Mining Archaeology and Micro‐Raman Analysis Associated with ESEM‐EDX: Toward a Chrono‐Spatial Definition of Ore Consumption in a Pyrenean Medieval Workshop, 14th–16th Centuries

The rapid expansion of non‐ferrous metallurgy in the late Middle Ages (14th–15th centuries) enhanced ore demand, which was supported by mining intensification. Metallurgical workshops developed various supply strategies based on geological, political and economic constraints. This is particularly true for the Pyrenean multi‐metals workshop of Castel‐Minier (Ariège, France), where recent excavations unearthed an exceptional corpus of non‐ferrous ores. A specific analytical methodology combining micro‐Raman spectroscopy and environmental scanning electron microscopy with energy dispersive X‐ray (ESEM‐EDX) was set up to study these artefacts. This composite methodology permitted the fast characterization of both mineral and gangue as well as a discussion of their economic potential. Ores identified were compared with ancient mines in neighbouring mining districts in order to sketch a geography of the mineral resources available to medieval metallurgists. Moreover, a chrono‐stratigraphic study of ore distribution in Castel‐Minier revealed the supply strategies, technological choices as well as spatializing of copper and lead metallurgies.     

Micro‐CT Imaging and Analysis of Enamel Defects on the Early Late Pleistocene Xujiayao Juvenile

Dental pathologies and enamel defects in East Asian hominins have rarely been reported. Here, we systematically document and describe a suite of enamel defects in the Xujiayao juvenile maxilla, an East Asian hominin from the early Late Pleistocene that may represent an unknown hominin lineage. In addition, we determine the chronology of growth disruptions represented by matched linear enamel hypoplasias, evaluate the long‐held hypothesis that the large brownish pit on the I¹ is evidence of dental fluorosis and assess the utility of micro‐computed tomography (micro‐CT) techniques in analyzing enamel defects. With the use of binocular microscopy, scanning electron microscopy (SEM) and micro‐CT imaging techniques, the Xujiayao teeth were found to exhibit a high number of pit‐form defects seldom seen in the fossil record. By matching the timing of linear enamel hyperplasia across multiple teeth, a minimum of five developmental disruptions were identified, indicating that the Xujiayao juvenile experienced several growth disturbances during its short lifespan. Our SEM and micro‐CT analyses suggest that the large pit on the I¹ is an enamel hypoplasia due to its morphology and pre‐eruptive enamel thinning. It is not a post‐eruptive fluorotic pit, and there is no evidence of chalkiness or opacity associated with dental fluorosis. The micro‐CT technique made it possible to verify the presence of enamel hypoplasia and to more precisely quantify defect dimensions, especially in unerupted teeth and shallow hypoplasias that are difficult to detect by binocular microscopy or SEM. Copyright © 2015 John Wiley & Sons, Ltd.     

Physico‐Chemical Characterization of Pigments and Binders of Murals in a Church in Ethiopia

Here, we report the physico‐chemical characterization of wall paintings from the Petros and Paulos church in Ethiopia. This work represents the first technical study of paintings located in Ethiopia, rather than paintings in museum collections outside the country, using diverse analytical techniques. In situ examination with a portable X‐ray fluorescence spectrometer (pXRF) was followed by analysis of samples using optical microscopy (OM), scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM/EDS), micro‐Raman spectroscopy (MRS), attenuated total reflection – Fourier transform infrared spectroscopy (ATR‐FT–IR), X‐ray powder diffraction (XRD) and pyrolysis gas chromatography – mass spectrometry (Py‐GC/MS). The paint stratigraphy, the compositions of the support material, the preparatory and painting layers were studied, as well as the morphology of the pigment particles. The results revealed the use of earth pigments and carbon black. The preparatory layer was uncommon; composed of dolomite, clay rich in clinochlore and sand, in contrast to the more common gypsum and calcite. The binder and the stratigraphic analyses suggested a distempera technique.     

A Technological Study of the Elamite Polychrome Glazed Bricks at Susa,South‐Western Iran

This study investigated the technological features of the Neo‐Elamite glazed bricks discovered at the Acropolis of Susa, south‐western Iran, by conducting micro‐Raman spectroscopy, differential thermal analysis/thermogravimetry (DTA/TG), X‐ray diffraction (XRD) and scanning electron microscopy–energy‐dispersive X‐ray spectroscopy (SEM–EDS). The results showed that calcium antimonate white and lead antimonate yellow were used as opacifiers in the white, yellow and green glazes, and that green and turquoise glazes were achieved using copper. Coloured glazes were separated by a Si‐rich brown glaze to prevent them from running together during firing. The glazed bricks most probably were not fired at temperatures higher than 900°C.     

