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.     

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 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.     

MICRO‐RAMAN SPECTROSCOPY CHARACTERIZATION OF DELLA ROBBIA GLAZES*

Micro‐Raman spectroscopy and the laser‐induced transformation technique were used for systematic study of five coloured glazes on Saint John the Baptist (29 inch tondo), a majolica terracotta relief attributed to Luca Della Robbia and on permanent exhibit in The John and Mable Ringling Museum of Art. We suggest that ions in a lead silicate matrix, called ‘lead ultramarine’, could contribute to the famous Della Robbia blue colour, in addition to the effect of Co atoms as suggested previously by Pappalardo et al. (2004 ). The original yellow glaze contains lead(II) antimonate. The green is a mixture of the yellow and blue pigments, the brown contains hematite, and the white glaze contains tin dioxide as an opacifier. The use of lead oxide as a main fluxing agent is confirmed by laser‐induced micro‐crystallization.     

NEUTRON RESONANCE CAPTURE ANALYSIS OF SOME GENUINE AND FAKE ETRUSCAN COPPER ALLOY STATUETTES*

The probability of nuclei capturing neutrons reveals sharp peaks, so‐called ‘resonances’, which occur at neutron energies that are specific for each element. These resonances are very suitable for analysing the elemental composition of objects. They are the basis of a new analytical method, ‘neutron resonance capture analysis’ (NRCA). This is a fully non‐destructive method, which is applicable to almost all stable isotopes, determines the bulk elemental composition, does not require any sample preparation and results in a negligible residual activity. Recently, NRCA has been applied in a study of a series of bronze statuettes, obtained from the National Museum of Antiquity in Leiden (NL).     

GAMBLING WITH ETRUSCAN DICE: A TALE OF NUMBERS AND LETTERS

The graphical and linguistic interpretation of the first six Etruscan numerals has long been confronted with the ambiguous assignment of the words huth and sa to either 4 or 6. Here, we show how the systematic combinatorial analysis of the numerals appearing on ancient southern Etrurian dice dated from the eighth to the third centuries bc , together with the careful comparison of the results with the only two existing dice carrying the alphabetical translations of the numerals conserved at the Bibliothèque Nationale de France, Paris, finally allows unambiguous mathematical resolution of the linguistic riddle, allowing the firm attribution of the numeral 6 to the graphical value huth and 4 to sa. Combinatorial analysis of the numerals distribution on the six faces of the die shows that only two of the 15 possible numerical combinations were actually in use in southern Etruria, and that during the fifth century bc there was a marked shift from the typical (1–2, 3–4, 5–6) combination used in the early seventh‐ to fifth‐century bc dice to the (1–6, 2–5, 3–4) combination used at later times and still largely adopted today. The largest body of archaeometric data on dice specimens from Etruria is presented, based on macroscopic examination, X‐ray diffraction, DRIFT spectroscopy and density measurements.     

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.     

SYNCHROTRON FTIR MICRO‐SPECTROSCOPY APPLIED TO THE STUDY OF POLISHED SERPENTINITE ARTEFACTS: A NON‐DESTRUCTIVE ANALYTICAL APPROACH

In prehistory, serpentinite was one of the most frequently used raw materials to produce polished stone artefacts. Several conventional analytical techniques can be applied to identify the serpentine minerals, but their application generally requires a powdered sample. This implies that the artefacts to be analysed must be damaged, and the possibility of analysing a mixture of different serpentine polytypes is high. The use of spatially resolved techniques is therefore a necessity to overcome this problem. Several thin sections of serpentinitic rocks and prehistoric axes have been analysed by synchrotron radiation Fourier transform infrared micro‐spectroscopy. The spectra were acquired directly on specific points of polished stone artefacts and this allowed the recognition of the different polytypes of serpentine minerals without causing any damage to the objects. The results show the infrared micro‐spectroscopy technique to be a useful tool for the characterization of archaeological lithic material.     

ANALYTICAL CHARACTERIZATION OF ROMAN PLASTERS OF THE ‘DOMUS FARINI’ IN MODENA*

The paper refers to the analytical characterization of Roman painted plasters dating back to the second century ad . The following techniques were used: optical microscopy (OM), scanning electron microscopy (SEM–EDS), micro‐Raman and Fourier transform infrared spectroscopies (µ‐Raman and FT–IR), X‐ray diffraction (XRPD), colorimetry and thermal analyses (TG/DTA). The investigation analysed the chemical composition and structure of the plasters, the chemical composition of the pigment layers, the use of binders and any chemical alteration of pigments as well as deterioration of the samples. Stratigraphic analysis of plasters allowed identification of their individual components, which proved helpful in finding out more about the mural painting technique employed.     

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.     

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.     

DNA FROM HUMAN ANCIENT BACTERIA: A NOVEL SOURCE OF GENETIC EVIDENCE FROM ARCHAEOLOGICAL DENTAL CALCULUS

We report a molecular methodology to obtain and analyse ancient bacterial DNA from archaeological dental calculus. Recent and archaeological DNA samples, as old as 4000 bp , were successfully extracted and amplified with species‐specific PCR primers. We propose this approach in order to: detect the presence of specific bacterial species infecting past human populations; compare the composition of ancient oral microbiomes among human populations; and analyse the genetic variability and covariation of bacteria and human host populations. Genomic analysis of bacteria from dental calculus is a promising source of evidence for palaeopathological and micro‐evolutionary studies, focused either on micro‐organisms or their human hosts.     

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.     

