Technological features of ‘gnathia’ pottery

‘Gnathia’ pottery samples, dating back to the mid‐fourth and third century BC, from the archaeological site of Egnazia (Fasano, Brindisi, Italy) have been characterised from the physical‐chemical, mineralogical and morphological points of view. Optical and scanning electron microscopy, X‐ray energy‐dispersive spectroscopy and X‐ray diffraction analyses have been carried out on the ceramic body, black gloss, white, yellow and red over‐paintings of fragments, with the aim of outlining technological features and defining the nature of coatings and decorations. Analytical results confirm from both a technological and morphological/decorative point of view the close relationship between ‘Gnathia’ pottery and red figured pottery, particularly with the Apulian red figured from which it takes its inspiration. At the same time the experimental results highlight shared characteristics and differences with both Attic and Apulian red figured productions. The biggest difference is in the utilisation of the ‘ingobbio rosso’ layer that covers the ceramic body. This does not seem to be based on aesthetic grounds, as in the case of Apulian red figured pottery, but on application of acquired production processes, since ‘Gnathia’ pottery was made in the same workshops as red figured pottery. Copyright © 2009 John Wiley & Sons, Ltd.     

An integrated spectroscopic approach to investigate pigments and engobes on pre‐Roman pottery

Painted Canosa ceramics were examined to identify the nature of the pigments employed and their manufacturing technology. A multi‐technique approach was used, comprising Raman microspectroscopy and laser ablation hyphenated to inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The analysed samples were mainly produced for burial in tombs and were not intended for everyday use. They belong to the period between the end of the mid‐7th century and the first half of the 4th century BC, and were excavated from the Toppicelli archaeological district near the suburbs of Canosa (Puglia, Italy). Forty‐eight pottery fragments were available for this study. No handling of the samples was required for the Raman study, and it was possible to excise the pigmented layer in such a way that the lacunae were not distinguishable to the naked eye due to the micrometric size of the laser spot as far as LA‐ICP‐MS is concerned. Their combination turned out to be quite useful for the investigation of these archaeological materials: the chemical nature of the white, red, brown and black pigments employed in the pottery manufacture was investigated. Iron and manganese compounds were identified as the red and brown/black main colouring substances, respectively; on the other hand, whites and engobes (whitish slips) were based on kaolinite. This set of colouring substances is of importance, as it enabled the artisan to obtain in one oxidising firing cycle brown, black and red paints. Finally, the finding of manganese black in these Canosa potsherds confirms that Canosa was an important centre connecting the near East to central Italy and Europe since the pre‐Roman age. Copyright © 2010 John Wiley & Sons, Ltd.     

Spectroscopic investigation of modern pigments on purportedly medieval miniatures by the ‘Spanish Forger’

Five miniatures by the so‐called ‘Spanish Forger’ were acquired by the Victoria and Albert Museum in 2008. Believed to be authentic medieval miniatures until the mid‐twentieth century, they are now considered to have been painted around the end of the nineteenth and the beginning of the twentieth century. To investigate this attribution and to gather detailed knowledge about the materials used by the artist, a comprehensive pigment analysis by Raman microscopy and X‐ray fluorescence was carried out. Although traditional materials such as vermilion, carbon black, red lead, lead white and indigo were identified, many others (chrome yellow, Scheele's green, emerald green and ultramarine blue) are modern and synthetic pigments, a result which provides a firm scientific basis for stating that the miniatures are forgeries. Copyright © 2009 John Wiley & Sons, Ltd.     

Pigments characterization of polychrome vases production at Lipára: New insights by noninvasive spectroscopic methods

One of the most impressive Sicilian pottery production is attributed to the so‐called Lipari Painter and his followers, whose vessels—found in the archeological site of Lipari (Aeolian Island, Sicily)—are decorated with characteristic blue, red, and white figures. From the archeological point of view, these artworks keep open many questions concerning dating, production technique, and cultural background. In this context, new data on the manufacture procedures and on the raw materials used for the pigments may contribute to a deeper comprehension of this early Hellenistic vase tradition. The preciousness of the vessels, exhibited at the Archeological Museum of Lipari, imposed the use of in situ nondestructive methods to address new insights on the nature of the colored layers. Thus, analyses by Raman and X‐ray fluorescence spectroscopy have been performed with portable instruments on a selection of vessels certainly attributed to Lipari Painter and to some others of his followers. The results of this study testify the use of different pigments: kaolin and gypsum, probably supplied locally, for white layers; Egyptian blue for blue hues; red ochre for brown‐reddish hues; and cinnabar for pink and red‐purple nuances. The identification of both Egyptian blue and cinnabar opens an interesting discussion about dating and circulation of the raw materials.     

