The Source of Iron‐Oxide Pigments Used in Pecos River Style Rock Paints

The likely sources of iron‐oxide pigments used in prehistoric rock paintings in the Lower Pecos Archaeological Region were identified on the basis of chemical fingerprinting using LA–ICP–MS. The chemical signatures of 13 red rock paint samples collected from two south‐west Texas sites were compared with three potential source materials (ochre, siltstone and rhyolite), and two pigment cakes (crayons) that were excavated near the sampling sites. The significant chemical similarities between the paint and siltstones suggest that siltstone was used as the source of the colour. The overlapping chemical signatures for one of the pigment cakes and siltstone further suggests that some of the prehistoric people inhabiting the area 3000–4000 years ago had acquired the skills to extract iron oxide from siltstone and process it into paint pigments.     

Unveiling the Use of Creta in Roman Plasters: Analysis of Clay Wall Paintings From Brixia (Italy)

The paper describes the analysis of a particular kind of plaster from the walls of the Roman Sanctuary (first half of the first century bce ) in the centre of Brixia (now Brescia, Italy), which is an outstanding example of Roman Republican architecture. The walls were plastered and painted with different patterns, imitating marble panels and curtains. Optical microscopy on thin sections, X‐ray diffraction and infrared spectroscopy were performed on several samples of the plaster in order to reveal the execution technique. The palette consisted of glauconite, celadonite, Egyptian blue, and red and yellow ochres. In some cases, an organic compound, possibly a lipidic compound, was present in the external paint layer, as a surface treatment. The plaster contains two superimposed coats: the render coat with lime binder and sandy aggregate; the finish coat with a clay fraction (illite, chlorite, kaolinite), together with calcite from slaked lime and grains of quartz, silicate and carbonate rocks. Although Vitrivius' De architectura reported the use of creta (clay) as daub smeared on reed vaults, the Sanctuary of Brixia represents the first documented use in Roman buildings in a painted plaster laid on a stone masonry wall.     

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.     

A Roman Egyptian Painting Workshop: Technical Investigation of the Portraits from Tebtunis,Egypt

Roman‐period mummy portraits are considered to be ancient antecedents of modern portraiture. However, the techniques and materials used in their manufacture are not thoroughly understood. Analytical study of the pigments as well as the binding materials helps to address questions on what aspects of the painting practices originate from Pharaonic and/or Graeco‐Roman traditions, and can aid in determining the provenance of the raw materials from potential locations across the ancient Mediterranean and European worlds. Here, one of the largest assemblages of mummy portraits to remain intact since their excavation from the site of Tebtunis in Egypt was examined using multiple analytical techniques to address how they were made. The archaeological evidence suggests that these portraits were products of a single workshop and, correspondingly, they are found to be made using similar techniques and materials: wax‐based and lead white–rich paint combined with a variety of iron‐based pigments (including hematite, goethite and jarosite), as well as Egyptian blue, minium, indigo and madder lake to create subtle variations and tones.     

Micro‐Raman And Micro‐Stratigraphic Analysis Of The Painting Materials In The Rock‐Hewn Church Of The Forty Martyrs In Şahinefendi,Cappadocia (Turkey)

This paper presents the results of analyses carried out on the paintings on the rock‐hewn walls of the Forty Martyrs church at ?ahinefendi in Cappadocia (a UNESCO World Heritage Site), a central region of Turkey, performed during conservation work from 2007 to 2012. The micro‐samples were investigated by spectroscopic, micro‐stratigraphic and scanning electron microscopy analysis in order to study the painting technique, the materials and the degradation products. The micro‐stratigraphic analysis showed a white, sometimes pinkish, plaster. Micro‐Raman analysis, performed on cross‐sections of the mortars, enabled the detection of calcite, gypsum, anhydrite and calcium oxalate. Scanning electron microscopy and energy‐dispersive spectroscopy revealed a similar composition among all investigated phases, aside from minor differences such as the presence of diatoms in the second and third phases and of biotite, lime lumps and plants fragments in the fourth one. Apart from traditional pigments of medieval wall paintings, micro‐Raman analysis revealed the presence of lead‐based compounds and jarosite.     

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.     

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).     

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.     

