FINE WARE FROM LOCRI EPIZEPHIRI: A PROVENANCE STUDY BY INDUCTIVELY COUPLED PLASMA EMISSION SPECTROSCOPY

Fifty-six sherds of fine ware from Locri Epizephiri were analysed by inductively coupled plasma optical emission spectroscopy (ICPOES) and flame emission spectroscopy (FES). The sherds had been excavated on the archaeological areas of Marasà Sud, Centocamere and San Cono, and represent local and imported products from the seventh to the second century BC. The samples were dissolved by fusion with lithium metaborate and analysed for nine elements (Al, Fe, Ca, Mg, Ti, Mn, Sr, Ba and Cr) by ICPOES, while Na and K were determined by FES. The analytical data were subjected to hierarchical agglomerative clustering and principal components analysis to classify the sherds into compositional groups. The results obtained indicated that Corinthian, Attic and Ionian products or imitations may be classified in a few separate groups, while most local products are found in a unique, large group.     

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.     

A PROVENANCE STUDY OF POTTERY FROM ARCHAEOLOGICAL SITES NEAR CANOSA,PUGLIA (ITALY)*

Studies have been carried out to assess the provenance of selected pottery excavated at archaeological sites near Canosa, Puglia (Italy). Sixty-six sherds, ranging in date from the mid-seventh century BC to the beginning of the third century BC, were analysed by atomic absorption spectroscopy and 16 elements were determined. The analysis data were subjected to multivariate classification procedures. Tests showed that the majority of the examined sherds came from ancient local kilns; a probable Ionian origin was established for some other sherds, while the rest were of unknown origin.     

GEOCHEMICAL ANALYSIS OF VITREOUS ROCKS EXPLOITED DURING THE FORMATIVE PERIOD IN THE ATACAMA REGION,NORTHERN CHILE*

Petrographic analysis and geochemical characterization studies were carried out on vitreous dacite and/or rhyodacite artefacts from Formative period archaeological sites in the upper Salado River Basin in the Atacama Desert, northern Chile. These were compared with samples taken from two source areas located within the subregion, named Linzor and Paniri. Source samples and archaeological specimens were analysed by inductively coupled plasma – mass spectrometry (ICP–MS) combined with optical emission plasma – mass spectrometry (ICP–OES) and atomic absorption spectroscopy (AAS). Results from the limited number of samples analysed indicate that the Linzor source seems to have been the primary source exploited during the Early and Late Formative periods in the Salado River Basin.     

A MICRO‐RAMAN AND INTERNAL MICROSTRATIGRAPHIC STUDY OF CERAMIC SHERDS FROM THE KILNS OF THE MEDICI CASTLE AT CAFAGGIOLO*

Nine representative sherds from the old (14th–16th century) kilns at the Castle of Cafaggiolo in Tuscany have been analysed by means of internal microstratigraphic analyses and micro‐Raman spectroscopy and classified as follows: six engobed and glazed fragments, of which three are covered with an opaque white, decorated layer, one is marbleized, and two are engobed. The surface of the two engobed sherds, fragments of unfinished products, indicates that at least two firing processes were used. Two samples show characteristics of Byzantine pottery, and three of them can be classified as Islamic ware or maiolica, whilst the other one displays intermediate characteristics. The variety of ceramic wares indicates the presence of craftsmen with differing expertise, and suggests that part of their work was dedicated to experimentation on new ceramic production techniques.     

INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION SPECTROSCOPY ANALYSES OF ROMAN MILITARY COPPER-ALLOY ARTEFACTS FROM THE EXCAVATIONS AT MASADA,ISRAEL*

A selection of Roman military fittings and associated copper-alloy artefacts was analysed by inductively coupled plasma-atomic emission spectroscopy. The method used was a variant on those previously published and gives very good precision and accuracy. The Roman metalwork analysed conforms extremely well to similar artefacts analysed from, contemporaneous European sites and suggests, despite the strongly ‘local’ nature of the Judaean legions, a considerable uniformity of alloying practice within the Roman army during the first century AD.     