An assessment study of tiles from Topkapı Palace Museum with energy‐dispersive X‐ray and Raman spectrometers

A limited number of studies concerning Ottoman ceramic technology have been performed using the scanning electron microscopy‐energy dispersive X‐ray spectrometry and micro‐Raman spectroscopy techniques. The discovery of the ceramics, which were described as ‘Iznik’, at excavation sites outside of the city of Iznik, caused disagreements over the exact origin of Iznik products. In this study, bodies, glazes, and pigments of 46 tile/ceramic shards of unknown origin, which were supplied from the vaults of Topkapı Palace Museum, and two reference tile fragments, known as Kütahya products, supplied from the demolished Surp Krikor Lusavoriç church and, additionally, two Iznik reference tiles were examined using the scanning electron microscopy‐energy dispersive X‐ray spectrometry and micro‐Raman spectroscopy techniques. Results of both techniques were evaluated together for the first time to determine the power of nondestructive Raman spectroscopy technique in differentiation of Ottoman tiles. In this work, bodies of the Kütahya tiles were found to be different than Iznik and Tekfur stone‐paste bodies, which are rich in clay rather than quartz. Two different lead‐alkali glaze compositions were found for Kütahya tiles; one was rich in PbO (over 35%) and the other one was rich in alkali (PbO less than 25%). Barite inclusions were detected in the bodies and in the glazes of some Ottoman tiles, which could be the fingerprint for the Kütahya products. It was found that the under glaze red decoration is essentially a mixture of hematite and quartz in different proportions. Shades of red decoration mainly depend on the amount of hematite in the mixture. Sixteenth century tomato red decoration contains more quartz compared with 17th century dark red decoration. This study showed that a similar technology was also applied at Kütahya in the 16th century. A linear correlation was found between the position of the Raman intense stretching peak Q₃ and lead oxide content of lead‐alkali glazes, which could allow for the differentiation of Ottoman tiles based on the nondestructive Raman analysis. This study provides an important additional reference data and discussion for the Ottoman tiles. Copyright © 2011 John Wiley & Sons, Ltd.     

Potentiality of non‐destructive XRF analysis for the determination of Corinthian B amphorae provenance

Numerous samples of archaic transport Corinthian B type amphorae coming from the archaeological excavations of Gela (Sicily, South Italy) were analysed using non‐destructive X‐ray fluorescence (portable InnovX‐Systems ‘Alpha 4000’). Between the 6th and the 5th century BC the Corinthian B amphorae were diffused throughout the Western Mediterranean regions and Greece. Some researchers assigned these amphorae to different production areas, both in Southern Italy and in Greece, although, up to now, the exact attribution to the production centres is still under discussion. In this paper, with the aim to characterise the production sites of this important typology of amphorae, common ceramics, undoubtedly produced in Corinth, Corfù and Sybaris, were also analysed as these important Greek and Magna Graecia cities are considered by the archaeologists as the production centres of ‘Corinthian B’ amphorae. The multivariate analysis, performed on selected elements, clearly distinguished two groups of amphorae which, on the basis of archeological considerations, and by the comparison with reference ceramics, were assigned to Magnae Grecia (Sybaris and surroundings) and Greek productions. Copyright © 2011 John Wiley & Sons, Ltd.     

FT‐Raman spectroscopy of pigments on a Hindu statue,Kali Walking on Siva

FT‐Raman spectroscopic analysis of eight pigmented specimens from an important Hindu statue group, Kali Walking on Siva, acquired in 1895 but of indeterminate age and now in the Horniman Museum, London, has revealed some interesting and unusual combinations of coloured pigments including cinnabar, minium, lapis lazuli and red ochre. Several specimens showed evidence of organic additives, which have been attributed to shellac resins commonly believed to have been used on this type of statuary. The Raman spectroscopic results confirm that the predominant black pigment on the Kali figure is lamp black or soot, in contrast to the SEM‐EDX data that suggests the origin of this pigment as from bone black or ivory black from the presence of phosphorus. An eclectic range of white pigments have been identified in this group including lead white, barytes, calcite and anhydrite; rutile and anatase found on one specimen on the jackal in this group have been ascribed to recent unrecorded restoration. Copyright © 2006 John Wiley & Sons, Ltd.     