OCCURRENCES OF GREEN EARTH PIGMENT ON NORTHWEST COAST FIRST NATIONS PAINTED OBJECTS*

An analytical study of First Nations painted objects from the Northwest Coast showed that green earth (celadonite) was used as a green pigment by Tlingit, Haida and Tsimshian artists. Green earth appears to have been used less frequently by Heiltsuk and Kwakwa ka ’wakw artists and was not found on Coast Salish or Nuu‐chah‐nulth objects. Microscopical samples of green paint from 82 Northwest Coast objects, as well as several pigment sources and mineral specimens, were analysed using Fourier transform infrared spectroscopy or X‐ray diffraction. Green earth was the most frequently identified green pigment, found in approximately 40% of the samples.     

GEOCHEMICAL AND ENGINEERING GEOLOGICAL PROPERTIES OF THE VOLCANIC TUFFS USED IN THE ETRUSCAN TOMBS OF NORCHIA (NORTHERN LATIUM,ITALY) AND A STUDY OF THE FACTORS RESPONSIBLE FOR THEIR RAPID SURFACE AND STRUCTURAL DECAY

The geochemical and engineering geological properties of the tuffs used in the rock‐cut cliff tombs of the Etruscan necropolis of Norchia were investigated to evaluate their susceptibility to different weathering agents and confirm their origin. For the first time, materials were characterized by X‐ray powder diffraction (XRD), Fourier‐transform infrared spectroscopy (FT–IR), thermogravimetric analyses (TGA, DGA and DTG), scanning electron microscopy (SEM–EDS) and energy‐dispersive X‐ray fluorescence (ED–XRF), and their different origins confirmed. Tests of material properties indicate that both tuffs are poorly durable, but one of them is less susceptible to weathering. Although tombs made with the more resistant material show limited surface weathering, they undergo severe structural damage because of stress release and plant root infiltration. This, combined with the microclimatic conditions established inside river canyons, can trigger rock falls, leading ultimately to the complete destruction of these tombs.     

ROMANO‐EGYPTIAN RED LEAD PIGMENT: A SUBSIDIARY COMMODITY OF SPANISH SILVER MINING AND REFINEMENT*

Samples of red pigment from a group of seven Roman‐period Egyptian mummies, known as red‐shroud mummies, are investigated. Elemental analysis by inductively coupled plasma time‐of‐flight mass spectrometry (ICP–TOFMS) shows that the samples contain mostly Pb (83–92% by weight), along with 0.2–2.0% Sn. All of the samples are found to have similar trace element distributions when normalized to the continental crust, suggesting that they share a common geological origin. Lead isotope ratios are found to match the mixed lead sources typically associated with Rio Tinto, Spain – a site extensively mined for silver during the first century ad . Raman microspectroscopy identifies the major phase of each sample to be red lead (Pb₃O₄) with a minor phase of lead tin oxide (Pb₂SnO₄). Lead tin oxide does not occur naturally, and its incidental occurrence within the sample indicates that the material was heated under oxidative conditions at temperatures in excess of 650°C. In archaeological contexts, the high‐temperature oxidative treatment of lead is typically associated with metallurgical refinement processes such as cupellation. Based on this evidence, it is argued that the pigment was produced out of litharge associated with silver cupellation at the Rio Tinto site.     

ARCHAEOMETRIC STUDY OF SHELLS OF HELICIDAE FROM THE EDERA CAVE (NORTHEASTERN ITALY)*

The Edera Cave, near Aurisina in the Trieste Karst, retains a stratigraphy that extends from the Mesolithic to the modern era. At Sauveterrian layers, many specimens of Helix cincta are present, which are considerably crushed, and a small percentage of which are also blackened. Chemical analyses show that the blackened specimens were exposed to a temperature of between 500 and 550°C, and suggest that many others were destroyed by fire at temperatures of above 700°C. Consequently, only a part of the Helix cincta shells is assumed to be the residue of human meals, since several factors render plausible an accidental combustion of shells already present in the ground before the lighting of Mesolithic hearths.     

STUDY OF ROMAN ANCHOR FROM THE DEAD SEA SHORE*

A wooden Roman anchor was discovered at the retreating shore of the Dead Sea, north of Ein Gedi. The anchor's wood material was coated by a thick veneer of aragonite and gypsum crusts. The wood was dated by radiocarbon to the early Roman time in the Levant. Lead isotope analyses carried out on the Pb–Fe–Cu anchor material (remains of the anchor's metal parts) yielded ratios that indicate origin of the metal in Italian ores (maybe Tuscan). For the wooden part of the anchor a local tree was used.     

CAMPANIAN POTTERY FROM ANCIENT BRUTTIUM (SOUTHERN ITALY): SCIENTIFIC ANALYSIS OF LOCAL AND IMPORTED PRODUCTS*

One hundred and fifty-seven sherds of Campanian pottery were analysed by inductively coupled plasma optical emission spectroscopy (ICP-OES) and flame emission spectroscopy (FES). The sherds were found in the course of archaeological excavations carried out at the sites of Sibari, Cosenza, Crotone, Locri, Reggio and Oppido Mamertina in southern Italy (ancient Bruttium, today Calabria). Analyses were carried out on dissolved samples, determining 15 elements per sample (Al, Fe, Ca, Mg, Ti, Mn, Sr, Ba, Cr, Cu, Y, La and Sc by ICP-OES, and Na and K by FES). Analytical data were subject to multivariate statistical treatment by hierarchical cluster analysis and principal components analysis. Results indicated different compositional groups, allowing one to separate suspected imports from Campania, Etruria and Sicily from each other and from likely local products. The latter could be further classified into different groups, comprising imitations of foreign forms as well as original local products.