ARTIFICIAL OR NATURAL ORIGIN OF HEMATITE‐BASED RED PIGMENTS IN ARCHAEOLOGICAL CONTEXTS: THE CASE OF RIPARO DALMERI (TRENTO,ITALY)

This study concerns those crystallographic and microstructural features that can provide indications on the actual origin of red pigments based on hematite (Fe₂O₃). The main features of natural and artificial hematite are recalled and used to discuss the results obtained from the characterization of red‐ochre samples coming from the Palaeolithic site of Riparo Dalmeri, a rock‐shelter located in northeastern Italy, dated to 13 000 cal. bp , and notorious for the presence, among the other finds, of red‐painted calcareous stones. Painting and the treatment of leather and hides obtained from the intensive hunting activity were the main uses of the hematite‐based red‐ochres at Riparo Dalmeri. It turns out that hematite was mostly obtained from the thermal treatment of goethite, which, unlike hematite, was and still is widely available in the neighbourhood of the site.     

COLOUR SYMBOLISM IN THE PREHISTORIC ARCHITECTURE OF CENTRAL ANATOLIA AND RAMAN SPECTROSCOPIC INVESTIGATION OF RED OCHRE IN CHALCOLITHIC ÇATALHÖYÜK

The use of red ochre in the prehistoric architecture of Central Anatolia has long been recognized. Scholars have often argued that its use in architecture has a symbolic role, and that it has been used in sacred parts of ritual buildings. This paper examines red‐painted buildings in the prehistoric settlements of Central Anatolia. Recently, a building with red‐coloured plastered walls and floors was found in Chalcolithic Çatalhöyük West. The technique of Raman Spectroscopy has been applied to identify the red pigment and results show that it is red ochre, which contains predominantly hematite, Fe₂O₃.     

Raman Spectroscopic Analysis of Ancient Egyptian Pigments

The application of FT‐Raman spectroscopy and visible Raman microscopy to the non‐destructive analysis of pigment specimens excavated from Tell el Amarna by Flinders Petrie in the 1890s has provided information about the chemical composition of the materials used by XVIIIth Dynasty artists in the New Kingdom at the time of King Akhenaten, c. 1340 bc. Comparison of the Raman spectra of the samples labelled ‘red and yellow ochre’ with documented, archival material from geological collections provided a clear indication of the materials used in the iron(III) oxide/hydroxide system, including α‐hematite, goethite, maghemite, magnetite and lepidocrocite. The yellow–orange specimen labelled ‘realgar’ proved to be a mixture of realgar and pararealgar; since the specimen had been sheltered from light since its excavation, this could indicate that the ancient Egyptian artists recognized the colour variation and may have used this to effect in their decorations. A specimen of yellow ochre contained goethite, α‐FeO.OH, with particles of crystalline, highly ordered graphite; in contrast, the red ochre specimens contained amorphous carbon particles.     

Cemented ash as a receptacle or work surface for ochre powder production at Sibudu,South Africa, 58,000 years ago

The white ash of Sibudu hearths sometimes became cemented and, when this was the case, some of these crusts were used as work surfaces or receptacles, particularly in occupations dating about 58,000 years ago. Substantial deposits of red and yellow ochre powder have been found on these crusts. This suggests that the ochre was not associated with hearths for heat treatment because yellow ochre readily transforms to red even at low temperatures. XRF readings suggest that the ochre used at the site derives from different geological sources. Micromorphological studies imply that phosphatization caused the cementation of the ashes in some hearths, while gypsum growth hardened one of the hearths described here.     

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.     

Chemical and mineralogical characterization of Aguada Portezuelo pottery from Catamarca,north-western Argentina: PIXE,XRD and SEM-EDS studies applied to surface pre- and post-firing paints,slips and pastes

Particle-induced X-ray emission (PIXE), X-ray diffraction (XRD), electron microprobe analysis (EDS) and scanning electron microscopy (SEM) analytical techniques were used to characterize surface paints in pre- and post-fired Aguada Portezuelo decorated pottery. Surface paintings in black, white, red, brown, burgundy and ochre were analysed. Major, minor and trace elements were detected by PIXE, whereas XRD and SEM-EDS gave information on the main mineral phases and the characteristic morphology for each analysed pigment. The results obtained indicate that the main colour groups can be easily discriminated by PIXE, and they are characterized by only one pigment for each colour: hematite (red) and manganese mineral oxides (black), respectively, whereas white pigments are characterized by calcite, ghelenite and gypsum.     

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.     

