CHARACTERIZATION OF PLASTERS FROM PTOLEMAIC BATHS: NEW EXCAVATIONS NEAR THE KARNAK TEMPLE COMPLEX,UPPER EGYPT*

The aim of the present work is to characterize plasters from Ptolemaic baths recently discovered in front of the Karnak temple complex, by the excavations of an Egyptian–French team. The characterization was carried out by means of optical microscopy (OM), scanning electron microscopy (SEM) equipped with an energy‐dispersive X‐ray detector (EDS), X‐ray diffraction analysis (XRD) and Fourier transform infrared spectroscopy (FT–IR). The results allowed the identification of the chemical composition and structure of these plasters. In addition, samples of red, yellow, black and white pigments were examined and identified. The results helped in providing an image concerning some materials used during the Ptolemaic era in ancient Egypt.     

COOKING AND PAINTED WARE FROM SAN GIUSTO (LUCERA,FOGGIA): THE PRODUCTION CYCLE,FROM THE SUPPLY OF RAW MATERIALS TO THE COMMERCIALIZATION OF PRODUCTS*

Archaeological excavation at the San Giusto site (Lucera, Italy) has unearthed a Late Antique kiln that was most certainly dedicated to the production of cooking ware. An archaeometric study of numerous specimens of cooking and painted ware found at this site was carried out using optical microscopy, scanning electron microscopy, micro‐Raman spectroscopy, X‐ray diffraction, X‐ray fluorescence, inductively coupled plasma mass and optical emission spectrometry and instrumental neutron activation analysis. The integration of historical–archaeological data with archaeometric data has revealed that these specimens can be attributed to the San Giusto site. Furthermore, the production cycle of this ware can thus be reconstructed: from the diversified supply of raw materials (fluvial and marine sediments), to the relatively complex preparation of the paste, to firing at variable temperatures (600–750°C for cooking ware; 850–1050°C for painted ware).     

A MULTI‐ANALYTICAL APPROACH FOR THE CHARACTERIZATION OF COMMODITIES IN A CERAMIC JAR FROM ANTINOE (EGYPT)*

This paper describes a multi‐analytical chemical study performed on the original, almost totally conserved, content of a small ceramic jar from the Antinoe archaeological site (fifth to seventh centuries ad, Roman Egypt) and now belonging to the archaeological collection of the Istituto Papirologico ‘Girolamo Vitelli’ (Florence, Italy). Scanning electron microscopy with an energy‐dispersive X‐ray spectrometer (SEM–EDX), Fourier transformed infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) were all used to characterize the inorganic components of the archaeological material. The organic substances were analysed using FTIR, direct exposure mass spectrometry (DE–MS) and gas chromatography – mass spectrometry (GC–MS). The inorganic component essentially consisted of halite (NaCl). Among the NaCl crystals, lamellar elements were identified. They were chemically characterized by carbonato‐apatite and showed a concentric morphology typical of the scales of small fish. The most prevalent organic constituents of the sample were monocarboxylic acids, α,ω‐dicarboxylic acids, and cholesterol and its oxidation products. The organic material composition was consistent with the occurrence of lipids of animal origin. In addition, diterpenes related to pine pitch were also identified. The overall results suggest that the material recovered in the small ceramic jar found in Antinoe is a residue of fish‐based pickles such as garum, muria, allex and liquamen, which were commonly used in Roman times.     

A SPECTROSCOPIC INVESTIGATION OF PIGMENT AND CERAMIC SAMPLES FROM COPÁN,HONDURAS*

A combination of micro‐Raman spectroscopy, micro‐infrared spectroscopy and SEM–EDX was employed to characterize decorative pigments on Classic Maya ceramics from Copán, Honduras. Variation in red paint mixtures was correlated with changing ceramic types and improvements in process and firing techniques. We have confirmed the use of specular hematite on Coner ceramics by the difference in intensities of Raman bands. Different compositions of brown paint were correlated with imported and local wares. The carbon‐iron composition of the ceramic type, Surlo Brown, was confirmed. By combining micro‐Raman analysis with micro‐ATR infrared and SEM–EDX, we have achieved a more comprehensive characterization of the paint mixtures. These spectroscopic techniques can be used non‐destructively on raw samples as a rapid confirmation of ceramic type.     

