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.     

THE COMPLEMENTARY USE OF NEUTRONS AND X‐RAYS FOR THE NON‐DESTRUCTIVE INVESTIGATION OF ARCHAEOLOGICAL OBJECTS FROM SWISS COLLECTIONS*

This paper shows the possibilities offered by the combined use of non‐destructive neutron and X‐ray beams in archaeological research on metallic finds. The following five artefacts from Swiss excavations were submitted to investigation, each with dedicated aims: a Roman sword, a Roman dagger, an Iron Age bucket, Iron Age spearheads and a Roman finger ring. The images obtained with both methods—neutrons and X‐rays—are discussed in length in this paper. The investigations took place at the Paul Scherrer Institute and the archaeologists who studied the objects come from the Universities of Lausanne and Zurich.     

The production and technology of glazed ceramics from the middle ages,found in the saepinum territory (Italy): a multimethodic approach*

A collection of ceramics from the Middle Ages found in Altilia and Terravecchia (the Saepinum area, Campobasso, Italy) were characterized by using different mineralogical analyses to investigate their provenance and production techniques. The body ceramic was investigated using Rietveld phase analysis of X‐ray powder diffraction patterns, X‐ray fluorescence spectrometry and scanning electron microscopy. The chemical compositions of the coatings were measured by scanning electron microscopy and their mineralogical compositions were determined using a particular technique of X‐ray small‐angle scattering (SAS) optimized for studies of thin films. Moreover, the material used for decoration was studied using micro‐Raman spectroscopy. The archaeometric results confirmed the distinction into two different ceramic classes, already individuated from archaeological analysis: the Altilia objects belong to the protomajolica class, whereas the objects from Terravecchia are RMR (ramina‐manganese‐red) ceramics. A comparison between the chemical and mineralogical compositions of good‐quality ceramic objects and those of waste products indicated local production of the ceramics. A sharp distinction was found in the chemical composition of the coatings: the Altilia products have tin‐opacified lead glazes, while the Terravecchia ones have transparent high‐lead glazes. Among the Altilia products, the unsuccessful process that produced a large quantity of discarded materials was attributed to the high lead content of the glazes. In fact, the principal advantage of the high lead content was to make the preparation and application of the glaze suspension easier, but the risk of reduction of lead oxide to metallic lead was greatly increased. Using micro‐Raman spectroscopy, the following minerals were identified as pigments: pyrolusite for the dark colour, malachite for green, lepidocrocite for yellow and hematite for red.     

A Unique Case of Prone Position in the Primary Cremation Tomb 252 of Monte Sirai Necropolis (Carbonia,Sardinia, Italy)

A series of graves belonging to the Phoenician period were investigated after the campaign excavation of 2007 in the Phoenician‐Punic necropolis of Monte Sirai (Carbonia, Sardinia, Italy). One tomb in particular (labelled 252) is presented here because of its uniqueness. Tomb 252 contained the cremated remains of an individual, probably male, and comparison of the excavation records alongside reconstruction of the bone material itself makes clear that the individual was cremated in a prone position. It represents the first case of prone cremation reported in the literature. To investigate whether the temperature of the cremation was homogenous across the entire body, we have conducted a combined physical–chemical analysis using X‐ray diffraction spectroscopy and Fourier transform infrared. Copyright © 2012 John Wiley & Sons, Ltd.     

The Belgammel Ram,a Hellenistic‐Roman Bronze Proembolion Found off the Coast of Libya: test analysis of function,date and metallurgy,with a digital reference archive

The Belgammel Ram was found off the coast of Libya in 1964, and examined during 2008–9. The following techniques were used: surface non‐contact digitizing using a laser scanner, reflectance transformation imaging using polynomial texture mapping and hemi‐spherical harmonics, digital photogrammetry with dense surface modelling, structured light optical scanning, and X‐ray fluorescence analysis. For internal structure the ram was examined by X‐radiography and 3‐D X‐ray tomography. Metallurgical composition was studied by micro‐drilling and subjecting the samples to scanning electron microscope X‐ray micro‐analysis, micro X‐ray fluorescence and X‐ray backscatter. The lead isotope composition was analysed. The alloy has average percentage composition Cu = 86.9, Sn = 6.3, Pb = 6.6, and Zn = < 0.10. The Belgammel Ram is probably a Hellenistic‐Roman proembolion from a small military vessel or tesseraria. The archived data are at the Faculty of Engineering and Environment, Engineering Sciences, Material Data Centre, University of Southampton ( muvis@soton.ac.uk ).     