SCIENTIFIC ANALYSIS OF ROMAN GLASS FROM AUGUSTA PRAETORIA

Fifty-five fragments of Roman glass from Augusta Praetoria (Aosta, Italy) were analysed by inductively coupled plasma optical emission spectroscopy determining 15 elements (Si, Na, Ca, Al, Fe, Mg, Mn, Ti, Sr, Ba, Cr, Ni, Cu, Co and Pb) on dissolved samples; in addition, potassium was determined by flame atomic absorption spectroscopy. The analytical results indicate that all the fragments, with one exception, are silica-soda-lime glasses; (he exception is a potash glass. Cluster analysis was performed on the analytical data by accounting for either 14 (all the elements searched for but Ni and Pb) or eight elements (after further removal of Si, Fe, Mn, Cr, Cu and Co from the data set). The results obtained indicate that, once colouring and decolouring agents are removed, the classification of the glasses seems to be mainly determined by chronology; separate groups within coeval fragments may indicate different provenances.     

A COMPARISON OF INDUCTIVELY-COUPLED PLASMA EMISSION SPECTROMETRY AND ATOMIC ABSORPTION SPECTROMETRY ANALYSIS ON STANDARD REFERENCE SILICATE MATERIALS AND CERAMICS

Analyses by inductively coupled plasma atomic emission spectrometry and atomic absorption spectrometry of 22 ceramic standards and sherds are compared. Further data from analyses of one of the ceramic standards analysed by both methods are also discussed. The results show that for most major elements, the methods are comparable, but that use of common standards would be advisable if data from the two methods are to be compared.     

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.     

ROMAN POTTERY FROM AUGUSTA PRAETORIA (AOSTA,ITALY): A PROVENANCE STUDY

Forty-five sherds of Roman pottery, 21 terrae sigillutae and 24 common wares excavated in Augusta Praeroria, were analysed for 12 elements by atomic absorption and emission spectroscopy. Hierarchical agglomerative cluster analysis, principal component analysis, and non-linear mapping were performed on the analytical data in order to classify the objects in groups which could account for different provenances; soft independent modelling of class analogy (SIMCA) and K nearest neighbours (KNN) were used for solving doubtful assignments. The classification results indicate that local productions of terra sigillatu can be easily distinguished from the imported ones, and that common wares have compositional patterns which differ from those of both local and imported terrae sigillatue.     

COMPOSITION AND ORIGIN OF IAPYGIAN POTTERY FROM ROCA VECCHIA,ITALY

We have studied 35 samples of fragments of ceramic containers dated between the eleventh and the eighth centuries BC, found at the archaeological site of Roca Vecchia, some 20 km from Lecce along the Adriatic (Salentine) coastline. Analysis of the elemental composition of the finds has been performed by means of atomic emission spectroscopy in plasma and the results obtained have been treated with diverse multivariate statistical techniques. Except for some minor differences, the statistical analysis confirms the grouping structures indicated by typological and stylistic evaluations of the samples, in accordance with the validity of the above methods.     

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).     

Characterization of Iron age pottery from eastern Turkey by laser- induced breakdown spectroscopy (LIBS)

Selected pottery sherds coming from the Ayanis, Dilkaya and Karagündüz excavations in eastern Turkey and dated from the Early to Middle Iron Age were examined as regards their composition by using laser-induced breakdown spectroscopy (LIBS). The objective of the study was first to investigate the potential of the LIBS technique in the compositional analysis of pottery and further to explore correlations in spectral data, by using chemometrics methods that would possibly enable discrimination among different sherds. This work is part of a broader study aiming to examine clay variability both before and during the Urartian State period and to explore possible relationships and differences among pottery objects from fortresses and settlements or settlements and cemeteries on the basis of the clay composition of sherds. Preliminary results demonstrate that by using the LIBS technique it is possible to analyse pottery sherds in qualitative and semi-quantitative ways, providing information on the clay and slip composition. Furthermore, encouraging results have been obtained by carrying out principal component analysis (PCA) on the LIBS spectra, which suggest that in certain cases, it is possible to directly correlate spectral information with the origin of pottery sherds.     

