Heat Treatment of Mineral Pigment During the Upper Palaeolithic in North‐East Italy

The use of red ochre for utilitarian, symbolic and artistic purposes is widely documented in prehistoric contexts. The absence of adequate red‐coloured raw materials influenced the development of technological activities aimed at modifying the original physiochemical properties of yellow ochre. The heat treatment of goethite to obtain hematite was investigated in the western sector of the Lessini Mountains in north‐east Italy, where red ochre was found in the (Proto)Aurignacian levels at Fumane cave and in the Late Epigravettian sequence at Tagliente rockshelter. The combination of X‐ray powder diffraction (XRPD) and transmission electron microscopy (TEM) proved that heat treatment was a common practice in the studied archaeological sites due to the scarce availability of suitable hematite‐based material in the region.     

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.     

SELECTION AND HEATING OF COLOURING MATERIALS IN THE MOUSTERIAN LEVEL OF ES‐SKHUL (c. 100 000 YEARS BP,MOUNT CARMEL,ISRAEL)

The transformation of yellow goethite into red hematite by heating has long been assumed for Palaeolithic red artefacts excavated close to fireplaces. However, this transformation is extremely rare. Using SEM–FEG–EDX, PIXE–PIGE, TEM and μXRD, we characterized the mineralogical and chemical compositions of four microsamples of colouring materials from the Mousterian layer B in the es‐Skhul rock‐shelter, from about 100 kya ago. For some colouring materials, the Mousterian people of es‐Skhul chose to gather remote yellow lumps for heating. Their significant transport distance provides evidence of the possible high cultural value of these colouring materials for transformation into red pigments.     

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。     

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.     

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.     

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.     

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.     

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.     

Analytical study of Roman and Arabic wall paintings in the Patio De Banderas of Reales Alcazares’ Palace using non-destructive XRD/XRF and complementary techniques

A portable XRD/XRF system and complementary laboratory techniques were employed to improve the knowledge of the procedures used to create Roman and Arabic wall paintings. Integrated physico-chemical investigations were conducted on fragments of artworks collected from the archaeological excavation of the Patio de Banderas in the Reales Alcazares’ Palace of Seville (Spain), and a comparative study on the pigments from both historical periods was performed. As a result, pigments such as vermilion, red ochre, yellow ochre, green earth, Egyptian blue, carbon and phosphor-based black pigments were detected in Roman samples; however, in the Arabic fragments, only haematite was observed. In addition, the size and shape of the particles of the wall paintings were studied with an XRD 2-dimensional detector and SEM-EDX.     

Identification of Pigments in Hellenistic and Roman Funeral Figurines

Microsamples removed from funeral figurines, which were found in two Hellenistic (third to second centuries bc ) and two Roman (first to second centuries ac ) tombs in the centre of Thessaloniki, Greece, are investigated following a multi‐analytical approach. Polarized light microscopy (PLM), X‐ray fluorescence (XRF) spectroscopy, micro‐Raman spectroscopy and high‐performance liquid chromatography coupled with a diode array detector (HPLC–DAD) are employed to identify both inorganic and organic pigments. PLM is useful to reveal the combinations of the colourants, which are identified as follows. Red ochre, cinnabar, yellow ochre, Egyptian blue, carbon black, calcite, dolomite and quartz are identified using XRF and Raman spectroscopy. HPLC–DAD is used to identify the organic colourants, which are rarely detected in painted objects of the Hellenistic and Roman period. In particular, cochineal and madder are found in six samples extracted from Hellenistic figurines. This is the first study describing the unequivocal identification of cochineal in Hellenistic objects. Furthermore, madder is identified in one sample dated to the Roman period. Madder lakes detected in the samples contain high amounts of purpurin; alizarin is either not detected or detected in trace amounts.     

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.     

新疆和田达玛沟佛寺遗址出土壁画颜料分析

达玛沟佛寺是新疆和田地区重要的佛教遗址,具有极高的佛教及艺术价值,对我国乃至东亚的佛教艺术都有着重要的影响。为研究新疆达玛沟佛寺遗址出土壁画颜料成分及工艺,以壁画文物残块为研究对象,利用体视显微镜、X荧光光谱仪、X射线衍射仪、拉曼光谱仪、偏光显微镜等多种仪器对其进行了分析鉴定。结果表明,达玛沟佛寺所使用的颜料全部为矿物颜料,其中蓝色颜料为青金石,绿色颜料为氯铜矿,白色颜料为石膏,红色颜料为朱砂,褐色颜料为铁红,赭黄色颜料为铁黄。该研究为探索中国西域佛教史、美术工艺史及后期修复保护材料、工艺选择提供科学依据。     

陕西旬邑西头遗址出土彩绘白灰面的成分和工艺分析

对陕西旬邑县西头遗址出土的彩绘白灰面进行了成分和制作工艺分析。采用偏光显微分析、扫描电镜能谱、X射线衍射,拉曼光谱分析了该彩绘面的颜料和石灰层成分,采用气相色谱-质谱联用技术(GC-MS)分析了该彩绘面的胶料成分。结果表明,该彩绘面的颜料由铁红,铁黄和绿土构成。白灰层由碳酸钙构成,部分样品中存在双层白灰层。GC-MS分析表明,该彩绘面的胶料含动物胶,可能还含蛋类。通过比较研究发现,旬邑彩绘白灰面的制作工艺和与后期壁画制作工艺相似,对其组成和工艺的研究将有助于探索先周时期关中地区壁画的起源和发展。     

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.     