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).     

Identification of the Residue in the Bolgar Medieval Sphero‐Conical Vessel by Gas Chromatography – Mass Spectrometry

The Golden Horde sphero‐conical vessel retrieved from the ruins of the medieval city of Bolgar (Russia, Republic of Tatarstan) during archaeological excavations, which contained residue in the form of encrustation on the bottom and the wall, was analysed in the NRC ‘Kurchatov Institute’ by X‐ray phase analysis and high‐performance liquid and gas chromatography with MS detectors (HPLC–MS, GC–MS). The GC–MS method established that the residue from the sphero‐conical vessel was comprised primarily of abietic acid derivatives (around 46%) and retene, which is polycyclic aromatic hydrocarbon (around 27%); this means that turpentine exuded from the stems of certain species of coniferous trees, called resin and subsequently heat‐treated, was poured into the vessel. Researchers have been trying to decipher the function of these mysterious vessels for 200 years, and this is the first time that resin stored in a sphero‐conical vessel has been documented. Potentially, this vessel was probably used as a personal ‘medical kit’.     

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).     

Investigation of Organic Materials From the ‘Royal’ Burials of Xiongnu (Noin‐Ula,Mongolia) by Srxrf and XAFS Methods

The burials of famous Xiongnu people are a unique source of information about Xiongnu culture, due to the variety of organic findings. SRXRF analysis of hair, clay, bones, teeth and woollen cloth was carried out. An anomalously high copper content was observed in all hair samples, whereas the levels of copper in bone and clay were low. To define the hair morphology and the elemental distribution in the hair cross‐section, high‐resolution X‐ray computed tomography (HRXCT) and energy‐dispersive spectroscopy (EDS) with scanning electron microscopy (SEM) were used. The X‐ray absorption fine‐structure method (XAFS) was applied to determine the local copper environment. The majority of the copper species in the hair and enamel samples are present as Cu²⁺ cations in a distorted octahedral (4 + 2) coordination, surrounded by light ligands (oxygen/nitrogen). A similar distorted octahedral coordination is typical for both inorganic mixed oxide/hydroxide Cu nanosystems and metal–organic Cu complexes (with oxygen/nitrogen).     

AN INVESTIGATION INTO THE RELATIONSHIP BETWEEN THE RAW MATERIALS USED IN THE PRODUCTION OF CHINESE PORCELAIN AND STONEWARE BODIES AND THE RESULTING MICROSTRUCTURES*

The microstructures of porcelain and stoneware bodies from north and south China, spanning the period from the Tang to the Ming dynasty (7th–17th centuries ad ), were examined in polished sections in a scanning electron microscope (SEM) after etching the sections with hydrofluoric acid (HF). Mullite, present as fine, mainly elongated crystals, is the dominant crystalline phase observed. The bulk chemical compositions of the bodies are determined by energy‐dispersive spectrometry in the SEM, and the relative amounts of mullite and quartz present in the different ceramics are estimated from X‐ray diffraction measurements. Mullite formed from areas of kaolinitic clay, mica particles and feldspar particles is distinguished through a combination of the arrangement of the mullite crystals, and the associated SiO₂/Al₂O₃ wt% concentration ratios. It is shown that very different microstructures are observed in ceramic bodies produced using kaolinitic clay from north China (Ding porcelain and Jun stoneware), porcelain stone from south China (qingbai and underglaze blue porcelain and Longquan stoneware), and stoneware clays from south China (Yue and Guan stonewares). Therefore, SEM examination of HF‐etched, polished sections of the bodies of high‐refractory ceramics has considerable potential for investigating the raw materials used in their production.     

Studying the process of enamel powder preparation for émail champlevé by colour measurements and μ‐X‐ray mappings

Colour measurements and non‐destructive μ‐X‐ray mappings have been used for the first time in a comprehensive study of medieval émail champlevé works from different production areas in France and Germany. This approach has given a new insight into the enamel powder preparation process of the glass material used for enamelling. Colour measurements demonstrated that all production centres used glass of very similar hues, but with large differences in colour saturation. The μ‐X‐ray mapping results of blue enamels are described by a semi‐qualitative approach. Significant variations in oxide contents of lead, cobalt, manganese and antimony oxides were found. The variations suggest that more than one glass material was used to prepare the powder for enamelling. The variations in antimony and cobalt show that glass had different degrees of opacity and colour depth. The manganese and lead contents, which do not correlate with the cobalt or antimony contents, indicate that probably glass of different base compositions was used to prepare the enamel powder for one champlevé field.     

