The chert from the Castelltallat Formation (south-central Pyrenees): archaeometric characterisation and archaeological implications

Chert from the limestones and marly limestones of Castelltallat Formation (Ebro Basin) was widely used throughout prehistoric times in north-eastern Iberia to produce stone tools due to its properties and accessibility. A rough estimate indicates that this rock—either as raw material or as lithic products—was distributed mainly to the north of the outcrops, over an area of 6000–8000 km². However, other rocks in the area have similar characteristics which can lead to confusion in the interpretation of its prehistoric use and distribution. In order to establish useful archaeometric criteria for differentiating this chert from other similar, the Castelltallat chert is characterised in petrographic, mineralogical and geochemical terms. The chert nodules are found to be homogenous at the macroscopic and microscopic level, with a significant presence of bioclasts, thus indicating they might be formed in a freshwater lake environment by the early diagenetic replacement of carbonates in shallow waters. The mineralogical composition is homogeneously uniform and of a flint type, characterised by an almost exclusive predominance of quartz, without any opaline phases, and a variable proportion of moganite. The iron oxide content is very low, whereas its chemical composition is unusually high in uranium which correlates positively with carbonate content and negatively with silica. Archaeometrical parameters are provided to reach a proper identification of tools knapped with this chert. This way, chert from Castelltallat Formation turns out to be a valuable lithological marker to evaluate the range of mobility of the human groups who lived in the north-eastern Iberia and their contacts with neighbouring areas.     

PAUL‐LOUIS CYFFLÉ'S (1724–1806) TERRE DE LORRAINE: A TECHNOLOGICAL STUDY

Fragments of four Terre de Lorraine biscuit figurines were subjected to porosity analysis, X‐ray fluorescence analysis, X‐ray diffraction analysis, backscattered‐electron image analysis—coupled with energy dispersive spectrometry—and electron backscatter diffraction analysis to determine the porosity, bulk, major, minor and trace element compositions, and the composition and the proportion of their constituent phases. Cyfflé's Terre de Lorraine wares embrace two distinct types of paste, a calcareous and an aluminous–siliceous one. Both are porous (9–25% water adsorption). The former consists of a mixture of different proportions of ground quartz or calcined flint, ground Pb‐bearing glass and calcium carbonate with a refractory clay. The firing temperature was between 950 and 1050°C. For the latter, Cyfflé mixed ground pure amorphous SiO₂, ground quartz or calcined flint, ground porcelain, ground Na–Ca‐glass and coarse‐grained kaolinite with a fine‐grained kaolinitic clay. The figurines were fired below 1000°C. The result was a porous, hard paste porcelain‐like material. Cyfflé's recipes for both pastes can be calculated from the chemical and the modal analyses.     

X‐ray Diffraction and SEM Investigation of Wall Paintings Found in the Roman Temple Complex at Horvat Omrit,Israel

In the present study, the fragments of wall painting found in the Roman Temple Complex at Horvat Omrit were analysed for the first time using the non‐destructive techniques of X‐ray diffraction (XRD) and scanning electron microscopy (ESEM) equipped with energy‐dispersive X‐ray spectroscopy (EDS). The application of these methods enabled unambiguous identifications of the pigments and plaster components of the samples. Quantitative information on mineral composition, crystallite size and elemental composition of each studied paint layer and plaster was collected. Based on the results of the XRD and EDS analyses, the green pigment was identified as celadonite. It was revealed that the Egyptian blue pigment does not contain impurities of tin and lead, and this excludes the use of bronze scrap in its synthesis. Comparison of the mineral composition of the paint layers indicates that a wider palette of colours was obtained by mixing the available mineral pigments. The study of cross‐sections of painted specimens revealed the usage of slaked lime for plastering. The obtained results give a new insight into the wall painting technique employed by ancient artists at Horvat Omrit, in northern Israel.     

THE CHEMICAL COMPOSITION OF SOME ARCHAEOLOGICALLY SIGNIFICANT FLINT FROM DENMARK AND SWEDEN

Flint was one of the most widely employed raw materials for artefact manufacture in Denmark and Sweden during the Stone Age, and it continued to be used during subsequent periods. Prehistoric flint mining and lithic manufacturing studies in these countries have attracted considerable attention, but there have been no recent attempts to chemically characterize the geological source materials. This paper builds on a pilot study ( Hughes et al. 2010 ) and uses energy‐dispersive X‐ray fluorescence (EDXRF) analysis to determine quantitative composition estimates for nine major, minor and certain trace elements in seven archaeologically significant flint sources in Denmark and Sweden, along with new data on a number of other sources of prehistoric significance. These data provide a geochemical foundation for ongoing research devoted to determining contrasts and continuities in the time and space utilization of flint sources in Scandinavian prehistory.     

