MINERALOGICAL INVESTIGATIONS OF MEDIEVAL BRICK SAMPLES FROM BÉKÉS COUNTY (SE HUNGARY)

Brick samples from nine archaeological sites representing seven contemporary medieval settlements in Békés County (SE Hungary) were analysed by quantitative X‐ray powder diffraction, optical microscopic, scanning electron microscopic and coupled thermal analytical – evolved gas analytical methods. The aims of this study were to give a mineralogical–petrographical characterization of the brick samples, to gain possible information on the raw clay and the admixed materials, and to determine the firing techniques applied in medieval southeastern Hungary. The mineralogical composition of the samples suggests that the locally extracted clay was mixed with fluvial sand and wheat (Triticum monococcum L.) chaff. The moulded bricks were fired in clamps. The different degrees of calcite consumption suggest that the firing temperature ranged from ～750°C to ～950°C. Moreover, the well‐developed reaction coronas on calcite grains indicate long firing times, lasting perhaps several days.     

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.     

DECORATED ARCHAIC POTTERY FROM THE HERACLES SANCTUARY AT THEBES: A MATERIALS,TECHNOLOGY AND PROVENANCE STUDY*

Forty‐seven decorated samples of Archaic pottery excavated at a Heracles sanctuary (Thebes, Boeotia) were studied through a combined surface and body approach, using non‐destructive techniques. Most of the samples were archaeologically classified as Theban/Boeotian, others as Corinthian and a few as possibly Euboean. The techniques employed were optical microscopy and SEM–EDAX (micromorphology and compositional analysis of the surfaces) and XRF for the analysis of the ceramic body. The results provided information on the technological level of the collected pottery as well as on the relation of the chemistry and micromorphology of the pigments, aimed at assisting provenance studies.     

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.     

CHARACTERIZATION AND PROVENANCE OF LIME PLASTERS FROM THE TEMPLO MAYOR OF TENOCHTITLAN (MEXICO CITY)

In this work, we present the results of the analyses of 20 lime plaster samples taken from the Templo Mayor (Great Temple), the main pyramid of Tenochtitlan (Mexico), the ancient capital of the Mexicas. The samples were analysed to recover information on the mixtures used in the fabrication of the plasters and for the provenance of the raw materials (in particular, limestone) used to make the plasters. The characterization of the samples was done by OM, SEM/EDS, XRF and LA–ICP–MS analyses, while the identification of the provenance of raw materials was done by studying the lumps present in the samples with LA–ICP–MS. The objective of the study was to establish if there was a relationship between changes in the construction techniques employed in the pyramid over time and if there were changes in the provenance of the raw materials. Six different construction phases of this pyramid are analysed, showing the similarities and differences among them, mainly based on differences in the sieving of the aggregates and in the raw materials employed. The provenance studies of the limestone used to make the plasters demonstrated that all the limestone comes from the Tula region.     

STAINING OF ARCHAEOLOGICAL GLASS FROM MANGANESE‐RICH ENVIRONMENTS*

It has been suggested that both internal and external sources of manganese may produce the black or brown staining that often occurs in buried archaeological glass. Modern potash glass of a manganese‐free medieval composition was scratched, etched and immersed in an aqueous solution containing dissolved manganese. After several weeks, immersion samples were sectioned and examined by SEM–EDX. Manganese was shown to be present in fissures and cracks within in the glass, where alkali had been depleted. Manganese from an external source is capable of blackening buried medieval potash glass.     

RELATIONSHIP BETWEEN THE COLORATION AND THE FIRING TECHNOLOGY USED TO PRODUCE SUSA GLAZED CERAMICS OF THE END OF THE NEOLITHIC PERIOD*

Ancient decorated potteries from Susa (Mesopotamia) dating from 4200 to 3700 bc , were studied in order to determine the origin and the nature of the raw materials used, and to identify the technological processes applied to make the ceramic bodies and their decorations. Bulk compositions were determined by particle induced X‐ray emission (PIXE), while the microstructure and the mineralogical phases were studied using scanning electron microscopy (SEM), energy dispersive X‐ray analyses (EDX) and X‐ray powder diffraction (XRD). The results showed that the raw materials used to elaborate these potteries were similar for all the ceramic bodies (carbonates and iron and magnesium‐rich clays containing sand), and for all the decorations (iron oxides, silica, potassic and alumina sources). The variations of coloration of the ceramics and of their decorations were due to different firing temperatures. The ranges of firing temperatures used by potters were evaluated on the basis of mineral stability domains.     

