THE ‘DELLA ROBBIA BLUE’: A CASE STUDY FOR THE USE OF COBALT PIGMENTS IN CERAMICS DURING THE ITALIAN RENAISSANCE*

The morphologies and elemental compositions of cobalt blue glazes are studied in 56 dated and undated terracotta sculptures from the Florentine della Robbia school. The data allow tracing of the pigments through correlations amongst elements that are known to be constituents of the cobalt minerals. The supply of such minerals from the Erzgebirge region in Renaissance times is compatible with our data. A substantial change in the materials is marked by the presence of arsenic and bismuth in the glaze, and by reduced amounts of iron and nickel just before 1520. We speculate that this is due to procedures introduced to industrialize the production of the blue pigment. The exploitation of different cobalt minerals in association with different production procedures may explain the variability of compositions that we observe in this unique ensemble.     

A MICRO‐RAMAN AND INTERNAL MICROSTRATIGRAPHIC STUDY OF CERAMIC SHERDS FROM THE KILNS OF THE MEDICI CASTLE AT CAFAGGIOLO*

Nine representative sherds from the old (14th–16th century) kilns at the Castle of Cafaggiolo in Tuscany have been analysed by means of internal microstratigraphic analyses and micro‐Raman spectroscopy and classified as follows: six engobed and glazed fragments, of which three are covered with an opaque white, decorated layer, one is marbleized, and two are engobed. The surface of the two engobed sherds, fragments of unfinished products, indicates that at least two firing processes were used. Two samples show characteristics of Byzantine pottery, and three of them can be classified as Islamic ware or maiolica, whilst the other one displays intermediate characteristics. The variety of ceramic wares indicates the presence of craftsmen with differing expertise, and suggests that part of their work was dedicated to experimentation on new ceramic production techniques.     

SYNCHROTRON FTIR MICRO‐SPECTROSCOPY APPLIED TO THE STUDY OF POLISHED SERPENTINITE ARTEFACTS: A NON‐DESTRUCTIVE ANALYTICAL APPROACH

In prehistory, serpentinite was one of the most frequently used raw materials to produce polished stone artefacts. Several conventional analytical techniques can be applied to identify the serpentine minerals, but their application generally requires a powdered sample. This implies that the artefacts to be analysed must be damaged, and the possibility of analysing a mixture of different serpentine polytypes is high. The use of spatially resolved techniques is therefore a necessity to overcome this problem. Several thin sections of serpentinitic rocks and prehistoric axes have been analysed by synchrotron radiation Fourier transform infrared micro‐spectroscopy. The spectra were acquired directly on specific points of polished stone artefacts and this allowed the recognition of the different polytypes of serpentine minerals without causing any damage to the objects. The results show the infrared micro‐spectroscopy technique to be a useful tool for the characterization of archaeological lithic material.     

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.     

PIGMENT IDENTIFICATION IN GREEK POTTERY BY RAMAN MICROSPECTROSCOPY*

Raman microspectroscopy (RMS) is now established as a key technique for the identification of pigments of archaeological pottery that permits the in situ study of art objects by a non‐destructive procedure. The information obtained represents a great aid to restoration and conservation techniques. In this work, the chemical nature of the red, black and white pigments of five samples of Greek pottery from the end of the fifth century and the first half of the fourth century bc , exhumed from the Iberian necropolis of Cabezo Lucero (Guardamar del Segura, Alicante, Spain), has been identified. The black and the red pigments are found to be magnetite (Fe₃O₄) and hematite (α‐Fe₂O₃), respectively. The white pigment is found, for the first time, to be composed of alumina (α‐Al₂O₃ and γ‐Al₂O₃) probably yielded by the thermal decomposition of Greek bauxite.     

IDENTIFICATION AND DIFFERENTIATION OF OPAQUE CHINESE OVERGLAZE YELLOW ENAMELS BY RAMAN SPECTROSCOPY AND SUPPORTING TECHNIQUES*

Using Raman spectroscopy, energy-dispersive X-ray fluorescence and X-ray diffraction, the Pb–Sn–Sb triple oxide yellow and lead–tin yellow have been identified on two pieces of cloisonné enamel (Falangcai) porcelains. Lead–tin yellow and lead antimonate yellow have been identified on famille rose porcelains manufactured before and after 1911, respectively. The replacement of the Pb–Sn–Sb triple oxide yellow by lead–tin yellow and that of the lead–tin yellow by lead antimonate yellow are discussed.     

DISCOVERY AND CHARACTERIZATION OF AN UNKNOWN BLUE‐GREEN MAYA PIGMENT: VESZELYITE*

Blue‐green mosaic and polychrome masks and funerary offerings from the royal tombs of Calakmul, Mexico, were analysed by scanning electron microscope equipped with energy dispersive X‐ray spectroscopy (SEM‐EDS), X‐ray diffraction (XRD), and particle induced X‐ray emission (PIXE). This led to the first identification of the use of veszelyite, a rare hydrated copper‐zinc phosphate, as green pigment. Analyses of a geological sample of this mineral have been done to confirm the characterization of this Mayan pigment, which might help determine pre‐Columbian trade routes of precious and luxury objects in the ancient Maya Classic period (ad 250–800).     