First Insights into the Technique Used for Heat Treatment of Chert at the Solutrean Site of Laugerie‐Haute,France

The earliest evidence of flint and chert heat treatment was found in the ~21.5–17 ka old European Solutrean culture. The appearance of pyrotechnology as part of the production of stone tools has important implications for our understanding of Upper Palaeolithic technological evolution and the specific adaptations during the last glacial maximum in Europe. However, the techniques and procedures used to heat‐treat rocks during the Solutrean remain poorly understood. No direct archaeological evidence has so far been found and the most promising approach is to understand these techniques by determining the parameters with which flint and chert were heated at that time. In this study, we investigate the heating temperature of 44 heat‐treated laurel‐leaf points from Laugerie‐Haute, using a non‐destructive technique based on infrared spectroscopy. Our results document that most of the artefacts were heated to a narrow interval of temperatures between 250 °C and 300 °C. This indicates a standardized technique that allowed to created similar conditions during successive heating cycles. The implications of these results for our understanding of the technical complexity during the Solutrean must be discussed in the light of different heating techniques used at different places and periods.     

UNDER THE HAMMER: RESIDUES RESULTING FROM PRODUCTION AND MICROWEAR ON EXPERIMENTAL STONE TOOLS*

This paper presents the results of an experimental programme investigating the effects of production processes on stone tools and their interference with use‐related features. In the first part of the experimental programme, a series of flint flakes was retouched with different kinds of hammers in order to assess the extent and nature of percussion residues. After careful environmental scanning electron microscope (ESEM) observation and energy‐dispersive X‐ray (EDX) analysis, the retouched flakes were thoroughly cleaned and the underlying flint deformation was recorded. The second part of the experimental programme involved selecting several uncleaned retouched pieces for use in short woodworking, hide‐processing and butchery experiments. These pieces were observed and analysed before, during and after use. Some of the percussion features proved to be surprisingly resistant to use, and in some cases turned out to be strikingly similar in appearance to use‐generated features.     

Carnelian,agate, and other types of chalcedony: the prehistory of Jebel al‐Ma'taradh and its semi‐precious stones,Emirate of Ra's al‐Khaimah

The Jebel al‐Ma'taradh and its surroundings contain exceptional deposits of lithic raw materials, including flint and chert, but especially chalcedony, agate, carnelian, and chrysoprase. These deposits were intensively exploited during the Neolithic, and some of the artefacts produced entered the trade network that included settlements on the coast and inland, sometimes as far as 300 km. During earlier periods, probably as early as the Pleistocene, only flint was used. Between the sixth and the fourth millennia, carnelian and agate were exploited to make beads, which are found in the necropolises and settlements of the UAE.     

COLOURED OPAQUE GLASS BEADS OF THE MEROVINGIANS*

Monochrome coloured opaque glass beads of the Merovingians have been examined by different analytical methods. A large number of mostly unprepared beads have been measured by X‐ray fluorescence analysis. X‐ray diffraction was used for the identification of the crystalline colouring and opacifying pigments, and electron probe micro‐analysis as well as scanning electron microscopy were applied to study the composition and the microstructure of a white, brown, green, orange and yellow glass bead. After subtracting the content of colouring oxides of the glass beads and normalizing the residual values to 100% an identical soda‐lime‐glass matrix was obtained. The origin of the colouring metal oxides is discussed.     

An Exceptional Case of Healed Vertebral Wound with Trapped Bronze Arrowhead: Analysis of a 7th–6th c. bc Individual from Central Kazakhstan

Projectile injury caused by an arrow shot is a common skeletal marker of interpersonal violence in archaeological populations. The injuries of the spine were usually fatal. Only few reports on healing of the vertebra pierced by flint arrowpoint can be found in bioarchaeological literature. This paper presents an exceptional case of a healed trapped bronze arrowhead wound in the spine of a 7th–6th c. bc elite nomad from Central Kazakhstan. Computed radiography and tomography as well non‐destructive X‐ray fluorescence spectrometry provide detailed information about the context and mechanism of the injury. Copyright © 2015 John Wiley & Sons, Ltd.     

The Use of Small‐Angle X‐Ray Diffraction Studies for the Analysis of Structural Features in Archaeological Samples

X‐ray diffraction or scattering analysis provides a powerful non‐destructive technique capable of providing important information about the state of archaeological samples in the nanometer length scale. Small‐angle diffraction facilities are usually found at synchrotron sources, although the potential of a laboratory source is also described. Specific examples of analysis using X‐ray diffraction of historic parchment, archaeological bone, a Central Mexico style pictograph and microdiffraction of calcified tissues are used to show the scope and versatility of the technique. Diffraction data is capable of giving fundamental structural information as well as quantifying the remodelling of structures influenced by environmental factors.     

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).     