Raman spectroscopy and scanning electron microscopy confirm ochre residues on 71 000‐year‐old bifacial tools from Sibudu,South Africa

Micro‐residue analysis of stone tools is generally performed with optical light microscopy and the visual observations are then compared with experimental, replicated pieces. This paper complements such archaeological research by providing physico‐chemical evidence. Raman spectroscopy and scanning electron microscopy have been used to confirm the presence of hematite on red‐stained medial and proximal parts of 71 000‐year‐old Still Bay bifacial tools from Sibudu Cave. Our results confirm the conclusion from optical light microscopy that the tools were hafted with an ochre‐loaded adhesive. However, we point to some instances when hematite residues are incidental or may be inclusions in the rock used to make the stone tools.     

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.     

Mineralogical and Chemical Characterization of Roman Slag from the Archaeological Site of Castra (Ajdovščina,Slovenia)

This study deals with the mineralogical and chemical characterization of archaeometallurgical material from the Roman archaeological site of Castra (Ajdov??ina, western Slovenia). Samples were initially analysed via optical microscopy and X‐ray powder diffraction, with the composition of individual phases then determined using scanning electron microscopy coupled with electron‐dispersive spectroscopy, and Raman microspectroscopy. Chemical investigation was carried out by using inductively coupled plasma atomic emission spectroscopy to measure the major element content. The results showed that the slag originated from iron smithing operations, with calcium‐rich olivines, as well as wuestite and leucite, the most abundant phases. The investigated slags were also found to be characterized by significantly high lime levels, which probably promoted the formation of the calcium‐rich olivines.     

No Place for the Political: Micro‐Geographies of the Paris Climate Conference 2015

Building upon post‐foundational political philosophies, this article scrutinizes the Paris Climate Conference in December 2015 from a micro‐geographical perspective. The analysis suggests that three different spaces exist at the site of the summit and reveals how their constituting practices and material arrangements rendered “Paris” post‐democratic. We begin with exposing the staged statements of the world's political elites in the meticulously orchestrated Leaders Event as different phenotypes of the post‐democratic condition. We then investigate the formal negotiations in the cordoned‐off backrooms, where positions within the system were at stake, but not the system as such. Finally, we wander through the strictly policed “trade fair” and unveil attempts to entice delegates into techno‐managerial solutions to the climate crisis. In the conclusion, we ponder over the prospects of environmental activism at the COPs in the light of their massive depoliticization.     

CHARACTERIZATION OF LATE CHALCOLITHIC MICRO‐BEADS FROM ÇAMLIBEL TARLASI,NORTH‐CENTRAL ANATOLIA

Micro‐bead manufacture is geographically widespread from the fifth millennium bc . Previous studies of comparable micro‐beads from sites in the Indus Valley region and the Near East suggest that many of these beads were formed from synthetic enstatite. Characterization of micro‐beads from the Late Chalcolithic site of Çaml?bel Tarlas? was carried out by optical microscopy (OM), scanning electron microscopy (SEM) and microanalysis with energy‐dispersive X‐ray spectroscopy (EDS), and X‐ray diffraction analysis (XRD). The chemical composition of the micro‐beads analysed indicated that they were made from three distinctive materials; namely, bulk talc (i.e., synthetic enstatite precursor), apatite and mineral‐rich clay pastes.     

Portuguese Blue‐on‐Blue 16th–17th Century Pottery

Blue‐on‐blue (‘berettino’) sherds have appeared in numerous production and consumption archaeological excavations in Lisbon and other archaeological sites in Portugal (dated from the mid‐16th century to the beginning of the 17th century). The abundance of this interesting faience led us to compare it with similar pottery from other well‐known production centres in Italy, namely Liguria (Savona and Albisola), Spain (the Triana kilns) and the Low Countries. Differences in the diffraction patterns of the sherds' pastes from the four countries were observed. In most samples, cobalt blue silicate (cobalt olivine) was identified in the dark blue or light blue glazes through the use of micro‐Raman spectroscopy and diffuse reflectance spectra. A remarkable difference in the calcite contents of the Lisbon and Seville pottery sherds was observed, in accordance with previous observations of high calcite contents of Seville ceramics. A comparison was also made for all of the blue‐on‐blue sherds studied here with many other 16th–17th century sherds from Lisbon using bivariate plots of K/Si versus Ca/Si. Lisbon and Seville pottery behave very differently, whereas sherds from Italy and the Low Countries occupy intermediate positions.     