Chemical characterization of ancient pottery from sudan by x‐ray fluorescence spectrometry (xrf), electron microprobe analyses (empa) and inductively coupled plasma mass spectrometry (ICP–MS)*

Sixty‐four sherds and seven natural clays from prehistoric sites in northwestern Sudan have been submitted to petrological and chemical analysis using XRF spectrometry, EMPA and ICP–MS. According to their texture, the sherds form five different groups. The high contents of P₂O₅ (more than 0.5 wt%) discerned in 19 samples and the variation of the P₂O₅ content in two samples of the same vessel can be explained by post‐depositional processes or by the ancient organic contents (e.g., milk) of the vessel. Chemical classification of the pottery bulk suggests that vessels were made locally, as only sherds from the same area show homogeneity of data.     

FIRING ANALYSIS OF SOUTH-EASTERN MISSOURI INDIAN POTTERY USING IRON MÖSSBAUER SPECTROSCOPY*

The Mössbauer spectra of prehistoric pottery and clay from the Malden Plain of south-eastern Missouri, USA, were examined. The pottery dates from AD 500 to 1400. The earlier sherds were tempered with sand and the later ones with shell. The sherds and clay contain a mixture of illite, smectite, and kaolinite. Most samples of clay and sherds contained both ferric and ferrous species. The spectral parameters for the ferric species were %DLE_Q～0. 7—1.1 mms^-1 and δ～0.0–0.3 mms^-1 for the ferrous species, ΔE_Q～2.1–2.7mms^-1 and δ～0.7–1.0mms^-1. The ferric to ferrous ratio is more accurately determined from the spectra than from consideration of the colour or the firing core of the sherds, which are not always related to the iron species ratio. Differences among sherds in the ferrous ΔE_Q can be related to original temperature of heating but with low precision.     

Classical and Hellenistic black glaze ware in the Mediterranean: A study by epithermal neutron activation analysis

Fifteen chemical elements have been measured quantitatively by epithermal neutron activation analysis in 58 sherds of black glaze pottery found in Carthage/Tunis (23 sherds), the Athenian Agora (9 sherds), Sicily (7 sherds), and several sites in Southern Italy (19 sherds). Detailed statistical analysis of the results clearly distinguishes five separate groups: (a) one of local Carthage/Tunis origin; (b) one of probable Sicilian origin; (c) a large group of Attic origin comprising sherds found at the Athenian Agora and at Carthage/Tunis; and (d) two separate groups from S Italy.     

THE DATING OF ANCIENT CHINESE CELADON BY INAA AND PATTERN RECOGNITION METHODS*

In 2005, sherds of a special type of ancient Longquan celadon ware were excavated at Maojiawan, in the city of Beijing, China. Although archaeologists agree that these sherds were fired in the period between the Yuan and Ming Dynasties, their specific date is unclear. In order to solve this problem, five other groups of ancient Longquan celadon sherds of known date were selected as reference samples. The elemental body composition of all the sherds was determined by Instrumental Neutron Activation Analysis (INAA). Using the same principles as in provenance research, pattern recognition methods were used to build classification functions to specify the date of the unknown sherds. After analysing the experimental data by discriminant analysis, three classification functions were built. All the unknown sherds were classified as Ming Dynasty. This prediction is well in accordance with the fact that these sherds are similar to other Longquan Ming celadon, and so they should be fired in the same dynasty. This also verified the judgement of the Beijing Institute of Cultural Relics.     