Magnetic Alteration of Soils by Late Holocene Hunter–Gatherer Groups (Tierra Del Fuego,South America)

The present work aims to analyse the magnetic signature from the Late Holocene open‐air archaeological deposits of hunter–gatherer ephemeral occupations. For this purpose, two profiles were sampled at the Marazzi 2 site in the north‐western Isla Grande de Tierra del Fuego, Chile, in order to carry out studies of magnetic susceptibility, hysteresis cycles, back‐field remanent magnetization, isothermal remanent magnetization and thermal variation of magnetic susceptibility at high and low temperature. Despite short‐term occupations, the P1 profile shows a magnetic peak at a depth of ~30–70 cm due to magnetite, probably formed by anthropogenic activity related to combustion. The P2 profile instead yields an anomalous peak of coercivity (at a depth of 20–40 cm), which could also be anthropogenic, due to the presence of finely dispersed ancient ‘red ochre’. The red ochre is proposed to form anthropogenic thermal alteration of goethite associated with volcanic ash, the remnants of which were found in thin sections from the P2 subsoil.     

Ochre fingerprints: Distinguishing among Malawian mineral pigment sources with Homogenized Ochre Chip LA–ICPMS

In this study, we compared the effectiveness of instrumental neutron activation analysis (INAA) of bulk ochre to laser ablation‐inductively coupled plasma mass spectrometry of homogenized ochre chips (HOC LA–ICPMS) at distinguishing among three ochre sources in northern Malawi. Both techniques upheld the Provenance Postulate; however, HOC LA–ICPMS required less sample material than INAA and facilitated fast, inexpensive replicate observations that allowed for more robust statistical analysis. Our results indicated that HOC LA–ICPMS is a maturing technique that will be a valuable option for analysing artefacts that require minimally destructive sampling but are too large to fit into the laser cell for direct ablation. With regard to the statistical procedures used, stepwise canonical discriminant analysis was demonstrated to be a highly effective method for distinguishing among ochre sources, even in the presence of significant intra‐source and intra‐sample heterogeneity. Continued development of the HOC sample preparation technique will expand the range of archaeological ochre artefacts that can be included in provenance studies and prevent bias towards artefacts of convenient‐to‐analyse dimensions.     

Ochre Provenance and Procurement Strategies During The Middle Stone Age at Diepkloof Rock Shelter,South Africa

Usually referred to in archaeological contexts simply as ‘ochre’, ferruginous rocks were commonly used during the Middle Stone Age (MSA) in South Africa. While ochre use by early modern humans has often been interpreted as reflecting complex behaviours, related procurement strategies and selection criteria remain poorly documented. Eight ochre sources from the surroundings of Diepkloof rock shelter in South Africa and 28 ochre pieces from the site's MSA levels were studied by XRD, ICP–OES and ICP–MS. Mineralogical and geochemical data demonstrate that ochre was both locally procured and transported to the site from more distant sources. Here, we investigate the reasons underlying the choice of particular local and non‐local ochre sources exploited at Diepkloof, emphasizing differences in their physico‐chemical properties. Regardless of the motivations behind ochre selection, our data shed new light on the behavioural complexity of MSA societies and suggest that ochre procurement strategies may be independent of subsistence concerns.     

陕西安康紫阳北五省会馆壁画颜料分析研究

陕西安康紫阳北五省会馆壁画是目前陕西省境内发现的最大的一处建筑壁画,为了解其颜料组成,本工作采用X射线荧光、偏光显微镜、X射线衍射、激光显微拉曼光谱及扫描电镜能谱分析相结合的分析方法,对颜料样品进行了分析。结果表明,北五省会馆壁画除正殿发现一处红色染料外,其他均为无机颜料;红色颜料主要是铅丹、朱砂、铁红;绿色颜料为氯铜矿、石绿、斜氯铜矿;蓝色颜料的主要成分是普鲁士蓝、smalt、石青;黄色颜料为雌黄、铁黄;褐色颜料的主要成分是铁红及铅丹的变色产物二氧化铅;黑色为炭黑;白色颜料主要是铅白,且多使用铅白作为调色颜料。研究结果对于了解清代民间壁画的制作工艺,丰富对陕西建筑壁画的认识具有重要意义。     

Ceremonial objects or household items? Non‐destructive μ‐XRD2 and μ‐XRF studies on three Neolithic hematite axes from Qatar

Three small stone axes were collected by the joint Qatari‐German South Qatar Survey Project (SQSP) at two places close to the eastern and western coast of Qatar in autumn 2012. Associated with settlement remains, flint artefacts and pieces of ?Ubaid pottery, the implements have been dated to the fifth millennium BCE. Non‐destructive μ‐XRD² and μ‐XRF analyses could, for the first time, prove the use of hematite as the raw material for the manufacture of these tools in Arabia. The absence of major hematite sources in the region and the special characteristics of hematite — a unique metallic shine of polished pieces and the blood‐red colour that appears during the manufacturing process — suggest the highly symbolic character of these objects.     