Multi‐technique study of archaeological cord‐marked wares decorated with red coatings from Taiwan

Archaeological finds of Neolithic to Iron Age pottery show clay potsherds characterized by red cord‐markings. The items date back from 5500 to 1500 B.P. To better understand temporal changes in the provenance of raw‐material sources, and the nature of materials used in the red colorant and ceramic bodies, micro‐Raman spectroscopy, X‐ray diffraction analysis (XRD), and micro X‐ray florescence spectroscopy (μXRF) were applied to 29 red‐coated potsherd samples found at twelve archaeological sites across Taiwan. The techniques identified the chemical and mineralogical composition of the red coatings and ceramic bodies as well as the production methods of ancient potters. Eighteen mineral phases were identified from the Raman spectra, including hematite, α‐quartz, and anatase. Feldspar, rutile, pyroxenes, calcite, gypsum, amorphous carbon, and graphite were also detected. XRD measurements, and μXRF analyses were used as complementary techniques to obtain mineral and chemical compositions. Hematite, anatase, calcite, plagioclase feldspar, and illite were present in potsherds, suggesting pottery produced from illitic clays fired at less than 850 °C under oxidizing conditions. Results further suggest that raw materials were sourced from or near local volcanic rock areas, and more broadly from metamorphic or sedimentary rocks and clays. Chemically, raw materials used for red coatings are different to those of the ceramic bodies. Objects from most sites used the same raw material sources; however, some sites contain objects made from changing sources over time. Pot coatings exhibit polygonal cracks, and loosened cementation strongly suggesting that finely processed moist clays were fired to a biscuit form with no second stage firing process. The non‐destructive Raman experiments identified and characterized mineral phases, which helped understand manufacturing techniques. Overall the multi‐technique approach gave extensive information on the finds, helping to differentiate raw material sources and production technologies. This approach is an important and effective method for investigating archaeological finds. Copyright © 2014 John Wiley & Sons, Ltd.     

Iron speciation in ancient Attic pottery pigments: a non‐destructive SR‐XAS investigation

The present work reports a detailed investigation on the speciation of iron in the pigments of decorated pottery fragments of cultural heritage relevance. The fragments come from the Gioiosa Guardia archaeological site in the area of the `Strait of Messina' (Sicily, Southern Italy), and date back to VI–V century BC. The purpose of this study is to characterize the main pigmenting agents responsible for the dark‐red coloration of the specimens using non‐destructive analytical techniques such as synchrotron radiation X‐ray absorption spectroscopy (SR‐XAS), a well established technique for cultural heritage and environmental subjects. Absorption spectra were collected at the Fe K‐edge on the Italian beamline for absorption and diffraction (BM8‐GILDA) at the European Synchrotron Radiation Facility in Grenoble (France). In order to determine the speciation of Fe in the samples, principal component analysis and least‐squares fitting procedures were applied to the near‐edge part of the absorption spectra (XANES). Details on the local structure around the Fe sites were obtained by analyzing the extended part of the spectra (EXAFS). Furthermore, an accurate determination of the average Fe oxidation state was carried out through analysis of the pre‐edge peaks of the absorption spectra. Samples resulted composed of an admixture of Fe₂O₃ (hematite or maghemite) and magnetite (Fe₃O₄), occurring in different relative abundance in the dark‐ and light‐colored areas of the specimens. The results obtained are complementary to information previously obtained by means of instrumental neutron activation analysis, Fourier transform infrared absorbance and time‐of‐flight neutron diffraction.     

Portable XRF study of pigments applied in Juan Hispalense’s 15th century panel painting

Several medieval paintings and polychrome sculptures have been analysed in the frame of a collaboration between the Fine Arts Museum of Seville and the National Centre of Accelerators, dedicated to a non‐destructive study of artworks that belong to the wide museum’s collection. Among the oldest artworks in the collection is the panel painting Archangel St. Michael attributed to Juan Hispalense, one of the first painters in the 15th‐century Seville known by name. The panel was analysed by a portable X‐ray fluorescence (XRF) to get more information about the pigments applied and to identify possible later interventions. The results showed that the pigments were those commonly used in that period. Lead white was found in the preparation of the painting and in colour layers. For yellow colour, yellow ochre was used, while for the red one, the painter usually mixed red earth and vermillion. Blue pigment is azurite, while the copper‐based green one could not be determined more specifically by XRF. Brown colour is made with yellow ochre and organic black or, in some cases, umbra. Black pigment is probably bone or ivory black. Many decorative parts of the panel are gilded, which were confirmed by Au peaks. Later interventions were carried out on the base of Ti–Zn white mixed with earth pigments, while for green areas such as Archangel's wings also chrome green was applied. The research is part of a larger study which is still going on, whose aim is to gain more knowledge about the 15th‐ and 16th‐century Spanish painting and polychromy. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman analysis assessed by Fourier‐Transformed infrared and X‐ray fluorescence spectroscopies: a multi‐analytical approach of ancient chromolithographs from the 19th century