Compositional and Microstructural Study of KoryŎ Celadon and Whiteware Excavated from SŎRi Kiln in Kyŏnggi Province

An extensive study of the composition and microstructure of celadon and whiteware sherds excavated at Sori, one of the most important sites that were active during the founding stage of the stoneware and porcelain industry in Korea, was carried out. The analysed sherds were organized according to four different levels of the excavation and four different styles of haemurigup foot rim. Principal component analysis of the chemical compositions of the sherds revealed slight differences in their body and glaze compositions between the levels of excavation. Porcelain stone with high silica and low aluminium contents was generally used as the body material and wood ash as the chief flux in the glaze. Over the period of operation, the aluminium content in the bodies of the ceramics decreased and the P₂O₅ content in the glazes increased. Glazed bodies were fired in a single step, in contrast to the two‐step method used in later ceramic production. Firing conditions were adjusted to produce vitrification of the glazes, which meant that vitrification of the ceramic bodies occurred to varying extents, mostly determined by the relative contents of flux in the body and the glaze.     

QUANTITATIVE ANALYSIS OF COPPER-TIN BRONZES BY MEANS OF GLOW DISCHARGE OPTICAL EMISSION SPECTROMETRY

Glow discharge optical emission spectrometry (GDOES) has been used for obtaining calibration curves for copper, tin, lead, silver, antimony, arsenic, zinc and iron from standards including copper-base alloys (Cu 61.33-99.95%) and from bronze Punic coins. The GDOES results were calibrated using atomic absorption spectroscopy with inductively coupled plasma atomization (ICPAAS) to analyse the standards and coins. For all these materials, the results show that via GDOES it is possible to obtain reliable and reproducible calibration curves for copper, tin, lead, zinc and iron with a linear behaviour as a function of the content. The quantitative GDOES and ICPAAS data for the coins have been also compared with those obtained via X-ray fluorescence (XRF) and it is shown that GDOES, ICPAAS and XRF agree well with one another considering that the bronze coins are inhomogeneous to some degree. As an example of GDOES analytical features, a depth concentration profile through a thin bronze patina is shown and briefly discussed.     

Non-destructive chemical characterization of ceramic sherds from Shipwreck 31CR314 and Brunswick Town, North Carolina

The purpose of this study was to chemically and texturally characterize ceramic oil jar sherds from North Carolina Shipwreck 31CR314 and to explore the utility of environmental scanning electron microscopy/X-ray energy dispersive spectrometry (SEM/EDS) for that purpose. The oil jar sherds, widely dispersed about Shipwreck 31CR314, are morphologically similar to each other, which suggests they could be from a single jar, but with so few joins this could not be concluded with certainty. Therefore, an aim of this study was to investigate whether chemical or textural characterization of the sherds might reveal unique attributes that could distinguish individual jars; results of characterization perhaps could give information on their origin and possibly site formation processes, such as whether environmental forces could have scattered sherds of a single jar during and after sinking of the ship. Previous studies have indicated this shipwreck is likely the remnants of the Queen Anne's Revenge, flagship of the pirate Blackbeard. Sherds from this shipwreck were compared with similar oil jar sherds excavated from a land site, Brunswick Town, North Carolina, to explore the use of composition and texture as hallmarks. The chemical components of the artifacts were determined by SEM/EDS. This method of analysis is valuable for archaeological research because it is rapid and non-destructive to the ceramic artifacts. Both groups of lead-glazed coarse red earthenware sherds were texturally similar except for the glazed sides of all 31CR314 sherds that exhibited small tracks of unique crescent-shaped marks. These marks may be due to manufacturing effects and immersion in seawater, and the marks may serve as hallmarks for individual jars or potentially individual manufacturers. The sherds were generally similar in composition, but the two groups exhibited distinct differences. Brunswick Town sherds consistently contained more phosphate on unglazed sides, an average 1.46 wt.% P₂O₅, and also contained trace elements not detected in the Shipwreck 31CR314 sherds. These distinct differences could be due to different manufacturing origins for Shipwreck 31CR314 and Brunswick Town ceramics but also could reflect their subjection to different environments during use and loss prior to archaeological recovery.