains and patterns of urban contamination.