CYPRIOT BYZANTINE GLAZED POTTERY: A STUDY OF THE PAPHOS WORKSHOPS

Twenty‐five samples of Byzantine glazed pottery from two archaeological sites between Limassol and Paphos region (Cyprus), dated between the 12th and 15th century ad were studied using micro X‐ray fluorescence spectroscopy, scanning electron microscopy and X‐ray diffraction analysis. It was found that all the glazes contain lead, following the main manufacturing process of medieval pottery in the Mediterranean territory, while some of them contain tin, possibly for better opacity. Furthermore, it is shown that copper, iron and cobalt with nickel are responsible for the decoration colours. Finally, the application of principal component analysis revealed significant differentiation for some of the samples.     

Wavelength‐dispersive X‐ray fluorescence analysis of ancient glasses*

The application of X‐ray fluorescence to the study of the composition of ancient glasses has been limited by the large amount of material required for samples. In this paper the setting of a reduced sampling XRF method for the analysis of ancient glasses is described. The method involves the preparation of glass beads by melting the sample with lithium tetraborate flux. By means of reference and synthetic samples, the method allows regression curves to be set, covering broad ranges from ppm to high concentrations. By means of a single program, up to 31 elements of interest in the study of ancient glass are analysed. The reproducibility, sensitivity and reliability of the method are discussed. The results demonstrate that 0.2 g of glass is sufficient to obtain accurate and sensitive analyses for most of the elements of interest.     

THE APPLICATION OF A PORTABLE X‐RAY FLUORESCENCE SPECTROMETER TO THE ON‐SITE ANALYSIS OF GLASS VESSEL FRAGMENTS FROM SOUTHERN THAILAND*

Ancient glass vessel fragments belonging to the seventh to ninth centuries ad , from the Ko Kho Khao, Laem Pho and Khuan Lukpad sites in southern Thailand, were studied. The glass vessel fragment samples are a collection belonging to the Department of Archaeology, the 15th Regional Office of Fine Arts of Thailand. The chemical compositions of the glasses were analysed using a modified portable energy‐dispersive X‐ray fluorescence spectrometer (OURSTEX 100FA‐II) by the introduction of a MOXTEK^® AP3.3 polymer window (5 mm²?) to the KETEK silicon drift detector for the measurement of light elements. The non‐destructive analysis was performed at the National Museum, Phuket, in Thailand. It is shown that the glass chemical compositions belong to mineral and plant‐ash based soda–lime–silicate glass. The origins of the glass artefacts are discussed in terms of raw materials and glass decoration, and compared with previously reported similar typological glasses from sites in the port city of Rāya and the Monastery of Wadi al‐Tur in Egypt.     

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.     

COLOURED OPAQUE GLASS BEADS OF THE MEROVINGIANS*

Monochrome coloured opaque glass beads of the Merovingians have been examined by different analytical methods. A large number of mostly unprepared beads have been measured by X‐ray fluorescence analysis. X‐ray diffraction was used for the identification of the crystalline colouring and opacifying pigments, and electron probe micro‐analysis as well as scanning electron microscopy were applied to study the composition and the microstructure of a white, brown, green, orange and yellow glass bead. After subtracting the content of colouring oxides of the glass beads and normalizing the residual values to 100% an identical soda‐lime‐glass matrix was obtained. The origin of the colouring metal oxides is discussed.     

THE CHEMICAL COMPOSITION OF SOME ARCHAEOLOGICALLY SIGNIFICANT FLINT FROM DENMARK AND SWEDEN

Flint was one of the most widely employed raw materials for artefact manufacture in Denmark and Sweden during the Stone Age, and it continued to be used during subsequent periods. Prehistoric flint mining and lithic manufacturing studies in these countries have attracted considerable attention, but there have been no recent attempts to chemically characterize the geological source materials. This paper builds on a pilot study ( Hughes et al. 2010 ) and uses energy‐dispersive X‐ray fluorescence (EDXRF) analysis to determine quantitative composition estimates for nine major, minor and certain trace elements in seven archaeologically significant flint sources in Denmark and Sweden, along with new data on a number of other sources of prehistoric significance. These data provide a geochemical foundation for ongoing research devoted to determining contrasts and continuities in the time and space utilization of flint sources in Scandinavian prehistory.     