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 CHARACTERIZATION OF PAINTS AND WATERPROOFING MATERIALS FROM THE SHIPWRECKS FOUND AT THE ARCHAEOLOGICAL SITE OF THE ETRUSCAN AND ROMAN HARBOUR OF PISA (ITALY)*

This work presents the results of a diagnostic survey on the shipwrecks from the archaeological site of the ancient harbour of San Rossore (Pisa, Italy). The original waterproofing, caulking and painting materials were characterized by Fourier transform infrared spectroscopy (FTIR), gas chromatography – mass spectrometry (GC–MS), energy‐dispersive X‐ray microanalysis (EDX) and X‐ray diffraction (XRD). The major constituents of the waterproofing and caulking materials detected on the planks were tricyclic abietanes showing a high degree of aromatization. These compounds are indicative of a pitch obtained from the wood of trees of the Pinaceae family. The analysis of the organic components of the paint samples revealed diterpenoid acids characteristic of Pinaceae resins together with linear long‐chain alcohols and fatty acids, highlighting the presence of beeswax. Noticeably, the characteristic odd carbon number alkanes that are normally present in beeswax were not detected. The EDX and XRD analyses showed that hematite, calcite, cerussite and kaolinite were employed as pigments to paint the ships’ hulls.     

DETERMINATION OF PIGMENTS AND BINDERS IN POMPEIAN WALL PAINTINGS USING SYNCHROTRON RADIATION – HIGH‐RESOLUTION X‐RAY POWDER DIFFRACTION AND CONVENTIONAL SPECTROSCOPY – CHROMATOGRAPHY

The employment of synchrotron techniques complemented by conventional laboratory systems has allowed us to deepen and improve our knowledge of Roman wall painting procedures. The palette identified in wall paintings from Pompeii and Herculaneum from the second century bc includes goethite, hematite, cinnabar, glauconite, Egyptian blue, and other components such as calcite and aragonite. Proof of the use of organic binders is provided by FTIR and PY–GC/MS. Therefore, the possibility of the use of ‘a secco’ techniques cannot be ruled out. Pigments in wall paintings are usually found in small percentages and conventional X‐ray diffractometers do not detect them. Synchrotron radiation – high‐resolution X‐ray powder diffraction has allowed identification with only a few micrograms of sample.     

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.     

THE TUNGSTEN AND TIN SIGNATURE OF IRON ORES FROM ELBA ISLAND (ITALY): A TOOL FOR PROVENANCE STUDIES OF IRON PRODUCTION IN THE MEDITERRANEAN REGION

The mineralogy, petrography and major‐ and trace‐element composition of iron ores from Elba Island (Tuscany, Italy), one of the most important iron sources in the Mediterranean area since the first millennium bc , revealed that hematite‐rich ores display prominent enrichments in W and Sn (up to 4950 μg g^?1 and 8400 μg g^?1, respectively). These two elements are hosted by tiny grains of W–Sn mineral phases (ferberite, scheelite and cassiterite) that are disseminated throughout the hematite matrix. A comparison with iron ores from many Italian and European localities (most of which were exploited in ancient times) suggests the uniqueness of the geochemical pattern of Elba Island hematite‐rich ores (i.e., high W and Sn, low Mo and low Cu, Pb and Zn). We suggest that this geochemical signature may represent a new provenance marker not only for discarded ore at smelting/smithing sites, but, possibly, also for metallurgical slag and smelted metal produced in the chaîne opératoire of the iron process.     

Plasters from Different Buildings of the Sacred Precinct of Tenochtitlan (Mexico City): Characterization And Provenance

In this work, we present the results of the characterization of 20 lime plaster samples taken from the Sacred Precinct of Tenochtitlan (Mexico City), the ancient capital of the Aztec empire. The samples come from different buildings of this precinct (A, B and D) and from the west façade of phase VI of the Templo Mayor pyramid. The objective of the work is to characterize the plaster samples, to understand the raw materials used, and to evaluate the presence of similarities and differences among the samples in the building techniques and raw materials employed. All the samples were studied with OM, SEM–EDS and LA–ICP–MS. The study provided evidence of the plastering and replastering practice in the same constructive phases. The results of the analyses showed the existence of important similarities and differences among buildings and constructive phases in the Sacred Precinct. In order to understand the provenance of the limestone used in the plasters, the lumps and the binder of the samples were analysed. The results were compared with those of the limestone outcrops located in central Mexico. The provenance study showed that all the limestone used in the construction of the analysed buildings of Tenochtitlan's Sacred Precinct comes from the Tula region.     

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.     

