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.     

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.     

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.     

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.     

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.     

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 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.     

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.     

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.     

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.     

THE PROVENANCE AND TECHNOLOGY OF NEAR EASTERN GLASS: OXYGEN ISOTOPES BY LASER FLUORINATION AS A COMPLEMENT TO STRONTIUM*

The ability to make rapid measurements on small samples using laser fluorination enhances the potential of oxygen isotopes in the investigation of early inorganic materials and technologies. δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values are presented for glass from two primary production sites, four secondary production sites and a consumer site in the Near East, dating from Late Antiquity to the medieval period. δ¹⁸O is in general slightly less effective than ⁸⁷Sr/⁸⁶Sr in discriminating between sources, as the spread of measured values from a single source is somewhat broader relative to the available range. However, while ⁸⁷Sr/⁸⁶Sr is derived predominantly from either the lime‐bearing fraction of the glass‐making sand or the plant ash used as a source of alkali, δ¹⁸O derives mainly from the silica. Thus the two measurements can provide complementary information. A comparison of δ¹⁸O for late Roman – Islamic glasses made on the coast of Syria–Palestine with those of previously analysed glasses from Roman Europe suggests that the European glasses are relatively enriched in ¹⁸O. This appears to contradict the view that most Roman glass was made using Levantine sand and possible interpretations are discussed.     

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.     

THE PROVENANCE OF OBSIDIAN ARTEFACTS FROM THE WĀDĪ ATH‐THAYYILAH 3 NEOLITHIC SITE (EASTERN YEMEN PLATEAU) BY LA–ICP–MS

The geological sources of obsidian in the Red Sea region provide the raw material used for the production of obsidian artefacts found in prehistoric sites on both sides of the Red Sea, as far afield as Egypt, the Persian Gulf and Mesopotamia. This paper presents the chemical characterization of five obsidian geological samples and 20 prehistoric artefacts from a systematically excavated Neolithic settlement in highland Yemen. The major element concentrations were determined by SEM–EDS analysis and the trace element concentrations were analysed by the LA–ICP–MS method, an almost non‐destructive technique capable of chemically characterizing the volcanic glass. A comparison of archaeological and geological determinations allows the provenance of the obsidian used for the Neolithic artefacts to be traced to definite sources in the volcanic district of the central Yemen Plateau.     

TECHNOLOGICAL STUDY OF PTOLEMAIC – EARLY ROMAN FAIENCE FROM MEMPHIS,EGYPT*

Fourteen fragments of faience vessels from the Ptolemaic/Roman period found at the Egyptian site of Memphis, near Cairo, were analysed by SEM. The fragments included high‐relief polychrome vessels, which are first produced in numbers in this period. Analysis allowed the composition and microstructure of the vessels to be assessed and conclusions drawn as to the raw materials of manufacture. Combining this information with archaeological evidence from excavation of the kilns and associated finds, it was possible to reconstruct the production technology of the vessels.     

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.