PETROGRAPHIC AND CHEMICAL CHARACTERIZATION OF POTTERY PRODUCTION OF THE LATE MINOAN I KILN AT HAGHIA TRIADA,CRETE*

Pottery from the Late Minoan I kiln at Haghia Triada in the Mesara Plain, southern Crete, was analysed by a range of techniques, comprising thin‐section petrography, scanning electron microscopy, X‐ray diffraction, X‐ray fluorescence and neutron activation analysis. The project characterizes the ceramic fabrics and probable raw materials, correlates paste recipes with shape, reconstructs the firing conditions of the kiln and establishes a chemical reference group, taking into account post‐burial alteration and contamination. Comparison of the reference group formed with that from the neighbouring, broadly contemporary, kiln at Kommos shows an unexpected differentiation of the two kilns.     

UNIQUE PRE‐ROMANESQUE MURALS IN KOSTOĽANY POD TRÍBEČOM,SLOVAKIA: THE PAINTING TECHNIQUE AND CAUSES OF DAMAGE

Pre‐Romanesque murals at Kosto?any pod Tríbe?om, Slovakia, have been investigated by portable X‐ray fluorescence and by microanalytical methods to identify painting materials (pigments and binders), and to explain the degradation of colours. Today, missing green and blue shades have been reconstructed according to residual concentrations of Cu, which correspond to copper chlorides—products of salt corrosion of the copper carbonates azurite and/or malachite, accelerated by micro‐organisms. As confirmed by powder X‐ray microdiffraction, original minium (Pb₃O₄) has been transformed to brown–black plattnerite (PbO₂). In increased humidity, even insoluble pigments are washing down from the walls and the intensity of colours further diminishes.     

MULTIVARIATE ANALYSIS OF THE ENERGY DISPERSIVE X-RAY FLUORESCENCE RESULTS FROM BLUE AND WHITE CHINESE PORCELAINS*

The energy dispersive X-ray fluorescence technique was employed to study non-destructively the surface of 66 samples of Chinese porcelain, of different periods and origins, and determine the contents of 13 chemical elements, namely, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ga, Pb, Rb, Sr, Y and Zr. Principal components analysis was performed on these 13 variables, and scatter plots, incorporating the first, second and third principal components, used to study the clustering behaviour of the data. Based on these results, discriminant analysis was then performed on the data, and discriminant functions established for attributing the period and origin of the porcelains.     

A SCIENTIFIC INVESTIGATION ON THE PROVENANCE AND TECHNOLOGY OF A BLACK‐FIGURE AMPHORA ATTRIBUTED TO THE PRIAM GROUP*

The restoration of a Greek black‐figure amphora provided an opportunity to study the provenance and production technology of the vase. The composition of the ceramic body, determined by inductively coupled plasma optical emission spectroscopy (ICP–OES), matches that of Attic products. Investigation by X‐ray diffraction and reflectance spectroscopy suggests a maximum firing temperature around 900°C and a body re‐oxidation temperature around 800°C, respectively. The morphology and composition of black, red and dark red surface areas were studied by scanning electron microscopy and X‐ray energy‐dispersive analysis; the black areas show the features of a typical well‐vitrified black gloss, while the red areas were most probably obtained by simple burnishing of the body; the dark red additions, on the other hand, are the likely result of a partial re‐oxidation of a clay–ochre mixture.     

