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.     

Analytical characterization of lacquer objects excavated from a Chu tomb in China

This work presents the results of an investigation of the lacquer objects excavated from a Chu tomb in China (Warring States, 481–221 BC). This study is engaged in the examination of the methods and the materials used for the urushi coating on the objects. X-Ray fluorescence and Scanning Electron Microscopy/Energy Dispersive Using X-Ray (SEM/EDX) analyses were applied for the pigment identification. The results show that vermilion was for the red colour, while carbon black was for the black colour. Pyrolysis gas chromatography and mass spectrometry (Py-GC/MS) was applied for the characterization of the lacquer resulting that it is based on urushi. The possibility to classify the drying oil (tung or linseed oil) present in the lacquer is highlighted and discussed in this paper. Py-GC/MS with in-situ hydrolysis and methylation reagent tetramethylammonium hydroxide (TMAH) were performed on reference materials of linseed oil and tung oil as well as on the lacquer object samples. The results show that it is possible to unambiguously identify the drying oil, in our case, linseed oil was identified to retard the rate of hardening.     

新疆阿斯塔那唐墓出土彩塑的制作工艺和颜料分析

新疆阿斯塔那古墓群出土了大量的彩塑,为了解其制作工艺与彩绘颜料成分,采用显微激光拉曼光谱,结合剖面观察和能量色散X射线荧光光谱等科技手段,对出土于唐墓的6个样品进行了分析鉴定.结果表明,泥胎表面先用硬石膏做打底层,再施以彩绘,且彩绘颜料厚薄有异.所使用的红、黄、黑、白和绿色颜料有铅丹、密陀僧、朱砂和土红、雌黄、炭黑、硬石膏及氯铜矿等无机颜料,而粉色彩绘是由铅丹(或铅丹和密陀僧的混合物)与硬石膏调和而成,且密陀僧作为彩绘颜料在新疆是较早的发现.其最为重要的发现是蓝色彩绘为植物性染料——靛蓝.这一研究结果,为进一步的彩塑修复与保护方案的制订提供了有价值参考.     

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.     

THE COLOURED TESSERAE DECORATING THE VAULTS OF THE FARAGOLA BALNEUM (ASCOLI SATRIANO,FOGGIA, SOUTHERN ITALY)

Twenty‐six tesserae (red, orange, yellow, light amber, green, blue and white) from the balneum of the villa at Faragola (Ascoli Satriano, Foggia) have been examined by colorimetry, ICP–MS, ICP–OES and SEM–EDS. Different types of calcareous sands have been used as the source of silica (network former), also providing the stabilizing agent. A natron‐type soda source served as the network modifier; however, the use of a sodium‐rich plant ash and the recycling process have been hypothesized for the production of two tesserae (FT 1 red and FT 3 orange). The colouring and opacifying agents were Cu oxide (cuprite, orange), metallic copper (red), Pb antimonates (yellow), Ca antimonates (white), a mixture of copper (Cu²⁺) and Pb antimonates (green), a mixture of cobalt (Co²⁺) or copper (Cu²⁺) and Ca antimonates (blue). The light amber tesserae should owe their colour to iron (Fe³⁺) alone or associated with sulphide (S^2?) and Ca antimonates. It is likely that the Faragola tesserae were locally produced in a secondary glass workshop.     

Red ochre decorations in Spanish Neolithic ceramics: a mineralogical and technological study

Some Neolithic ceramics from south-eastern Spain have red to brown external decorations called “almagras” (red ochre). The pigment layer is essentially composed of a mixture of clay and iron oxides: haematite (red) and maghemite (brown). It is suggested that maghemite was formed during the firing process of ceramic in a reducing atmosphere. Several laboratory tests have been carried out to obtain maghemite by adding charcoal or pinewood sawdust to similar ceramic pastes. In fact, maghemite was formed, even when the piece was simply covered with pinewood sawdust before firing. The diverse original red colours are due to variations in iron oxide (or calcite) content and to redox conditions in the firing procedure. Brown- coloured ceramics owe their colour to maghemite and must be considered as a “fabrication defect”, due to the position of the ceramic piece in a zone where a reducing atmosphere prevailed in the course of firing.     

Petrology and Geochemistry of Late Intermediate Period Ceramics,Southern Peru

Multiple petrological and geochemical analytical techniques revealed significant similarities in element and mineral distribution between the 47 ceramic samples from Chillo (southern coast, Peru), a Late Intermediate Period (ad 1000–1400) archaeological site. The similarity indicates a common raw material source. The analytical results of Holocene fluvial sediment samples, Cretaceous clay layers and fired and non‐fired bricks, only eliminated the Cretaceous clay layers as a potential source material. Applying Raman spectroscopy, the red and violet colour of the slip is due to hematite, the yellow colour to a mixture of hematite, graphite and gypsum, and the black colour is either graphite or jacobsite.     