ANALYSIS OF NASRID POLYCHROME CARPENTRY AT THE HALL OF THE MEXUAR PALACE,ALHAMBRA COMPLEX (GRANADA,SPAIN), COMBINING MICROSCOPIC,CHROMATOGRAPHIC AND SPECTROSCOPIC METHODS*†

The pigments, binders and execution techniques used by the Nasrids (1238–1492) to polychrome carpentry in the Hall of the Mexuar Palace at the Alhambra (Granada, Spain) were studied using optical microscopy, scanning electron microscopy with EDX analysis, selective staining techniques and gas chromatography – mass spectrometry. This pioneering investigation presents the first results of a research project devoted to filling gaps in the knowledge of Nasrid art, traditionally approached by stylistic studies. Moreover, it is essential for the polychromy conservation of the studied artworks, and will help to clarify historical and painting uncertainties in the Alhambra monument. The palette consists of a limited range of colours: white (lead‐base pigment), red (cinnabar and red lead), blue (lapis lazuli), black (carbon‐based) and false gold (golden tin). Tempera grassa was the painting technique identified. Two types of grounds were used: (i) gypsum in calligraphy decoration for the false gold technique, and (ii) synthetic minium in geometric drawings in carpentry. Organic insulating layers of linseed oil were used between paint strata. Artists applied synthetic minium to protect the wood (Juglans regia and conifer) against attack by xylophages. To lighten the surface darkened by this ground layer, powdered tin was added to achieve a metallic lustre.     

THE PROVENANCE AND PRODUCTION TECHNOLOGY OF BRONZE AGE AND IRON AGE POTTERY FROM TELL MISHRIFEH/QATNA (SYRIA)*

This work deals with the archaeometric study of the Bronze Age and Iron Age pottery from Tell Mishrifeh/Qatna (central‐western Syria), where the complete cycle of ceramic production is well documented. Petrographic, chemical and diffractometric analyses were carried out on both potsherds and a clayey material found in a separation basin within the area of the workshops. Petrographic groups were defined and maximum firing temperatures and redox firing conditions were estimated, providing constraints on identifying the production technology and its evolution with time. The studied potsherds turned out to be locally produced, with only a few cases of possible similarities with those described for other localities along the Orontes Valley, and in a couple of cases with evidence of pottery exchange.     

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.     

SHAFT‐HOLE AXES FROM CAPUT ADRIAE: MINERALOGICAL AND CHEMICAL CONSTRAINTS ABOUT THE PROVENANCE OF SERPENTINITIC ARTEFACTS*

The change of raw materials used to produce stone axes during the Neolithic to Copper Age transition in northeastern Italy, central and western Slovenia and northwestern Croatia (Caput Adriae) has been recently linked to the development of early European metallurgy. Serpentinite shaft‐hole axes occur commonly in the archaeological context of this region and their rounded irregular shape suggests that the raw material was mainly sourced from secondary deposits. The aim of the present study is to characterize with multiple analytical methods, including synchrotron radiation, the axes and locate the primary outcrop(s) of raw materials and related secondary exploitation areas. All the analysed artefacts are manufactured from peridotites and probably pyroxenites completely metamorphosed in greenschist facies and characterized by antigorite, diopside and magnetite, sometimes rimmed by penninite. Mineralogical and petrographic data exclude most Eastern Alps outcrops as possible raw material sources, thus limiting the research to the Hohe Tauern. Chemical data reveal a close homogeneity for the peridotite‐derived axes and therefore demonstrate a selection of the most suitable raw material for axe production. Provenance from Hohe Tauern and related secondary deposits of the Drava River hydrographical system agrees with previous studies, as this region is rich in copper ore deposits, which have been exploited since prehistory.     