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.     

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.     

Vietnamese (15th Century) Blue‐And‐White,Tam Thai and Lustre Porcelains/Stonewares: Glaze Composition and Decoration Techniques*

EDS, X‐ray fluorescence, Raman spectroscopy, thermal expansion–shrinkage measurement and scanning electron microscopy were applied to determine the elemental components, structural phases and glazing temperatures of the transparent glazes, blue underglaze and overglaze tam thai (including gold‐like lustre) decorations from the 15th‐century Vietnamese porcelains/stonewares found at the Chu Ðâu–My Xa kiln site and in the Cù Lao Chàm (Hôi An) cargo. The ancient technology for colouring the glazes is discussed. The various blue tones in the underglazed décor result from cobalt‐containing manganese ore, with the intentional addition of iron oxide. The overglaze copper‐green and the gold‐like lustre were obtained by dispersing copper in lead‐based glass. The red colour was made using hematite dispersed in lead‐rich flux.     

Polychromy Analysis on Cypriot Archaic Statues by Non‐ and Micro‐Invasive Analytical Techniques

The polychromy of limestone and terracotta statues from Cyprus attributed to the sixth to fifth centuries bc is analysed using non‐ and micro‐invasive techniques in order to shed light on the use of pigments during the studied period. The strengths and limitations of these methods for the present application are discussed. The identified pigments are iron‐containing compounds (red, yellow, green earths and iron–manganese black). No copper‐containing compounds were detected on the studied objects, despite the wide availability of copper minerals in Cyprus.     

A CASE STUDY OF ARTHROPODS PRESERVED ON ARCHAEOLOGICAL BRONZES—MICRO‐ARCHAEOLOGICAL INVESTIGATION HELPS RECONSTRUCTING PAST ENVIRONMENTS

This paper offers new perspectives for improving our knowledge of arthropods in wet and aerobic archaeological contexts. The very‐near environment of uncleaned buried bronze artefacts, two ronde‐bosse ornaments of a Celtic grave from the Iron Age (275 to 250 bc , La Fosse‐Cotheret, Roissy‐en‐France), was studied by means of optical and scanning electron microscopies. Taking into account recent knowledge on bronze corrosion (decuprification), this micro‐investigation (micro‐archaeology) allowed identification of two fossilized arthropods—Cryptophagus sp. (Insecta, Coleoptera, Cryptophagidae) and Coccotydaeolus sp. (Acari, Tydaeoidea, Iolinidae)—which sheds some light upon the complex taphonomic process that occurred after the burial of a Celtic chariot. These first results support the idea that the local corroded metal/soil system has to be investigated for a better understanding of archaeological microenvironments. Efficient minute investigation of soiled bronzes could be performed prior to systematic cleaning of artefacts.     

The Structure and Chemical Composition of Wall Paintings From Islamic and Christian Times in the Seville Alcazar

Wall paintings from the Islamic epoch (10th to 12th centuries) and the Christian monarchy (14th to 16th centuries) have been recovered in discarded materials and on walls after reconstruction works in the Seville Alcazar. These paintings have spent centuries underground or under a plaster coat. Portable X‐ray fluorescence (XRF) and combined XRF/X‐ray diffraction (XRD) were employed in situ, as well as scanning electron microscopy (SEM–EDX), grazing angle incidence XRD and micro‐Raman spectroscopy, on cross‐section samples to fully characterize the materials in the wall paintings. Using these methods, the fresco technique was demonstrated, and many kinds of pigments were identified in accordance with the various periods of the history of the Alcazar, thus assessing the authenticity of all the wall paintings studied here.     

Compositional Analysis of 14th–15th Century Enamels from the Altar of San Giovanni in Florence: an Integrated Study by Portable X‐Ray Fluorescence and Electron Probe Microanalysis

The enamels of the Altar of San Giovanni, from the Baptistery of Florence, were investigated using both non‐invasive and micro‐invasive analysis in order to elucidate the glass melting and colouring techniques. A few fragments detached from the altar and recovered by the restorers were analysed in cross‐section by electron probe microanalysis. Moreover, non‐invasive investigations by portable XRF allowed a large number of enamelled plaques to be investigated. The results showed a good agreement between the two techniques and made it possible to identify similarities or differences in the enamels of the three manufacturing periods of the altar.     

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.     

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).