The Intentional Use of Lead–tin Orange in Indian Islamic Glazes and Its Preliminary Characterization

We describe the historical appearance, composition and texture of a little‐known orange pigment in 17th‐century northern India. The pigment shares similarities with lead–tin yellow type II, but has between 6 and 7 wt% zinc oxide instead of silica as a minor element in its structure, in addition to the dominant lead and tin oxide. The consistency of its occurrence and composition across several important and highly decorated monuments and relatively wide chronological and geographical ranges of use indicate the controlled and intentional production of this pigment. We propose to use the name lead–tin orange for this material, indicating its similarity to lead–tin yellow but highlighting its independent character and distinct colour.     

Building an Experimental Comparative Reference Collection for Lithic Micro-Residue Analysis Based on a Multi-Analytical Approach

Residue analysis applied to stone tools is a useful aid for better understanding their past function and, by extension, reconstructing early human behaviour. However, if the nature of residues found on the lithic tools is misinterpreted, so will be our understanding of their archaeological context. As a consequence, correctly identifying residues in the domain of lithic studies is of paramount importance. With this main goal in mind, we analysed different experimental materials likely to have been involved in daily tasks in the prehistoric context (e.g. bone, wood, meat). Microscopic analyses were then carried out using two (comparable) techniques: Optical Light Microscopy and Scanning Electron Microscopy. Also, energy dispersive X-rays spectroscopy (EDX or EDS) was applied to the experimental samples to determine their elemental composition. Advantages and disadvantages of both microscopic methods and their implications for correct residue identification are discussed. The distribution of residues on lithic surfaces is also considered. This study resulted in the construction of a data-set including both photographic material and EDX spectra for each residue analysed. The main result is that, compared to OLM scanning, SEM analyses highly improves the accuracy of residue identification.     

A Study of Biodeterioration and Chromatic Alterations of Painted and Gilded Mummy Cartonnage at the Saqqara Museum Storeroom,Egypt

Microbial biofilms have developed on the surfaces and within the painted and gilded layers of mummy cartonnage at the Saqqara museum storeroom in Giza, Egypt. SEM–EDX, XRD and FT–IR–ATR techniques were applied to analyse the coloured and gilded materials, ground layer, textile support and binder used for the cartonnage. Aspergillus niger (24.8%), Penicillium chrysogenum (21.5%) and a novel cartonnage‐biodegrading bacterium, Bacillus sonorensis (23.7%), were the most abundant microbes growing over the cartonnage surface. In addition, Aspergillus tamari (15.4%), A. fumigates (8.1%) and Fusarium solani (6.5%) were identified. The pigments comprised Egyptian blue (cuprorivaite), cinnabar (red), orpiment (yellow) and green pigment made from a mixture of cuprorivaite and orpiment. Gold leaf was used for the gilded layer, calcium carbonate and gypsum comprised the ground layer, gum arabic was the binding medium and the fibre base was a fine linen textile. Microbial colonization tests were performed on aged cartonnage replica samples made from linen and pigments of similar composition to ancient pigments found in the cartonnage. Each sample was inoculated separately with A. niger, P. chrysogenum and B. sonorensis. Yellow orpiment samples were the exception, as no colour change was detected after colonization by the examined micro‐organisms.     

Painted plaster from Bronze Age Thebes, Boeotia (Greece): a technological study

From the rather difficult excavations that have taken place in Thebes since the beginning of the last century, many fragmentary but often well-preserved paintings on plaster have been unearthed. These belong to several contexts and periods: House of Kadmos (Late Helladic IIIA), Treasury Room (Late Helladic IIIB1) and Oikopedon Spourli (Late Helladic III). Their iconography, style and technology fit well with other paintings from the Late Bronze Age sites found in the vicinity of Thebes (e.g. Gla and Orchomenos). This paper presents a technological study of the Bronze Age painted plaster from Thebes, Greece. The paintings were investigated by means of X-ray diffraction; stereo, reflected light and scanning electron microscopy; some by laser-induced breakdown spectrometry and by micro-Raman spectroscopy, in order to identify the pigments and the composition of the plaster layers, and to determine the painting technique(s) that the artisans may have employed. The plaster layer onto which the paint layer was applied was often the only layer and consisted mainly of calcite, while a clay plaster formed the backing between the lime plaster coat and the actual wall surface. The pigments identified were: yellow ochre, haematite (red), cuprorivaite (Egyptian blue), indigo and possibly riebeckite for blue, charcoal (black), calcite (white), and a combination of black and red for purple. A detailed macroscopic study of the painted surface revealed several features, which indicated that the technique of al fresco painting was employed extensively, a technique already in use since the start of the Late Minoan I phase on Crete. A generally lower level of quality in the appearance of the later paintings (Treasury Room and Oikopedon Spourli) was also noted, but this was not reflected in the materials used or in their overall manipulation.     