PROVENANCE DETERMINATION OF LAVA FLAGSTONES FROM THE ROMAN ‘VIA CONSOLARE FLAMINIA’PAVEMENT (CENTRAL ITALY) USING PETROLOGICAL INVESTIGATIONS*

Trachyte lava flagstones from the northernmost stretch of the Roman ‘Via Consolare Flaminia’pavement and trachyte lavas from the most exploited quarries in Roman times were compared from a petrological point of view. ‘Via Consolare Flaminia’was the most important route used by the Romans to reach northern Italy and all the northern provinces of the Empire. A provenance for the flagstones as coming from the trachyte quarries of the Euganean Hills (Veneto region, northern Italy) is suggested by the similarity of both the fundamental mineral assemblage and the major trace element geochemistry. The location of the quarries of the Euganean Hills next to the harbours of the northern Adriatic Sea strongly supports the hypothesis that the Romans carried the flagstones by ship towards the coasts of the central Adriatic Sea.     

A STUDY OF GLASS BEADS FROM THE HALLSTATT C–D FROM SOUTHWESTERN POLAND: IMPLICATIONS FOR GLASS TECHNOLOGY AND PROVENANCE*

Eighty‐one samples taken from 68 glass beads found in southwestern Poland on sites of the Lusatian culture from the Hallstatt C and Hallstatt D subphases were analysed by EPMA. A subsample of 18 of these were additionally subjected to analysis by means of LA–ICP–MS in order to validate the results obtained by EPMA. Some glass was made using mineral soda and some using plant ash rich in sodium. Both high‐magnesium soda–lime glass (HMG) and low‐magnesium soda–lime glass (LMG) were identified. A large number of samples are characterized by low MgO content and medium K₂O content (LMMK glass), combined with low concentrations of CaO and high Fe₂O₃ and Al₂O₃. All the LMMK glass contains numerous silica crystals and inclusions composed of a number of elements (most frequently Cu, Co, Sb, As, Ag, Ni and Fe). The LMMK glass was presumably made in Europe during the Hallstatt C.     

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.     

THE PROVENANCE OF IRON ARTEFACTS FROM MANCHING: A MULTI‐TECHNIQUE APPROACH*

Iron finds from the Celtic oppidum of Manching in southern Bavaria (Germany) are analysed in view of their possible provenance. The exceptional size and the location of Manching are usually attributed to the presence of abundant iron ores in its vicinity. After a review of previous approaches for source determination of iron artefacts, we introduce lead isotope analysis as a new approach. However, only by combining the trace element patterns of slag inclusions and iron metal with lead isotope ratios in the metal is it possible to distinguish various iron ore formations near Manching. As a result, it turns out that, indeed, the most obvious ones—namely, bog ores near the Danube—constituted the main resources for iron production at Manching. It was even possible to select one occurrence as the most likely ore source.     

MICROANALYTICAL METAL TECHNOLOGY STUDY OF ANCIENT NEAR EASTERN BRONZES FROM TELL BEYDAR*

Forty‐six bronze objects have been investigated to assess their composition and microstructure, using SEM–EDX and optical microscopy. The bronzes originate from Tell Beydar, a site in the northeastern part of Syria that was mainly occupied during the third millennium bc . The compositional results of the metals show a clear chronological sequence in the use of the alloying elements arsenic and tin. In addition, the microstructure indicates advancement in the metalworking techniques that were used.     

METHODOLOGICAL DEVELOPMENTS IN THE LUMINESCENCE DATING OF BRICK FROM ENGLISH LATE‐MEDIEVAL AND POST‐MEDIEVAL BUILDINGS*

Fired clay brick samples, obtained from a group of seven high‐status late‐medieval and post‐medieval buildings in England ranging in age from c. ad 1390 to 1740, were dated by the luminescence method using an optically stimulated luminescence (OSL) technique. The results obtained indicate that, when applied to quartz extracted from brick, the technique is capable of producing dates that are in consistently good agreement with independent dating evidence for the buildings. For six samples taken from a group of four dating ‘control’ buildings the mean difference between the central values of luminescence and assigned ages was 5 ± 10 years (SD, n = 6). The methodology used is appropriate for application to other standing buildings in other temporal and geographic regions, and may be used with confidence where conventional dating methods are less certain. The study also examines the luminescence characteristics of quartz and the characteristics of the lithogenic radionuclides in brick samples and identifies various aspects related to the assessment of experimental uncertainty in testing the reliability of the method.     