First large‐scale provenance study of pigments reveals new complex behavioural patterns during the Upper Palaeolithic of south‐western Germany

The use of red iron‐based earth pigments, or ochre, is a key component of early symbolic behaviours for anatomically modern humans and possibly Neanderthals. We present the first ochre provenance study in Central Europe showing long‐term selection strategies by inhabitants of cave sites in south‐western Germany during the Upper Palaeolithic (43–14.5 ka). Ochre artefacts from Hohle Fels, Geißenklösterle and Vogelherd, and local and extra‐local sources, were investigated using neutron activation analysis (NAA), X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that local ochre sources were continuously and systematically accessed for c.29 500 years, with periodic events of long‐distance (about > 300 km) ochre acquisition during the Aurignacian (c.35–43 ka), suggesting higher mobility than previously suspected. The results reveal previously unknown long‐term, complex spatio‐temporal behavioural patterns during the earliest presence of Homo sapiens in Europe.     

NORTH APULIAN COARSE WARES AND FINE PAINTED WARES: A REAPPRAISAL ACCORDING TO NEW DATA FROM HERDONIA AND CANUSIUM

Late Antique coarse cooking wares and painted fine wares found at Herdonia (second half of the fourth century to mid‐fifth century ad ) and Canusium (late sixth century to early seventh century ad ) have been chemically and mineralogically characterized. A total of 74 samples (40 of coarse ware and 34 of fine painted ware) was investigated through optical microscopy, scanning electron microscopy, X‐ray powder diffraction, inductively coupled plasma optical emission spectrometry, inductively coupled plasma mass spectrometry, neutron activation analysis and X‐ray fluorescence. A new statistical method, namely the classification tree methodology, was used for the treatment of geochemical data. The characterization of the Herdonia and Canusium assemblages was combined with a review of earlier results obtained for San Giusto and Posta Crusta, in order to get an insight on Late Antique ceramic trades in northern Apulia. It appears possible to reconstruct a production pattern organized at multiple production sites, both rural and urban, that exploited similar raw material deposits, specialized in certain productions, and commercialized products at different geographical scales. Imports from outside northern Apulia may be identified for coarse wares. A likely area of production is difficult to establish; however, the northern Adriatic coast and the area of Greece may be suggested.     

The dark colour of the Ploutonion at Hierapolis of Phrygiae (Turkey)

The dark colour of some excavated architectural elements of the Ploutonion, in the archaeological site of Hierapolis of Phrygiae (Turkey), was investigated. The Ploutonion, visited by numerous ancient writers, such as Cicero and Strabo, was a sanctuary dedicated to Pluto and Kore, constructed during the early Imperial period above the entrance to a natural cave, from which thermal waters and poisonous gases emerge. It was used for sacred rituals: sacrifices, incubation and healing. A multi‐analytical approach (X‐ray diffraction, X‐ray fluorescence, optical and electronic microscopy, and chemical analyses of the thermal spring water) was used in order to define the composition and origin of darkening phenomena of some architectural elements of the Ploutonion.     