CHARACTERIZATION AND PROVENANCE OF LIME PLASTERS FROM THE TEMPLO MAYOR OF TENOCHTITLAN (MEXICO CITY)

In this work, we present the results of the analyses of 20 lime plaster samples taken from the Templo Mayor (Great Temple), the main pyramid of Tenochtitlan (Mexico), the ancient capital of the Mexicas. The samples were analysed to recover information on the mixtures used in the fabrication of the plasters and for the provenance of the raw materials (in particular, limestone) used to make the plasters. The characterization of the samples was done by OM, SEM/EDS, XRF and LA–ICP–MS analyses, while the identification of the provenance of raw materials was done by studying the lumps present in the samples with LA–ICP–MS. The objective of the study was to establish if there was a relationship between changes in the construction techniques employed in the pyramid over time and if there were changes in the provenance of the raw materials. Six different construction phases of this pyramid are analysed, showing the similarities and differences among them, mainly based on differences in the sieving of the aggregates and in the raw materials employed. The provenance studies of the limestone used to make the plasters demonstrated that all the limestone comes from the Tula region.     

Scientific study of the pigments and binders used in mural painting from the 16th-century ce St Mary's Church of Cheriapally,Kottyam, Kerala,and its relevance to conservation

The aim of this investigation was to analyze the materials and techniques of the paintings in the 16th-century ce St Mary's Church, to evaluate deterioration of the paintings, and to propose a suitable conservation treatment for their preservation. The material analysis of ground, pigments, binders, and plasters was undertaken using binocular microscopy, field emission scanning electron microscopy (SEM)–energy dispersive X-ray spectroscopy, X-ray fluorescence, Fourier transform infrared spectroscopy in reflectance (KBr) and transmittance mode (attenuated total reflection), thin-film X-ray diffraction, and micro-Raman spectroscopy. Gas chromatography–mass spectrometry (GC-MS) was used for identifying proteinaceous and lipidic materials extracted from the micro-samples. The study generated data on two different red and green pigments used as decorative materials. The red pigments were identified as cinnabar along with traces of hematite and clay minerals, and green as malachite and the minor presence of other minerals. SEM analysis identified cotton fiber embedded in the coarse plaster layer that provided better strength to the plaster. Plant oils and proteins found as the binder in the pigment samples suggested that the painting technique was executed as tempera. Lead white and gypsum materials were used in previous restoration works.     

中国明代木质古建西安鼓楼彩绘的分析研究

鉴于有关中国木质古建彩绘材料及技术的研究报道较少,本工作通过光学显微镜、扫描电镜能谱(SEMEDX)、X射线衍射及气相色谱质谱(GC/MS)分析方法,对建于公元1380年的中国西安明代鼓楼木建表面彩绘样品进行了科学检测研究,分析了其中的无机材料组成及彩绘所用粘合剂,并收集了所涉及到的相关历史资料。分析结果表明,木建表面彩绘的材料组成和制作技术与历史调查获得的信息完全吻合。地仗层主要由粘土、石灰、干性油(桐油)及纤维织物组成,且地仗层保持最初的原材料。颜料分析结果显示,尽管修复时所使用的粘合剂与最初建造时的粘合剂完全相同,但目前彩绘的颜料即有原来使用的材料,也有十八世纪修复时所使用的材料。     

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。     

DEEPLY COLOURED AND BLACK GLASS IN THE NORTHERN PROVINCES OF THE ROMAN EMPIRE: DIFFERENCES AND SIMILARITIES IN CHEMICAL COMPOSITION BEFORE AND AFTER ad 150*

In this work we attempt to elucidate the chronological and geographical origin of deeply coloured and black glass dating between 100 bc and ad 300 on the basis of their major and trace element compositions. Samples from the western and eastern parts of the Roman Empire were analysed. Analytical data were obtained by means of a scanning electron microscope – energy‐dispersive system (SEM–EDS, 63 samples analysed) and laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS, 41 samples analysed). Among the glass fragments analysed, dark brown, dark purple and dark green hues could be distinguished. Only among the dark green fragments could a clear compositional distinction be observed between fragments dated to the periods before and after ad 150. In the early samples (first century bc to first century ad ), iron, responsible for the green hue, was introduced by using impure sand containing relatively high amounts of Ti. In contrast, a Ti‐poor source of iron was employed, containing Sb, Co and Pb in trace quantities, in order to obtain the dark green colour in the later glass samples. The analytical results obtained by combining SEM–EDS and LA–ICP–MS are therefore consistent with a differentiation of glassmaking recipes, detectable in glass composition, occurring in the period around ad 150.