甘肃泾川罗汉洞石窟壁画及制作工艺研究

罗汉洞石窟始凿于北朝,是泾川百里石窟长廊的重要组成部分。作为古代丝绸之路上的重要历史文化遗产,其赋存的石窟壁画内容丰富,制作工艺特殊,对于研究泾川佛教的发展及丝绸之路文明有着重要的价值。通过罗汉洞壁画材质组成、结构特征等综合分析,壁画主体结构由内到外依次为支撑体,粗泥层(添加有麦秸),细泥层(添加有棉花),白底层,颜料层。壁画多处可看出重层现象,内层早期壁画所采用颜料均为矿物颜料,其中红色颜料为朱砂,绿色颜料为氯铜矿,蓝色颜料为石青。而外层清代光绪年间壁画红色颜料为铁红,绿色颜料为巴黎绿,蓝色颜料为群青,橙色颜料为铁黄,黑色颜料为炭黑。通过对罗汉洞石窟壁画制作工艺进行诠释与解读,并与其他丝路沿线壁画颜料应用方面进行比对,以期促进这一丝路文化遗产的保护和利用。     

Evaluation of Fe isotope values as a provenance tool for chert artefacts from the north-eastern United States

Iron (Fe) isotope compositions of prehistoric stone tools and geological sources were compared to evaluate the robustness of this isotopic fingerprinting technique. Artefacts and source materials were collected from the Hatch site in central Pennsylvania, United States, where both veined chert (Bald Eagle chert) and stone tools coexist within several metres. Yellow artefacts (δ⁵⁶Fe = 0.38 ± 0.1, n = 7) and source materials (δ⁵⁶Fe = 0.42 ± 0.1, n = 8) isotopically matched within error. The source values also overlap yellow chert samples from three other Bald Eagle chert locations in the area. These values are different from six other chert locations in the north-eastern United States. These data suggest that the Fe isotope composition of chert artefacts reflect distinct geological sources. To enhance the mechanical characteristics of the stone tools, the chert experienced heat treatment, which induced a phase shift of the Fe oxide mineral goethite to hematite. This phase shift changes the colour of the chert to red. The red chert artefacts and source material also have overlapping Fe isotope values, but are 0.2‰ higher than the initial yellow chert. Experimental work where cherts were heated with different clays shows that Fe exchange with site soils induces the +0.2 fractionation. These data demonstrate that predictable Fe isotope fractionation occurs during heating, resulting in isotopically distinct artefacts.     

埃及晚期的木基质彩画：赛加拉和法国博物馆

埃及文明在矿物方面的知识总是超出了我们的想象。这方面就包括使用多种黄色矿物绘制颜色相近的色彩。对这些颜料的准确鉴定将拓展人们在彩画方面的研究。画家所使用的颜料非常丰富,除了同时代直接从埃及地面采集的自然颜料外,还有大量像埃及蓝这类合成颜料的应用。对法国的这些藏品的研究将使人们可以追溯几个世纪以来这些颜料的演变和替代过程以及一些从其它地区尤其是东方国家引进颜料的过程。一些颜料的稳定性及其它特性使得其保存状况令人惊讶。卢浮宫博物馆在塞加拉的任务是进行一个埃及晚期（公元前378年一公元前341年）典型群葬墓的发掘工作。发掘出的木质棺材上记载了该墓葬的埋藏时间是Nectanebo二世法老执政的第2年,这是埃及第三十王朝的最后一任法老。该研究涉及以木质为基材的出土物,它包括二十个完整的或破碎成碎块的像盒子一样的棺材。研究通过在双筒显微镜下对文物进行微量取样,而后将样品进行扫描电子显微镜一能谱分析以及显微拉曼光谱分析,从而确定样品中矿物的成分。此外还对样品进行微量化学分析以确定其残存的痕量胶料。彩色颜料包括埃及彩画同时代的传统颜料一黑色,白色,红色,黄色,蓝色,绿色和镀金,同时还包括一些不常见的粉红色或橘色颜料,它是一种外来的、易碎的颜料,成分为五硫化二砷,又称雄黄。     

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.     