Monitoring fluid chemistry in iron oxide–copper–gold‐related metasomatic processes,eastern Mt Isa Block,Australia

Most researchers in the Proterozoic eastern Mt Isa Block, NW Queensland, Australia, favour magmatic fluid and salt sources for sodic‐(calcic) alteration and iron oxide–copper–gold mineralization. Here we compare spatial, mineralogic and stable isotope data from regional alteration assemblages with magmatic and magmatic‐hydrothermal interface rocks in order to track chemical and isotopic variations in fluid composition away from inferred fluid sources. Tightly clustered δ¹⁸O values for magnetite, quartz, feldspar and actinolite for igneous‐hosted samples reflect high temperature equilibration in the magmatic‐hydrothermal environment. In contrast, these minerals record predominantly higher δ¹⁸O values in regional alteration and Cu–Au mineralization. This dichotomy reflects partial equilibration with isotopically heavier wallrocks and slightly lower temperatures. Increases in Si concentrations of metasomatic amphiboles relative to igneous amphiboles in part reflect cooling of metasomatic fluids away from igneous rocks. Variations in X_Mg for metasomatic amphiboles indicate local wallrock controls on amphibole chemistry, while variations in X_Cl/X_OH ratios for amphiboles (at constant X_Mg) indicate variable aH₂O/aHCl ratios for metasomatic fluids. Biotite geochemistry also reflects cooling and both increases and decreases in aH₂O/aHCl for fluids away from plutonic rocks. Decreased aH₂O/aHCl ratios for metasomatic fluids reflect in part scavenging of chlorine out of meta‐evaporite sequences, although this process requires already saline fluids. Local increases in aH₂O/aHCl ratios, as well as local decreases in δ¹⁸O values for some minerals (most notably haematite and epithermal‐textured quartz), may indicate ingress of low salinity, low δ¹⁸O fluids of possible meteoric origin late in the hydrothermal history of the region. Taken together, our observations are most consistent with predominantly magmatic sources for metasomatic fluids in the eastern Mt Isa Block, but record chemical and isotopic variations along fluid flow paths that may be important in explaining some of the diversity in alteration and mineralization styles in the district.     

FIELD AND LABORATORY MULTI‐TECHNIQUE ANALYSIS OF PIGMENTS AND ORGANIC PAINTING MEDIA FROM AN EGYPTIAN COFFIN (26TH DYNASTY)

This paper describes the physico‐chemical analyses performed on an Egyptian wood coffin on the occasion of its restoration in the hall of the National Archaeological Museum of Parma (Italy), with the aim of investigating the pigments and organic materials originally used. Pigment determination was performed both in situ by a portable energy‐dispersive X‐ray fluorescence (EDXRF) spectrometer and in the laboratory using a micro‐Fourier‐transform‐infrared (micro‐FTIR) and a Fourier‐transform (FT) Raman spectrometer. The identification of organic materials was performed through gas chromatography – mass spectrometry (GC–MS) and micro‐FTIR analysis. Amongst the pigments, special attention was paid to the green, which appeared to be severely degraded and was examined using powder X‐ray diffraction (XRD) and scanning electron microscopy – energy‐dispersive X‐ray (SEM–EDX) in addition to the above‐cited techniques. Other materials used in the polychromatic decorations are Egyptian blue, cinnabar and possibly orpiment, while calcium carbonate was used for the ground layer. The organic materials were identified as beeswax, mastic and gum arabic, sometimes as mixtures.     

PIGMENTS AND PLASTERS FROM THE ROMAN SETTLEMENT OF THAMUSIDA (RABAT,MOROCCO)

A total of 22 samples were taken both from plasters still in situ and from collapsed material recovered by French, Italian and Moroccan teams at the Roman settlement of Thamusida (Rabat, Morocco). The sample characterization was obtained using optical microscopy, scanning electron microscopy, image analysis and Raman micro‐spectroscopy. Plaster aggregate was made using a mixture of sands and clays that outcrop nearby, while lime was probably produced using the local limestone crust, as was further verified for the mortars. The plasters from the bath complexes (public buildings) and the Temple à trois cellae (sacred building) were very poorly made, while those from areas VII and XX (private buildings) indicated the involvement of more expert masons. The pigments used were cinnabar, red ochre, yellow ochre, Egyptian blue, green earth, chalk white and carbon black. The overall manufacture was of low quality, and hence perfectly comparable to that observed in other Roman Provinces. With respect to Italy and to other Mediterranean Roman sites, Thamusida fits well within an aesthetic and technical koinè that differentiates sites of the Italian peninsula from those in the Provinces.     

AN 8500‐YEAR‐OLD BLADDER STONE FROM UZZO CAVE (TRAPANI): FOURIER TRANSFORM–INFRARED SPECTROSCOPY ANALYSIS*

A calcium carbonate (calcite) bladder calculus was found in the pelvis of an adult female buried in a Mesolithic cave‐tomb on the coast of Sicily; it was dated by ¹⁴ C to around 6500 bc . Its chemical composition, which was not known before, was determined by means of Fourier transform–infared microspectroscopy (FT–IR–M) using the high‐pressure diamond cell, a device that makes it possible to analyse a small amount of the sample (1–2 µg). In this way, the analysis of all the laminations of the calculus was performed without destroying the sample. Although calcite was the main component, carbonate apatite was also detected in the nucleus and in a more external layer.     