ELECTRON BACKSCATTER DIFFRACTION (EBSD): A NEW TECHNIQUE FOR THE IDENTIFICATION OF PIGMENTS AND RAW MATERIALS IN HISTORIC GLASSES AND CERAMICS

Coloured samples of glass and ceramic were selected for EBSD investigation to verify the potential (advantages and limitations) of this technique in the characterization of the raw materials used and the neoformation phases originating from the manufacturing processes. In the case of copper‐bearing red glasses, it was verified that micrometric droplets, residuals of the original copper source, can be ascribed to metallic copper or to a low‐Sn bronze, due to strongly similar lattice parameters. From the same samples, micrometric flakes were identified by EBSD as magnetite and interpreted as residues of the reducing agent used in the production of such red glasses. Further, the technique allowed the pigment responsible for the yellow colouring of some incised slipware to be recognized as bindheimite. In a third case, the black pigment, contained in some Nestorian decorated pottery, was identified as an amorphous phase of Mn oxide. The accurate identification of the colouring particles and other products or materials offered a more precise comprehension of the production technique, period and site of the examined artefacts, together with scientific parameters for the identification of the raw materials, their transformation during the production cycle and an evaluation of the most reliable recipes used for their preparation.     

THE EMIGRATION OF PREALPINE LAKE MASTERS: A STUDY OF A 17TH‐CENTURY MANTELPIECE ATTRIBUTED TO THE CARLONE FAMILY OF ROVIO (TICINO,SWITZERLAND)*

This work illustrates the possible connections between the phenomenon of the seasonal emigration of lake masters and the production of artistic artefacts. Within the ambit of these dynamics, a stucco mantelpiece was taken into consideration. Nothing was known about the object: neither its origin, nor the artist who produced it, nor the period of execution. Historical, stylistic and formal analyses of the materials and of the technique with which the work was executed allow us to verify that the mantelpiece was produced using the stucco technique in the 17th century, in Rovio (southern Switzerland, Ticino), and that it comes from one of the exponents of the Carlone workshop, whose representatives were important in the tradition of itinerant artistic workers. Due to their good technical and professional specialization, the Carlone workshop served both public and private buyers. Tommaso Carlone is the principal representative artist of the Carlone workshop; it is certain that his workshop produced the stucco mantelpiece. The migrations of the artists were seasonal and they maintained a close bond with their country of origin. When they returned to the country of origin, they produced works of great artistic value, of which the mantelpiece represents a splendid example. Through the employment of conventional analytical techniques (optical and electron microscopy, infrared spectroscopy and porosity measurements), it has been possible to study the technique with which the work was executed, the materials used and the decay. The mantelpiece was produced using the stucco technique by means of a body layer (slaked lime and silicate and carbonate aggregates) and a marmorino finishing layer (slaked lime and pointed calcite crystals). Above this layer, whose thickness varies in relation to the executed result, there is a thin lime plaster whitewash, pigmented with the dispersion of yellow ochre particles; chromatic alterations are an oxalate patina caused by firm adhesion to the marmorino layer, due to the denaturation of the proteic substances employed. The final treatment was made with beeswax, which increased the marmoreal effect. Several additional layers of lime plaster whitewash have also been applied over the centuries. The figurative central square of the plastic decoration was made using red ochre.     

NEUTRON ACTIVATION PATTERNING OF ARCHAEOLOGICAL MATERIALS AT THE NATIONAL CENTER FOR SCIENTIFIC RESEARCH ‘DEMOKRITOS’: THE CASE OF BLACK‐ON‐RED NEOLITHIC POTTERY FROM MACEDONIA,GREECE

A short history of the application of NAA in the characterization of archaeological materials at the National Center for Scientific Research ‘Demokritos’, Athens, is presented. NAA was first applied in archaeology in 1974 at the Radioanalytical Laboratory, and since 1989 has been one of the primary analytical techniques of the ‘Demokritos’ archaeometry programme. A case study is also presented, concerning chemical patterning of the black‐on‐red Neolithic pottery class from Macedonia. Four chemical groups were identified, each corresponding to a different area of production. It is shown that this standardized concept of pottery technology and style was spread out within at least eastern Macedonia.