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.     

Elemental Analysis of Ochre Outcrops in Southern British Columbia,Canada

Ochre is a red mineral pigment that was a key element of social and ceremonial practices among cultures of the Pacific Northwest Coast. It is recovered routinely from archaeological excavations, is visible as pigment for pictographs, and is described in the historical record as a trade item and component of ceremonial practices. Despite its ubiquity in the archaeological record, it is difficult to interpret its significance without first understanding the nature of its procurement and distribution. As a step towards identifying procurement practices, trade and resource use, it is necessary to thoroughly characterize ochre outcrops with regard to their intra‐source and regional variability. We analysed ochre from three outcrops using INAA to determine their elemental chemistry. The purpose of this study is threefold: to provide an example of the range of elemental variability within and between outcrops, to illustrate the effect of scale and geomorphological processes on elemental compositions and statistical interpretation, and to create a database of known deposits in southern British Columbia. The results demonstrate that ochre deposits may be differentiated on the basis of their chemistry, and that conservative statistical interpretation needs to be employed to assess true elemental variability within and between ochre deposits and regions.     

PIGMENTS AND PLASTERS FROM THE ROMAN SETTLEMENT OF THAMUSIDA (RABAT,MOROCCO)

A total of 22 samples were taken both from plasters still in situ and from collapsed material recovered by French, Italian and Moroccan teams at the Roman settlement of Thamusida (Rabat, Morocco). The sample characterization was obtained using optical microscopy, scanning electron microscopy, image analysis and Raman micro‐spectroscopy. Plaster aggregate was made using a mixture of sands and clays that outcrop nearby, while lime was probably produced using the local limestone crust, as was further verified for the mortars. The plasters from the bath complexes (public buildings) and the Temple à trois cellae (sacred building) were very poorly made, while those from areas VII and XX (private buildings) indicated the involvement of more expert masons. The pigments used were cinnabar, red ochre, yellow ochre, Egyptian blue, green earth, chalk white and carbon black. The overall manufacture was of low quality, and hence perfectly comparable to that observed in other Roman Provinces. With respect to Italy and to other Mediterranean Roman sites, Thamusida fits well within an aesthetic and technical koinè that differentiates sites of the Italian peninsula from those in the Provinces.     

Identification of colourants in icons of the Cretan School of iconography using Raman spectroscopy and liquid chromatography

The stratigraphies of twenty five (25) samples removed from twenty (20) icons of the Cretan School of iconography are studied using Optical Microscopy and micro-Raman spectroscopy. The objects are dated in 15th–17th c. and belong to the collection of the Benaki Museum, Athens, Greece. Cinnabar, red ochre, minium, yellow ochre, azurite, malachite, lapis lazuli, lead white, carbon black, and indigo are identified in the cross-sections of the icon samples using Raman spectroscopy.     

The death and burial of sunghir 1

The Mid Upper Paleolithic Sunghir 1 burial of an older adult male is one of the most elaborate burials known, with red ochre, thousands of mammoth ivory beads, and other body ornaments. Reanalysis and cleaning of the skeletal remains revealed a perimortem incision in the ventral–lateral first thoracic vertebra (T1) body, most likely from a sharp blade or point and the probable cause of death. Context indicates that the trauma was most likely from a hunting accident or social altercation. The unusual cause of death may be correlated with the exceptional burial elaboration of Sunghir 1, adding to the high frequency of unusual individuals in the ‘red ochre’ burials of the Mid Upper Paleolithic. Copyright © 2010 John Wiley & Sons, Ltd.     

IDENTIFICATION,PROCESSING AND USE OF RED PIGMENTS (HEMATITE AND CINNABAR) IN THE VALENCIAN EARLY NEOLITHIC (SPAIN)

The results of the first elemental and structural physicochemical analyses (SEM–EDX, TXRF, XRD, FTIR, GC and EDXRF) of Early Neolithic red pigment samples from the region of Valencia confirm one of the earliest uses of cinnabar (HgS) in Spain (5300 to 5000 cal bc ). They also inform on the storage of massive quantities of hematite and the development of specific technologies of hematite‐based paint production and use. The samples were recovered at the three most significant Early Neolithic sites of the Mediterranean coast of Spain: Cova de l'Or (Beniarrés, Alacant), Cova de la Sarsa (Bocairent, Valencia) and Cova Fosca (Vall d'Ebo, Valencia), which together have provided the most important European collection of Cardial ceramic ware (chronoculturally diagnostic of the Early Neolithic).     

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.