INSIGHTS INTO NORTH MESOPOTAMIAN ‘METALLIC WARE’*

With the aim of shedding new light on the still poorly understood North Mesopotamian metallic ware, ceramic and soil samples from Tell Beydar (northeastern Syria, third millennium bc ) were investigated using a range of analytical techniques, including optical microscopy, SR–XRD and SEM–EDX. The objective of this work was to differentiate calcareous metallic ware from non‐calcareous ware without the aid of chemical analyses and to find further validation of the existing hypothesis that the former group is an imitation of the latter. A third group of metallic wares from Tell Beydar is believed to be of non‐local, still regional origin.     

THE USE OF TRACE ELEMENT ANALYSIS OF ENTRAPPED SLAG INCLUSIONS TO ESTABLISH ORE – BAR IRON LINKS: EXAMPLES FROM TWO GALLO‐ROMAN IRON‐MAKING SITES IN FRANCE (LES MARTYS,MONTAGNE NOIRE,AND LES FERRYS,LOIRET)*

Knowledge of the iron trade in ancient times rests on determining the source of the objects recovered during archaeological excavations. Unfortunately, attributing the origin is not always possible using archaeological tools alone. Trace element data of the ore and the archaeological material (reduction and reheating slags, entrapped slag inclusions from the bloom, bar iron and iron blades) from two Gallo‐Roman iron‐making centres, Les Martys (Montagne Noire) and Les Ferrys (Loiret), were determined using ICP–AES/MS and LA–ICP–MS. The results highlight a continuity of composition that makes it possible to establish a link between the initial ore and the semi‐finished iron products.     

ARCHAEOMETRIC ANALYSES ON ‘CORINTHIAN B’ TRANSPORT AMPHORAE FOUND AT GELA (SICILY,ITALY)*

The aim of this work is to throw light on the archaic production of ‘Corinthian B’ amphorae, which are widely diffused in the Western Mediterranean basin and are also present in Greece, but whose geographical provenance is still under discussion. We analysed a group of 37 samples belonging to different ceramic classes dated to the sixth and fifth centuries bc . In particular, there were 19 sherds of trade amphorae of the so‐called archaic ‘Corinthian B’ type, from archaeological excavations in Gela (Sicily, Italy). As a comparison, we also investigated 18 samples of tiles and local coarse pottery from Sibari (Calabria, Italy). The samples were analysed using different techniques, such as optical analysis with a polarized‐light microscope (OM), X‐ray diffraction (XRD), Fourier transform–infrared absorption (FT–IR) and inductively coupled plasma–optical emission spectroscopy (ICP–OES). The combination of these complementary analytical methods allowed us to characterize the samples, determine their firing temperatures and identify the probable provenance. The study of thin sections of sherds by OM allowed us to divide the investigated amphorae into two main groups: the first was characterized by a composition that suggested a Western provenance, in particular from the Calabrian–Peloritan region; the second one was very similar to the ‘Corinthian B’ amphorae that come from Corinth and have been classified as ‘fabric class 1’ by Whitbread (1995 ). The XRD and FT–IR results permitted us to determine the mineral composition of the findings and to estimate their firing temperature. The ICP–OES technique was particularly useful in identifying the production centres. In fact, in the studied pottery, this analysis revealed Ni and Cr values that were noticeably different between Greek and southern Italian production.     

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.     

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.     

Colouring Agents in the Pottery Glazes of Western Anatolia: New Evidence for the Use of Naples Yellow Pigment Variations During The Late Byzantine Period

A group of the late 12th–13th century Byzantine pottery glazes, mostly related to Zeuxippus Ware Type pottery from the Ku?adas? Kad?kalesi/Anaia site in western Anatolia, was characterized non‐destructively using Raman spectrometry. SEM–EDX was also used complementarily for the glaze characterization. The nature and composition of the glazes, firing conditions, aspects of colour formation and pigments used were discussed. The glazes were found to be lead‐rich silicates, fired close to 700°C on the basis of the Si–O stretching peak maxima of the Raman spectra recorded at ～920–980 cm^–1, as also confirmed by SEM–EDX analysis. The polymerization index values calculated are between approximately 0.05 and 0.1. The use of biscuit‐fired bodies prior to glaze application was suggested based on the results of SEM–EDX analysis. In particular, the detection of Naples yellow pigment variations on a locally produced pottery sample is quite significant, since the use of this type of pigment has hardly ever been reported between the Roman period and the Renaissance.     