CHARACTERIZATION OF LATE CHALCOLITHIC MICRO‐BEADS FROM ÇAMLIBEL TARLASI,NORTH‐CENTRAL ANATOLIA

Micro‐bead manufacture is geographically widespread from the fifth millennium bc . Previous studies of comparable micro‐beads from sites in the Indus Valley region and the Near East suggest that many of these beads were formed from synthetic enstatite. Characterization of micro‐beads from the Late Chalcolithic site of Çaml?bel Tarlas? was carried out by optical microscopy (OM), scanning electron microscopy (SEM) and microanalysis with energy‐dispersive X‐ray spectroscopy (EDS), and X‐ray diffraction analysis (XRD). The chemical composition of the micro‐beads analysed indicated that they were made from three distinctive materials; namely, bulk talc (i.e., synthetic enstatite precursor), apatite and mineral‐rich clay pastes.     

ANALYTICAL CHARACTERIZATION OF ROMAN PLASTERS OF THE ‘DOMUS FARINI’ IN MODENA*

The paper refers to the analytical characterization of Roman painted plasters dating back to the second century ad . The following techniques were used: optical microscopy (OM), scanning electron microscopy (SEM–EDS), micro‐Raman and Fourier transform infrared spectroscopies (µ‐Raman and FT–IR), X‐ray diffraction (XRPD), colorimetry and thermal analyses (TG/DTA). The investigation analysed the chemical composition and structure of the plasters, the chemical composition of the pigment layers, the use of binders and any chemical alteration of pigments as well as deterioration of the samples. Stratigraphic analysis of plasters allowed identification of their individual components, which proved helpful in finding out more about the mural painting technique employed.     

ELEMENTAL ANALYSES OF A GROUP OF GLAZED TERRACOTTA ANGELS FROM THE ITALIAN RENAISSANCE,AS A TOOL FOR THE RECONSTRUCTION OF A COMPLEX CONSERVATION HISTORY*

A group of Italian glazed terracotta sculptures, attributed to the della Robbia workshop of Florence, is partly displayed in the Louvre Museum. Analyses of the apparently homogeneous sculptures by techniques such as PIXE, SEM, ICP/AES and ICP/MS have identified differences in the materials used. The data provide a subdivision of the sculptures, which is compatible with what is known from historical documents and artistic considerations, and suggest a date for this ensemble at the end of the 15th century, when the della Robbia family was involved in the decoration of the San Frediano church in Florence.     

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.     

A CASE STUDY OF ARTHROPODS PRESERVED ON ARCHAEOLOGICAL BRONZES—MICRO‐ARCHAEOLOGICAL INVESTIGATION HELPS RECONSTRUCTING PAST ENVIRONMENTS

This paper offers new perspectives for improving our knowledge of arthropods in wet and aerobic archaeological contexts. The very‐near environment of uncleaned buried bronze artefacts, two ronde‐bosse ornaments of a Celtic grave from the Iron Age (275 to 250 bc , La Fosse‐Cotheret, Roissy‐en‐France), was studied by means of optical and scanning electron microscopies. Taking into account recent knowledge on bronze corrosion (decuprification), this micro‐investigation (micro‐archaeology) allowed identification of two fossilized arthropods—Cryptophagus sp. (Insecta, Coleoptera, Cryptophagidae) and Coccotydaeolus sp. (Acari, Tydaeoidea, Iolinidae)—which sheds some light upon the complex taphonomic process that occurred after the burial of a Celtic chariot. These first results support the idea that the local corroded metal/soil system has to be investigated for a better understanding of archaeological microenvironments. Efficient minute investigation of soiled bronzes could be performed prior to systematic cleaning of artefacts.     

SIENESE ‘ARCHAIC’ MAJOLICA: A TECHNOLOGICAL STUDY OF CERAMIC BODIES AND COATINGS*

The aim of the present study is to reconstruct the production technology of Sienese ‘archaic’ majolica in the early decades of the 14th century ad . The integration of archaeological data with archived data revealed the presence of numerous workshops, suggesting that the Sienese tradition of majolica production was well developed up until the end of the 16th century. Sixty‐seven uncoated and coated waste products were analysed. The ceramic bodies were examined by OM, XRDp, SEM–EDS, XRF, ICP–OES, ICP–MS and INAA. The coatings (enamels and glazes) were analysed by SEM–EDS and Raman microspectroscopy. The results showed that ceramics were rejected due to poor control of the firing temperature (technological wastes), faulty production technology (wastes of uncertain classification) and accidents (post‐firing wastes). Finally, the analyses revealed extreme homogeneity of the ceramic bodies, indicating the continued use of the same raw material over the whole period studied.     