THE HISTORY OF THE LAWRENCE BERKELEY NATIONAL LABORATORY INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS PROGRAMME FOR ARCHAEOLOGICAL AND GEOLOGICAL MATERIALS

The Lawrence Berkeley National Laboratory pottery provenance group developed standards and instrumental neutron activation analysis (INAA) methods that are used at many archaeometry laboratories around the world. The background and development of ‘Standard Pottery’ and of methods for INAA are described. Early pottery provenance studies are described, and other research programmes, involving obsidian and magmatic mixing, the origin of the stone used for the Colossi of Memnon, and the ‘Plate of Brass’, are mentioned. Research work by the Laboratory included the discovery of the world‐wide iridium anomaly and extensive subsequent research on what has come to be known as the ‘Asteroid Impact Theory’. Characteristics of the analytical programme for pottery provenance work, including overall aims, precision and accuracy, intercalibration, and irradiation and measurement protocols, are discussed. New research areas developed in the past 15 years, to broaden the usefulness of chemical compositional data for archaeological investigation, and examples of recent work, are described. This research, which makes use of high‐precision X‐ray fluorescence analysis in addition to INAA measurements on sample splits, includes distinguishing the products of different workshops located at the same production site, studies on the significance of the distribution of silver in archaeological pottery and the use of high‐precision chemical compositional data as an aid for making chronological distinctions.     

NATURE AND MICROSTRUCTURE OF GALLIC IMITATIONS OF SIGILLATA SLIPS FROM THE LA GRAUFESENQUE WORKSHOP*

The red glaze (slip) that characterizes the Terra Sigillata potteries greatly contributed to their success during the Roman period. The colour of the slip can in fact be partially explained by the microstructure (crystalline phases, grain sizes) and the physico‐chemistry (composition) of the ceramics. However, the precise process and the diffusion of this technique are still not fully known. In particular, we do not know yet how the production of sigillata took place in the south of Gaul, and the role that was played by the production under Italian influence (pre‐sigillata) preceding the first local sigillata. In this work, a combination of transmission electron microscopy (TEM) and X‐ray synchrotron diffraction techniques was used to study the microstructure of pre‐sigillata slips from the main southern Gaul workshop (La Graufesenque), in order to compare their characteristics with those of high‐quality sigillata. These first results seem to indicate that the antique potters chose clays adapted to their firing conditions and to the type of coating that they wanted to make. These productions cannot be described as an initial phase for the later sigillata production and, rather, seem to correspond to the intention of developing a specific type of pottery only inspired by the famous Italian sigillata forms.     

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.     

ON STATISTICAL APPROACHES TO THE STUDY OF CERAMIC ARTEFACTS USING GEOCHEMICAL AND PETROGRAPHIC DATA*

The scientific analysis of ceramics often has the aim of identifying groups of similar artefacts. Much published work focuses on analysis of data derived from geochemical or mineralogical techniques. The former is more likely to be subjected to quantitative statistical analysis. This paper examines some approaches to the statistical analysis of data arising from both kinds of techniques, including ‘mixed‐mode’ methods where both types of data are incorporated into analysis. The approaches are illustrated using data derived from 88 Late Bronze Age transport jars from Kommos, Crete. Results suggest that the mixed‐mode approach can provide additional insight into the data.     

DISCOVERY AND CHARACTERIZATION OF AN UNKNOWN BLUE‐GREEN MAYA PIGMENT: VESZELYITE*

Blue‐green mosaic and polychrome masks and funerary offerings from the royal tombs of Calakmul, Mexico, were analysed by scanning electron microscope equipped with energy dispersive X‐ray spectroscopy (SEM‐EDS), X‐ray diffraction (XRD), and particle induced X‐ray emission (PIXE). This led to the first identification of the use of veszelyite, a rare hydrated copper‐zinc phosphate, as green pigment. Analyses of a geological sample of this mineral have been done to confirm the characterization of this Mayan pigment, which might help determine pre‐Columbian trade routes of precious and luxury objects in the ancient Maya Classic period (ad 250–800).     