AN EVALUATION OF ANALYTICAL AND INTERPRETATIVE METHODOLOGIES FOR THE EXTRACTION AND IDENTIFICATION OF LIPIDS ASSOCIATED WITH POTTERY SHERDS FROM THE SITE OF SAGALASSOS,TURKEY*

Three lipid analysis methods were applied to extracts of archaeological potsherds from the ancient city of Sagalassos, south‐west Turkey. In the fatty acid methyl ester fraction, obtained by selective transesterification of acylglycerols, the ratio of methyl palmitate to methyl stearate was determined. Secondly, by means of gas chromatography– combustion–isotope ratio mass spectrometry (GC–C–IRMS), stable carbon isotope ratios were measured for the same methyl esters. Finally, triglyceride composition was determined via high‐performance liquid chromatography–mass spectrometry (HPLC–MS). All three methods can be used to trace the origin of animal fat. Agreement between them is reasonable, especially in recognizing ruminant adipose fat. One sample was found to be of dairy origin using both GC–C–IRMS and HPLC–MS. The advantages of the various methods are discussed. Variations in lipid composition were observed between samples from different periods and excavated in diverse areas within the city of Sagalassos.     

CHALLENGES IN THE ANALYSIS OF HETEROGENEOUS POTTERY BY LA–ICP–MS: A COMPARISON WITH INAA*

Tempers added to pottery have the potential to obscure geographical variation in the chemistry of exploited clay resources when analysed using bulk methods. A pilot study was conducted to assess the possibility of using LA–ICP–MS to analyse clay matrix in pottery with extremely subtle partitions between INAA chemical groups. LA–ICP–MS was used to analyse the clay matrix of 32 pottery samples from seven Middle and Late Woodland period (c. ad 200–800) sites in north‐east Florida and results were compared to data from INAA of the same samples. The results reveal many of the challenges in analysing highly heterogeneous materials with LA–ICP–MS. However, the study also generated data that are potentially useful in the determination of pottery provenance. In some respects, LA–ICP–MS of clay matrix replicated the chemical variation recorded by INAA, and in other respects the results are divergent. The similarities and differences between these results are explained by specific differences between the methods and the materials analysed (matrix versus bulk analysis). Suggestions for improving the method are discussed.     

CUERDA SECA CERAMICS FROM AL‐ANDALUS,ISLAMIC SPAIN AND PORTUGAL (10TH−12TH CENTURIES AD): INVESTIGATION WITH SEM–EDX AND CATHODOLUMINESCENCE*

Since little is known about the cuerda seca technique, our aim has been to complete an initial analysis of 11th‐century cuerda seca by studying fragments from the 10th century (Pechina, Almería) and the 12th century (Mértola and Almería), so as to establish the diachronic evolution of this technique. Characteristics specific to cuerda seca ceramic glazes were investigated using scanning electron microscopy (SEM) and quantitative chemical analysis with energy‐dispersive X‐ray spectrometry (EDX). The chemical compositions of the different‐coloured glazes (green, black, yellow and white) have given us valuable indications about the evolution of the technique. The opacification mode and the firing process were also investigated. With the help of cathodoluminescence (CL) and the study of modern ‘cuerda seca’ glazed ceramics, new hypotheses regarding the number of firing stages, taking into account glaze and paste transformations and their interactions, are put forward.     

SCIENTIFIC INVESTIGATION OF FAIENCE FRAGMENTS ATTRIBUTED TO THE TOWN MOSAIC AT KNOSSOS*

We analysed a faience fragment from Bristol Museum and Art Gallery, to determine whether it belonged to the Town Mosaic, excavated at Knossos. Three Town Mosaic fragments from the Ashmolean Museum, Oxford were also examined. The objects were analysed using non‐destructive variable‐pressure scanning electron microscopy with energy‐dispersive X‐ray spectrometry. The Bristol object's composition and microstructures are similar to those of the Town Mosaic samples. Our results are also comparable to those from polished samples of Minoan faience (Tite et al. 2009 ), showing that VP SEM–EDX gives reliable results without invasive sampling. Silicaceous, copper‐rich microspheres were identified for the first time in two of the Ashmolean objects.     

IDENTIFICATION OF POST‐DEPOSITIONAL CHEMICAL ALTERATION OF CERAMICS FROM THE NORTH COAST OF PAPUA NEW GUINEA (SANDUAN PROVINCE) BY TIME‐OF‐FLIGHT–LASER ABLATION–INDUCTIVELY COUPLED PLASMA–MASS SPECTROMETRY (TOF–LA–ICP–MS)*

The measured chemical composition of archaeological ceramics can result from a variety of geological, cultural and taphonomic factors. In the present study, we evaluate the likelihood that elevated barium concentrations in ceramics from the archaeological site of Wom/Aiser, located on the northern coast of Papua New Guinea, result from post‐depositional enrichment. Using time‐of‐flight–laser ablation–inductively coupled plasma–mass spectrometry, we mapped chemical compositional profiles across cut sections of ceramic sherds from four archaeological sites, all previously chemically characterized. We identify the formation of pronounced concentration gradients in samples from Wom/Aiser relative to sherds with low barium concentrations, consistent with post‐burial uptake.