FIELD AND LABORATORY MULTI‐TECHNIQUE ANALYSIS OF PIGMENTS AND ORGANIC PAINTING MEDIA FROM AN EGYPTIAN COFFIN (26TH DYNASTY)

This paper describes the physico‐chemical analyses performed on an Egyptian wood coffin on the occasion of its restoration in the hall of the National Archaeological Museum of Parma (Italy), with the aim of investigating the pigments and organic materials originally used. Pigment determination was performed both in situ by a portable energy‐dispersive X‐ray fluorescence (EDXRF) spectrometer and in the laboratory using a micro‐Fourier‐transform‐infrared (micro‐FTIR) and a Fourier‐transform (FT) Raman spectrometer. The identification of organic materials was performed through gas chromatography – mass spectrometry (GC–MS) and micro‐FTIR analysis. Amongst the pigments, special attention was paid to the green, which appeared to be severely degraded and was examined using powder X‐ray diffraction (XRD) and scanning electron microscopy – energy‐dispersive X‐ray (SEM–EDX) in addition to the above‐cited techniques. Other materials used in the polychromatic decorations are Egyptian blue, cinnabar and possibly orpiment, while calcium carbonate was used for the ground layer. The organic materials were identified as beeswax, mastic and gum arabic, sometimes as mixtures.     

OPTICAL PROPERTIES OF TIN‐OPACIFIED GLAZES*

Tin glazes contain SnO2 particles, with a diameter similar to the wavelength of visible light, which are responsible for glaze opacification. In this paper a theoretical model to explain the optical behaviour of these glazes is developed. This model is tested by measurement of the reflectance and transmittance spectra for different optical paths in Spanish Islamic and mudejar glazed ceramics and it is shown to be valid by total reflectance non‐destructive measurements on a wide range of other Islamic and related glazed ceramics.     

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.     

ROMANO‐EGYPTIAN RED LEAD PIGMENT: A SUBSIDIARY COMMODITY OF SPANISH SILVER MINING AND REFINEMENT*

Samples of red pigment from a group of seven Roman‐period Egyptian mummies, known as red‐shroud mummies, are investigated. Elemental analysis by inductively coupled plasma time‐of‐flight mass spectrometry (ICP–TOFMS) shows that the samples contain mostly Pb (83–92% by weight), along with 0.2–2.0% Sn. All of the samples are found to have similar trace element distributions when normalized to the continental crust, suggesting that they share a common geological origin. Lead isotope ratios are found to match the mixed lead sources typically associated with Rio Tinto, Spain – a site extensively mined for silver during the first century ad . Raman microspectroscopy identifies the major phase of each sample to be red lead (Pb₃O₄) with a minor phase of lead tin oxide (Pb₂SnO₄). Lead tin oxide does not occur naturally, and its incidental occurrence within the sample indicates that the material was heated under oxidative conditions at temperatures in excess of 650°C. In archaeological contexts, the high‐temperature oxidative treatment of lead is typically associated with metallurgical refinement processes such as cupellation. Based on this evidence, it is argued that the pigment was produced out of litharge associated with silver cupellation at the Rio Tinto site.     

COLOURED OPAQUE GLASS BEADS OF THE MEROVINGIANS*

Monochrome coloured opaque glass beads of the Merovingians have been examined by different analytical methods. A large number of mostly unprepared beads have been measured by X‐ray fluorescence analysis. X‐ray diffraction was used for the identification of the crystalline colouring and opacifying pigments, and electron probe micro‐analysis as well as scanning electron microscopy were applied to study the composition and the microstructure of a white, brown, green, orange and yellow glass bead. After subtracting the content of colouring oxides of the glass beads and normalizing the residual values to 100% an identical soda‐lime‐glass matrix was obtained. The origin of the colouring metal oxides is discussed.     

FIRING ANALYSIS OF SOUTH-EASTERN MISSOURI INDIAN POTTERY USING IRON MÖSSBAUER SPECTROSCOPY*

The Mössbauer spectra of prehistoric pottery and clay from the Malden Plain of south-eastern Missouri, USA, were examined. The pottery dates from AD 500 to 1400. The earlier sherds were tempered with sand and the later ones with shell. The sherds and clay contain a mixture of illite, smectite, and kaolinite. Most samples of clay and sherds contained both ferric and ferrous species. The spectral parameters for the ferric species were %DLE_Q～0. 7—1.1 mms^-1 and δ～0.0–0.3 mms^-1 for the ferrous species, ΔE_Q～2.1–2.7mms^-1 and δ～0.7–1.0mms^-1. The ferric to ferrous ratio is more accurately determined from the spectra than from consideration of the colour or the firing core of the sherds, which are not always related to the iron species ratio. Differences among sherds in the ferrous ΔE_Q can be related to original temperature of heating but with low precision.