Analysis of Heavy Metals in Smoke Deposits in the Limewash of the Royal Artillery Factory of Seville (17th Century): Contributions to the Location of the Furnaces

The Royal Artillery Factory of Seville in Spain originated from pre‐existing private bronze foundries dating from the 16th century. The paper analyses the stratigraphy of wall cladding in the areas traditionally known as the ‘Old Foundry’ and the ‘New Foundry’, through its characterization by optical microscopy, scanning electron microscopy with energy‐dispersive X‐ray spectrometry (SEM‐EDX), micro‐X‐ray fluorescence (μ‐XRF) and micro‐X‐ray diffraction (μ‐XRD), in order to analyse the metal deposits that have accumulated since the 17th century. The data obtained allowed the verification of the available historiographical information and the location of the original bronze smelting furnaces. The analysis of patinas deposited on the overlapping layers of lime also confirmed that neither the raw materials nor the composition of the alloys used presented any substantial changes.     

Black Gloss Pottery: Production Sites and Technology in Northern Etruria,Part II: Gloss Technology

The present study aims to understand the reasons for the visual differences of black gloss pottery found in northern Etruria. The results obtained by conventional (scanning electron microscope, electron microprobe) and synchrotron (X‐ray diffraction, X‐ray absorption spectroscopy) techniques indicate that the thickness, porosity or chemical composition of the different types of gloss cannot be used as the principal distinguishing factor. The size of quartz or feldspar crystals may well be a critical factor responsible for the matt effect in some samples, while the range of mixtures of iron compounds indicated by XRD and XAS could be the reason for differences in colour and reflectivity. The Fe L‐edge XAS results in particular show that a correlation does exist between the oxidation state characteristics and the visual appearance. The Si, Fe and Al contents seem to further discriminate the different types of gloss that have differing visual appearances.     

Petrographic and geochemical characterization of chert artifacts from Middle,Upper, and Epi-Paleolithic assemblages in the Jebel Qalkha area,southern Jordan

This study conducted petrographic and geochemical analyses of chert artifacts from the Late Middle Paleolithic, the Initial Upper Paleolithic, the Early Upper Paleolithic, and the Epi-Paleolithic assemblages in the Jebel Qalkha area, southern Jordan, to examine their correlations with the visual attributes and diachronic variability. The results revealed two different aspects of the petrographic and geochemical signatures. The first aspect showed some correlations with the visual chert types that were characterized by the abundance/preservation of fossils, the enrichment of several elements (i.e., Ca, Sr, and Ba), and the quartz crystallite size. The second aspect of geochemical signatures, such as Fe, Mn, Ni, Cr, and Co, showed no correlation with the visual types but was correlated with the chrono-cultural groups. Given the chert occurrences and variability in and around the study area, the first aspect of the chert variability likely represents the variations of different chert outcrops as well as the internal variations within the same sources. Whether the second aspect represents chrono-cultural changes in the use of chert sources needs to be clarified in future by our ongoing examination of geological chert samples in the study area.     

The Earliest High‐Fired Glazed Ceramic in China: Evidence from a Glazed Ceramic Sample from the Lajia Site,Qinghai Province

In the Majiayao cultural stratum of the Lajia site in Minhe County, Qinghai Province, much earthenware of rich variety and strong character has been found, among which the most special item is a suspected glazed white ceramic fragment. This study investigates this ceramic sherd and many other overfired objects. Energy‐dispersive X‐ray fluorescence spectroscopy, scanning electron microscopy – energy‐dispersive X‐ray spectroscopy, X‐ray diffraction and thermodilatometry were employed to analyse the composition, microstructure, phase composition and firing temperature of the white ceramic. In addition to large condensed glaze droplets, the white ceramic showed a thin and uneven glaze layer, which might represent the earliest results of the exploration of glaze‐making technology by Lajia inhabitants, and provide a new perspective on the study of the origin of Chinese proto‐porcelains.     

Materials Characteristics of Roman and Arabic Mortars and Stuccoes from the Patio De Banderas in the Real Alcazar of Seville (Spain)

This study discusses the materials and traditional knowledge used in the manufacture and application of lime mortars and stuccoes by Romans and Arabs in Seville (southern Iberian Peninsula). All of the samples studied contain calcite as a binder, combined with aggregates based on river sand from the filling materials of the Guadalquivir River's depression, located in the vicinity of the Real Alcazar Palace in Seville, Spain, where the artefacts were discovered. The Romans used high‐quality production technology, as evidenced by the careful selection of raw materials as well as by the adequate binder‐to‐aggregate ratio and the elevated homogeneity of the mortars and stuccoes. The suitable distribution of aggregates resulted in higher density values for Roman fragments than for Arabic ones. Results derived from Arabic samples suggest a decline in technology manufacture over time. This work provides useful information, particularly regarding the Roman and Arabic periods in the Iberian Peninsula. The analytical techniques employed in this study were X‐ray diffraction (XRD), X‐ray fluorescence (XRF)—using conventional and portable systems, scanning electron microscopy (SEM), petrographic microscopy, differential thermal analysis/thermogravimetry (DTA/TG), particle‐size analysis and mercury intrusion porosimetry.