MICROSTRUCTURAL CHARACTERIZATION OF EARLY WESTERN GREEK INCUSE COINS*

In this research, we studied the compositional, crystallographic and microstructural properties of a series of incuse silver didrachmae stemming from the Achaean colonies of Metapontum and Caulonia. In this paper, we address the following points: (i) the metal sources, (ii) the fabrication process and (iii) degradation phenomena, such as incrustation and embrittlement. In this investigation, we employed energy‐dispersive X‐ray fluorescence spectroscopy, X‐ray diffractometry, and scanning electron and optical microscopies. The patina is mainly composed of chlorargirite. The coins consist of a silver‐rich alloy containing ～ 1% of Au and Cu. Metallographic and local compositional analyses revealed a complex scenario of inclusions. In one instance, unalloyed copper grains, two‐phase copper/bismuth globuli and high‐bismuth filaments were observed. In other cases, globular Cu ₂ S (chalcocite) inclusions were noticed. The presence of SiO ₂ and iron oxide inclusions is ubiquitous in these samples. Distorted twin lines and strain lines can be detected, denoting work‐hardening of recrystallized flans. Grain polygonalization can occasionally be noticed, hinting at secondary recrystallization processes. The irregularly shaped iron oxide particles often act as crack initiation sites. Fracture facets are generally intergranular. On some areas, intergranular decohesion is also observed. Open cracks sometimes contain AgCl. The strain lines that can be noticed on the fracture surfaces indicate work‐hardening and residual microstructural deformation. Information regarding inclusions and the presence of significant amounts of gold can be tentatively used to address provenancing and fabrication issues.     

MULTIANALYTICAL STUDY OF PALAEOLITHIC REINDEER ANTLER. DISCOVERY OF ANTLER TRACES IN LASCAUX PIGMENTS BY TEM*

Palaeolithic and modern reindeer antler were analysed using complementary techniques to evaluate the conservation state of bone material. X‐ray diffraction, FT‐IR spectroscopy, scanning electron microscopy (SEM–EDX) and transmission electron microscopy (TEM–EDX) as well as proton induced X‐ray and γ‐ray emission (PIXE–PIGE) at the particle accelerator AGLAE, C2RMF were applied. This study enabled us to define the chemical and structural features of ancient antler at the micro‐ and nanometre scale and compare them to those of other bone materials such as bone and ivory. Antler is richer in its organic fraction compared to bone and ivory. Its mineral fraction, carbonated hydroxylapatite, shows very specific crystal shapes at the nanometre scale. This specific property allowed us to recognize antler traces in pigment samples originating from rock art paintings in the Lascaux cave, Dordogne, southwestern France, Magdalenian period. Therefore, TEM–EDX is the technique of choice for characterizing antler traces in complex mixtures. In the paint material of Lascaux, antler seems most likely to be a pollutant introduced either by stirring the pigments in water with a piece of antler or by carving antler artefacts next to the preparation of paint material. However, it could eventually be used as a marker of paintings that were created contemporaneously.     

Pottery technology in the Tang dynasty (ninth century ad): archaeometric analyses of a Gongyi sherd found at Siraf,Iran

In 1969–70, a single Tang dynasty blue‐spotted Gongyi sherd was found at Siraf, Iran, the main trading port on the Persian Gulf in the early Islamic period. This is the only known example of Chinese blue‐and‐white ware, whether low‐ or high‐fired, found in the Middle East from such an early date. The sherd provides direct archaeological evidence for the Indian Ocean trade between China and the Middle East in the ninth century ad . The body paste, clear glaze and blue glaze or pigment were analysed by thin‐section petrography, scanning electron microscopy with energy‐dispersive X‐ray spectrometry (SEM‐EDX) and X‐ray fluorescence (XRF). The technological analysis reveals the different steps of the chaîne opératoire: clay mixing, slip and glaze application, and decoration with the cobalt blue glaze before high‐temperature firing. These steps are characteristic of Tang stoneware production at Gongyi in Henan province, China. The use of cobalt blue pigment as part of a simple spotted decoration scheme on the Gongyi sherd, and its find context within the Middle East, provides evidence for the complex interplay and influence occurring between Chinese and Middle East ceramic industries at this time. Closely comparable examples of contemporary low‐fired earthenware ceramics with cobalt blue decoration on a white tin glaze manufactured within the Middle East also occur within the same assemblage from Siraf.     

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.     

Coloured Prints of the 16th Century: Non‐Destructive Analyses on Coloured Engravings from Albrecht DÜrer and Contemporary Artists

Qualitative investigations of pigments and dyes using micro X‐ray fluorescence spectrometry (micro‐XRF) and visible spectrophotometry (VIS) are suitable non‐destructive methods for the characterization of different colorants in art objects. In this study, several rare coloured engravings from the work of Albrecht Dürer—and, in addition, from the work of Cornelis Cort, Servatius Raeven and Johannes Sadeler—were investigated. The analyses result in specific palettes of colours that were used by different artists or in different workshops for the coloration of engraved images. Starting from these different palettes, it is possible to distinguish coeval colorations that were added in the 16th century from those that were carried out at a later date (e.g., the 19th century).