A set of chromolithographs from the 19th century were analysed to identify the fillers and pigments used for their elaboration. Because of the delicacy of the chromolithographs, the research involved the use of Raman, Fourier‐transform infrared and energy dispersive X‐ray fluorescence spectroscopies for a complete characterization of the works on paper without removing any microsamples. Despite the high fluorescence of the samples when analyzed by Raman spectroscopy, in this paper, we demonstrated that ink spectra can be successfully enhanced by subtracting the spectra of the supporting background paper. The results of the study showed that, apparently, the lithographer used a limited range of common inorganic pigments from the 19th century (carbon black, chrome yellow, Prussian blue, red ochre, red lead and vermilion) together with organic pigments (indigo blue, gamboge and a red organic pigment). The study also found that despite the fact that during the 19th and early 20th century the use of mixtures of several pigments was a common practice, unusual admixtures were used for the preparation of some colours of the studied chromolithographs. Copyright © 2011 John Wiley & Sons, Ltd.     

Inside the glassmaker technology: search of Raman criteria to discriminate between Emile Gallé and Philippe‐Joseph Brocard enamels and pigment signatures

The development of solid‐state chemistry at the end of the 19th century offered a variety of routes to colour a glass matrix. Eight enamelled glass objects made by Philippe‐Joseph Brocard and two representative objects made by Emile Gallé have been analysed using a mobile Raman instrument at the Musée des arts décoratifs (Paris) in order to compare their colouration technology. White, blue, yellow, green, orange, red, brown and black pigments have been identified. If most of the pigment palette is common to both craftsmen and typical of the second half of the 19th century, innovative uses are recognized for Gallé (wollastonite as an opacifier, manganese oxides in black mixtures) and Brocard (specific black and grey, pigment mixture, shade modification by small addition of white and red pigments). This preliminary work confirms the potential of Raman spectroscopy, not as a simple analytical method but as a way to document the ancient technology of fine art objects and to discriminate between different genuine productions and/or copies. Copyright © 2014 John Wiley & Sons, Ltd.     

Non‐destructive, ‘in situ’, characterization of pigments in Minoan pottery at the stratigrafical museum of Phaistos (Crete)

This paper presents preliminary results of measurements of chemical composition of pigments on the Middle Minoan pottery coming from Festos and Hagia Triada excavations. The measurements were carried out ‘in situ’ with the use of the PIXE‐alpha spectrometer, with Po‐210 radioisotope as a source of sample excitation, built at Laboratorio Nazionale del Sud. The method of measurements is described in detail and the limits are discussed. The preliminary results confirm the use of the reduced iron technique to obtain the black slips and of the talc to produce the white ones. Similarly, the presence of Manganese in some orange pigments can be associated with the use of red ochre mixed to talc, the latter being used as whitening material. Copyright © 2010 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopy analysis of 16th century Portuguese Ferreirim Masters oil paintings

In the present work a set of eight altarpieces of the 16th century (1532–1534), attributed to the Ferreirim Masters (Gregório Lopes, Garcia Fernandes and Cristóvão de Figueiredo), from the Santo António de Ferreirim Monastery (North of Portugal), were analysed by micro‐Raman spectroscopy. For this purpose some samples were taken from the paintings to characterise its artist's ‘school’. It was found that the preparation was made with chalk and gypsum and the palette composed mainly of lamp black, azurite, lead white (mixed with other pigments), lead–tin yellow type I, goethite (the main constituent of yellow ochre), red lead (as under painting), haematite (the main constituent of red ochre) and vermilion. Indigo was detected in one sample. Some derivatives and degradation products were found mainly in the panels subjected to high temperatures during a fire occurred in 1954: a degradation product from massicot or red lead, lead carbonate (dehydrated derivative of lead white), bassanite and anhydrite (hemi‐ and dehydrated forms of gypsum). These results are compared with those of previous total reflection X‐ray fluorescence spectroscopy (TXRF) analyses. Copyright © 2009 John Wiley & Sons, Ltd.     