THE SECTILIA PANELS OF FARAGOLA (ASCOLI SATRIANO,SOUTHERN ITALY): A MULTI‐ANALYTICAL STUDY OF THE RED,ORANGE AND YELLOW GLASS SLABS*

SEM–EDS, EMPA, ICP–MS and ICP–OES were applied to the study of three sectilia panels made of red, orange and yellow glass slabs. In order to determine the chemical state of Cu, XAS was also performed. The results indicate that, with the exception of the red samples, all slabs were made by mixing a siliceous sand with natron. The red slabs show significant compositional differences with respect to K₂O and MgO contents, probably linked to the use of plant ashes as a source of alkali. The red, orange and yellow slabs are coloured by metallic copper, cuprite and Pb antimonates, respectively. The comparison between the chemical composition of the Faragola samples and several glass reference groups did not provide conclusive evidence of provenance.     

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.     

The painting of the Etruscan “Tomba della Quadriga Infernale” (4th century BC), in Sarteano (Siena, Italy): technical features

This work presents the results of an investigation of the painting technique used in the Etruscan tomb “Tomba della Quadriga Infernale”. This tomb was discovered in Sarteano (Siena, Italy) in October 2003 and dated back to the second half of the 4th century BC. Red, dark red, pink, yellow, white, black, and grey colours were used in the tomb in order to create paintings, which now represent a very precious record of the Etruscan art of wall painting in a hypogeal environment. The technical features of the painting were revealed by stratigraphy using optical and electronic microscopy. The components and preparatory layers of the painted areas were characterized using Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray microanalysis (SEM-EDS), X-ray diffraction (XRD), and gas chromatography/mass spectrometry (GC/MS). XRD, SEM-EDS, and optical microscopic techniques were also used for mineralogical analysis of the rock substrate. The SEM-EDS and FTIR analyses showed that red and yellow ochre, calcite, and vegetable charcoal were used to paint the walls of the tomb: the pigments, either alone or mixed together, were utilized to produce pure colours (red, yellow, white, and black) and intermediate tonalities (pink, dark red, and grey). SEM-EDS, FTIR, and XRD highlighted that the painting was made on a preparatory layer of calcite, applied onto a levelling material made up of calcite, clay minerals, quartz, and iron oxides. GC/MS analyses revealed that egg was used as an organic binder to disperse the pigments.     

From riches to rags: organic deterioration at Star Carr

The 11,000-year old lake edge archaeological site of Star Carr in the Vale of Pickering of North Yorkshire is one of the most famous Mesolithic sites in Europe, and one of the earliest, dated to the period of climatic warming that immediately followed the final termination of the last ice age. One of the main reasons for this international importance is the richness of its organic artefacts, faunal assemblage and environmental data. However, recent investigations have demonstrated that these organic remains have severely deteriorated over the last 60 years due to the decay and acidification of the surrounding peat. This paper presents research into the effects on the bone (histological analysis using light and polarising microscopy, and Transmission Electron Microscopy, bulk collagen analysis, and amino acid analysis), antler (visual and metrical analysis, loss on ignition and Scanning Electron Microscopy) and wood (visual analysis, decay assessment tests and Scanning Electron Microscopy).     

Palaeomagnetic dating of fluid-flow events in dolomitized rocks along the Highland Boundary Fault, central Scotland

Palaeomagnetic and geochemical studies of Cambrian–Ordovician serpentinite in the Highland Border Complex (HBC), a tectonic terrane along the Highland Boundary Fault (HBF) in Scotland, indicate that the HBF was a conduit for fluids in the Carboniferous–Permian. The fluids caused dolomitization, silicification, and haematite authigenesis. Both red dolomitized serpentinite and relatively unaltered serpentinite were sampled at multiple localities. The unaltered serpentinite contains a poorly defined magnetization with westerly declinations that resides in magnetite and has a pole which plots well off the apparent polar wander path. Most specimens of the red dolomitized serpentinite contain a magnetization with southerly declinations and negative inclinations that resides in haematite. A regional fold test suggests that this magnetization post‐dates tilting and the pole positions for the different locations fall on the Carboniferous to Permian part of the apparent polar wander path. In some specimens of red dolomitized serpentinite, alternating field (AF) demagnetization prior to thermal treatment removes a component with a similar direction. Dolomitized basement rocks along the fault contain a similar although apparently slightly older magnetization. Fluid inclusion and geochemical studies indicate that the fluids were hydrothermal in origin (110–240°C) and had a range of sources. The Carboniferous–Permian magnetization in haematite is interpreted as a chemical remanent magnetization that formed when warm fluids moved along the fault zone and caused haematite authigenesis. The component removed by AF treatment is interpreted as a thermal resetting of primary magnetite by the fluids. The variability of the palaeomagnetic, fluid inclusion, and stable isotope results suggests that there were probably multiple flow events that caused the alteration. The origin of the fluids could be related to the intrusion of late Carboniferous dikes in central Scotland and/or to reactivation of the HBF in the Carboniferous–Permian.