TECHNOLOGY AND PROVENANCE OF A COLLECTION OF ISLAMIC COPPER‐BASED OBJECTS AS FOUND BY CHEMICAL AND LEAD ISOTOPE ANALYSIS*

Chemical and lead isotope analyses were utilized to determine the composition, technology and origin of a collection of Islamic copper‐based objects found in Jordan. The atomic absorption spectrometry results show that the objects were made of different types of copper‐base alloys that contain various amounts of zinc, tin and lead. The use of brass, highly leaded brass and quaternary alloys of Cu‐Zn‐Sn‐Pb in the manufacture of everyday, household objects strongly points to Islamic traditions. The lead isotope compositions of the objects match very well that of the copper ore mined from the Dolomite‐Limestone‐Shale unit of the Arabah copper mines.     

NON‐DESTRUCTIVE ANALYTIC METHOD USING XRF FOR DETERMINATION OF PROVENANCE OF ARCHAEOLOGICAL OBSIDIANS FROM THE MEDITERRANEAN AREA: A COMPARISON WITH TRADITIONAL XRF METHODS*

A non‐destructive analytical method using wavelength‐dispersive X‐ray fluorescence (WDXRF) that allows the establishment of the provenance of archaeological obsidians was developed and a comparison with the classical XRF method on powders is discussed. Representative obsidian samples of all the geological outcrops of archaeological interest of the Mediterranean area (Lipari, Pantelleria, Sardinia, Palmarola and the Greek islands of Melos and Gyali), were analysed with the normal procedures used in rock analysis by XRF (crushing, powdering and pelletizing). The non‐destructive XRF analysis was instead conducted on splinters taken from the original geological pieces, with the shape deliberately worked to be similar to the refuse usually found at archaeological sites. Since the analysis was conducted on the raw geological fragment, intensity ratios of the suitably selected chemical elements were used, instead of their absolute concentrations, to avoid surface effects due to the irregular shape. The comparison between concentration ratios (obtained by traditional XRF methods) and the intensity ratios of the selected trace elements (obtained from the non‐destructive methodology) show that the different domains of the chemical composition, corresponding to the geological obsidians of the source areas, are perfectly equivalent. In the same way, together with the geological splinters, complete archaeological obsidians, from Neolithic sites, may be analysed and their provenance may be determined. The proposed non‐destructive method uses the XRF method. Due to its sensitivity, low cost and high speed, it is surely an extremely valid instrument for the attribution of the provenance of the archaeological obsidian from Neolithic sites.     

THE CHARACTERIZATION OF PAINTS AND WATERPROOFING MATERIALS FROM THE SHIPWRECKS FOUND AT THE ARCHAEOLOGICAL SITE OF THE ETRUSCAN AND ROMAN HARBOUR OF PISA (ITALY)*

This work presents the results of a diagnostic survey on the shipwrecks from the archaeological site of the ancient harbour of San Rossore (Pisa, Italy). The original waterproofing, caulking and painting materials were characterized by Fourier transform infrared spectroscopy (FTIR), gas chromatography – mass spectrometry (GC–MS), energy‐dispersive X‐ray microanalysis (EDX) and X‐ray diffraction (XRD). The major constituents of the waterproofing and caulking materials detected on the planks were tricyclic abietanes showing a high degree of aromatization. These compounds are indicative of a pitch obtained from the wood of trees of the Pinaceae family. The analysis of the organic components of the paint samples revealed diterpenoid acids characteristic of Pinaceae resins together with linear long‐chain alcohols and fatty acids, highlighting the presence of beeswax. Noticeably, the characteristic odd carbon number alkanes that are normally present in beeswax were not detected. The EDX and XRD analyses showed that hematite, calcite, cerussite and kaolinite were employed as pigments to paint the ships’ hulls.