Analysis of paintings from the nineteenth century Brazilian painter Rodolfo Amoedo using EDXRF portable system

The pigments used in four of the most representative paintings of the Brazilian artist Rodolfo Amoedo were characterized by means of the EDXRF technique. The analyzed paintings were ‘The Last Tamoyo’ (1883), ‘Study of a Woman’ (1884), ‘Bust of Mrs. Amoedo’ (1892) and ‘Bad News’ (1895). EDXRF measurements were carried out with a portable system developed by the Nuclear Instrumentation Laboratory, consisting of an x‐ray tube Oxford TF3005 with a W anode, operating at 25 kV and 100 µA, and a Si‐PIN XR‐100CR detector from Amptek. Several spectra were obtained in each color and distinct hue of the paint layer, with an acquisition time of 300 s and a beam collimation of 2 mm. Some pigments used by the artist were zinc white, lead white, ochre, umber, vermilion, Prussian blue, cobalt blue, cadmium yellow, black iron oxide and manganese violet. In the painting ‘The Last Tamoyo’, titanium white was identified in some alteration areas, which were restored during the twentieth century. These results—together with computed radiography analyses—will be used to create a database about the nineteenth‐century collection of the National Museum of Fine Arts, in order to assist restorers, conservators, art students and researchers in the field of archeometry. Copyright © 2009 John Wiley & Sons, Ltd.     

Nondestructive analysis of jade artifacts from the Cemetery of the Ying State in Henan Province,China using confocal Raman microspectroscopy and portable X‐ray fluorescence spectroscopy

Confocal Raman microspectroscopy and portable X‐ray fluorescence spectroscopy were used nondestructively to characterise 18 intact jade artifacts from the Cemetery of the Ying State in Pingdingshan, Henan Province, China. These jade artifacts date from the early to the middle of the Western Zhou Period (the mid‐11^th to the mid‐9^th century BC). Thirteen jade artifacts made of tremolite and two jade artifacts made of actinolite were discriminated from each other by their hydroxyl stretching modes, and a malachite pendant, a muscovite dagger‐axe, and a crystal pendant were also identified. Black graphite was analysed in three jade artifacts composed of tremolite, and the mineralization temperatures were estimated and compared. A red powder was found on the surface of all of the jade artifacts, and this was found to be cinnabar (HgS), which is thought to have been added to the tomb environments during burial ceremonies. The chemical compositions and the possible provenances of the jade artifacts are briefly discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Combined XRF‐SEM analysis of varnished pottery: the case of Syracuse and Adrano (Sicily) archaelogical finds

Micro‐destructive and non‐destructive X‐Ray fluorescence techniques and scanning electron microscopy coupled with energy‐dispersive spectrometry have been applied for the analysis of ten samples of Hellenistic black‐varnished pottery, coming from archaeological excavations in Syracuse and Adrano (South Italy, Sicily). Micro‐morphological and compositional investigations, together with statistical data processing, have shown several differences among the varnishes of the specimen found in the two sites. In particular, Syracuse varnishes are characterised by a more homogeneous composition and well‐defined raw materials, whereas Adrano samples show a higher variability, probably linked to the use of different raw materials and the poorer quality of the varnish as well. The obtained results attest that, as Syracuse black pottery is concerned, the production technique is at an advanced level, whereas Adrano manufacture seems to be less specialised. Copyright © 2012 John Wiley & Sons, Ltd.     

Microanalysis of clay‐based pigments in painted artworks by the means of Raman spectroscopy

FT Raman spectroscopy and micro‐Raman spectroscopy with lasers of three different wavelengths (1064 nm, 785 nm and 532 nm) were used for analysis of reference samples of natural clay pigments including white clay minerals (kaolinite, illite, montmorillonite), green earths (glauconite and celadonite) and red earths (natural mixtures of white clay minerals with hematite). In addition, eight micro‐samples obtained from historical paintings containing clay pigments in ground and colour layers have been examined. Powder X‐ray diffraction and micro‐diffraction were used as supplementary methods. It was found that laser operating at 1064 nm provided the best quality Raman spectra for distinguishing different white clay minerals, but the spectra of green and red earths were affected by strong fluorescence caused by the presence of iron. Green earth minerals could be easily distinguished by 532 or 785 nm excitation lasers, even in small concentrations in the paint layers. On the other hand, when anatase (TiO₂) or iron oxides (such as hematite) were present as admixtures (both are quite common, particularly in red earths), the collection of characteristic spectra of clay minerals which form the main component of the layer was hindered or even prevented. Another complicating factor was the fluorescence produced by organic binders when analysing the micro‐samples of artworks. In those cases, it is always necessary to use powder X‐ray micro‐diffraction to avoid misleading interpretations of the pigment's composition. Copyright © 2013 John Wiley & Sons, Ltd.