CORRESPONDENCE AND DISCRIMINANT ANALYSES OF SAND AND SAND TEMPER COMPOSITIONS,TONTO BASIN,ARIZONA*

Geologists use petrographic modal analysis to relate fluvial sand composition to source rock composition, thus establishing provenance. Archaeologists seeking to establish provenance of sand temper in pottery can use similar petrographic methods, but their finer scale of investigation requires more precise statistical tools than those employed by geologists. A quantitative method for performing that task is presented. It utilizes correspondence analysis and discriminant analysis of logratio transformed point‐count data to define petrofacies, or sand temper resource procurement zones. The procedure is illustrated with sand and sand‐tempered sherd samples collected from the Tonto Basin, central Arizona; temporal trends in utilitarian ceramic production c. AD 100–1350 are reviewed.     

ANALYSING ARCHAEOLOGICAL BASALT USING NON‐DESTRUCTIVE ENERGY‐DISPERSIVE X‐RAY FLUORESCENCE (EDXRF): EFFECTS OF POST‐DEPOSITIONAL CHEMICAL WEATHERING AND SAMPLE SIZE ON ANALYTICAL PRECISION*

Energy‐dispersive X‐ray fluorescence (EDXRF) has been commonly used to determine geological sources of volcanic glass artefacts, but its ability to discriminate between basaltic sources is less developed. We examine the precision and accuracy of non‐destructive EDXRF for basalt artefacts by analysing varying size and weathering characteristics. The experiments identified no appreciable effect in reproducibility or measured composition due to thickness (down to 1 mm) or natural weathering of pre‐contact flake scars for the 17 elements measured in this study. Samples with surface area less than 100 mm², however, show significant variability in measured composition and reproducibility.     

SCIENTIFIC ANALYSIS OF SEVENTH‐CENTURY GLASS FRAGMENTS FROM THE CRYPTA BALBI IN ROME*

Inductively coupled plasma emission spectroscopy, reflectance spectroscopy and X‐ray diffraction were used to study seventh‐century AD glass fragments from the Crypta Balbi in Rome. All the samples were found to be silica‐soda‐lime glasses. Iron determines the colour of blue‐green, green and yellow‐green transparent glasses; chemical composition suggests deliberate addition of iron and/or manganese in about half the samples. Copper was found as the main colourant in red, pale blue and blue‐green opaque fragments; elemental copper acts as an opacifier in red glass, and calcium antimonate in white, pale blue and blue‐green glasses. Detection of antimony in transparent fragments suggests recycling of opaque mosaic tesserae.     

A STUDY OF GLASS TESSERAE FROM MOSAICS IN THE MONASTERIES OF DAPHNI AND HOSIOS LOUKAS (GREECE)

In this work 51 glass mosaic tesserae from decorations of the two Greek monasteries of Daphni and Hosios Loukas were analysed by inductively coupled plasma optical emission spectroscopy, electron microprobe analysis and X‐ray powder diffraction. On the basis of the chemical analyses, after discrimination between the tesserae of the original decorations and those from other periods, it was possible to outline the distinctive traits of Byzantine mosaic tesserae. In both the monasteries, the original mosaics were decorated with tesserae produced with plant ash based glass, either of the typical composition or a mixture with natron type glass. The samples from the Hosios Loukas decorations show a more homogeneous composition compared with those from Daphni. The major differences among the original samples are due to the presence of opacifiers and colourants.     

RIETVELD X-RAY DIFFRACTION AND X-RAY FLUORESCENCE ANALYSIS OF AUSTRALIAN ABORIGINAL OCHRES*

Rietveld phase analysis of X-ray powder diffraction patterns and chemical analysis by X-ray fluorescence spectroscopy have been used to characterize a series of red and yellow ochre samples from Aboriginal ochre deposits in South and Western Australia. The ochres were found to have diverse mineralogy, being mixtures of up to seven minerals, and also to have complex trace element signatures. The mineralogical characteristics and geochemistry of the ochres can be used to identify the source quarries. Using this combination of analytieal techniques it may be possible to trace the source of ochres in burial sites and on objects back to the original quarries.