SPECTROSCOPIC INVESTIGATION OF RED STAINS AFFECTING THE CARRARA MARBLE FAÇADE OF THE CERTOSA OF PAVIA

The nature of the large red stains exhibited on the Carrara marble elements of the Certosa of Pavia façade was investigated by means of spectroscopic techniques and scanning electron microscopy. Although previous microbiological analysis has demonstrated the presence on the stone of a bacterial strain identified as Micrococcus roseus, that is capable of carotenoid production, it has been ascertained in the present study that an inorganic pigment, namely Pb₃O₄, is responsible for the observed coloration. On small green spots, the presence of photosynthetic micro-organisms has been demonstrated by microbiological analysis and confirmed by resonance Raman spectroscopy.     

Black limestones used in antiquity: the petrographic,isotopic and EPR database for provenance determination

We compiled a database of some of the most important black limestone quarries used in Roman times to be able to determine the provenance of ancient artifacts. For this purpose, we adopted a multimethod approach using the techniques commonly applied to study the provenance of white marbles: petrographic observations, carbon and oxygen isotope composition, electron paramagnetic resonance (EPR) spectra characteristics. Few black limestones were quarried and traded in ancient times; indeed, the importance of most of these quarries was restricted to the areas in which they were located. In this work, we selected a limited number of quarries that produced material believed to have been exported and used throughout the Mediterranean area; most of the quarries selected are found in northern Tunisia, i.e. the Roman proconsular Africa: Djebel Oust, Djebel Azeiz, Ain al Ksir and (presumably) Thala. The “Nero Chiota” limestone quarried on the Aegean island of Chios (Greece) was also included in the database.     

Characterization of Pigment and Binder in Badly Conserved Illuminations of a 15th‐Century Manuscript

In this work we report a pre‐restoration spectroscopic study by a multi‐technique approach on the green pigment and the binder used in illuminations in a codex of the late 15th century. Our analysis aimed to characterize the badly deteriorated parts of the codex, mainly the green parts, by electron paramagnetic resonance (EPR), X‐ray diffraction (XRD), X‐ray fluorescence (XRF) and infrared spectroscopy (ATR‐IR). We will show that a combined study by EPR and IR spectroscopies on model systems allowed us to refine the general information obtained with the other techniques and to identify the binding media surrounding the chromophore Cu(II) ion.     

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.     

The Asiatic marbles of the Hadrian's Villa at Tivoli

Multi-method provenance studies, including petrographic, isotopic, electron paramagnetic resonance and trace chemical analyses, have been carried out on 20 white, 9 black and 1 red artifacts purposely selected to investigate the use and distribution of sculptural marbles at the Hadrian's Villa. A large fraction of the marbles tested (21 samples, 70%) are shown to be from Asia Minor, mostly originating from the recently discovered site of Göktepe near Aphrodisias (15 or 71%). All the 9 black samples investigated and 6 out of 11 white Asiatic marbles are from Göktepe, the remaining being Docimium marble from Iscehisar (4 samples) and Aphrodisias marble from the city quarries (1 sample). The single red sculpture tested proved to be Carian red marble from the Iasos quarries, whereas non-Asiatic marbles include 3 Carrara and 6 Pentelicon samples. The selection of marbles tested is preliminary and incomplete, but, despite this, the results are noteworthy, especially since the marble of other sculptures from the Villa has already been identified as Göktepe. Together with other published results, the marble distribution at the Hadrian's Villa seems to suggest that the use of sculptural marbles in the Roman world underwent considerable changes around the turn of the 1st and the 2nd century AD. The evidence supporting this hypothesis is briefly summarized in the conclusions.     

COLOUR ATTRIBUTES OF MEDIEVAL WINDOW PANES: ELECTRON PARAMAGNETIC RESONANCE AND PROBE MICROANALYSES ON STAINED GLASS WINDOWS FROM PAVIA CARTHUSIAN MONASTERY*

Stained glass windows from the Carthusian Monastery of Pavia, dating back to the 15th century, were studied by combining two analytical techniques: electron probe micro‐analysis (EPMA) and electron paramagnetic resonance (EPR). Chemical compositions and oxidation states of the transition ions, present as minor elements, were investigated by EPMA and EPR, respectively, in order to ascertain the role played by chromophorous ions in the glass coloration. The investigated glass can be defined as K–Ca glass, and the panes with red, green and blue colours were produced using flashing techniques.     

COOKING AND PAINTED WARE FROM SAN GIUSTO (LUCERA,FOGGIA): THE PRODUCTION CYCLE,FROM THE SUPPLY OF RAW MATERIALS TO THE COMMERCIALIZATION OF PRODUCTS*

Archaeological excavation at the San Giusto site (Lucera, Italy) has unearthed a Late Antique kiln that was most certainly dedicated to the production of cooking ware. An archaeometric study of numerous specimens of cooking and painted ware found at this site was carried out using optical microscopy, scanning electron microscopy, micro‐Raman spectroscopy, X‐ray diffraction, X‐ray fluorescence, inductively coupled plasma mass and optical emission spectrometry and instrumental neutron activation analysis. The integration of historical–archaeological data with archaeometric data has revealed that these specimens can be attributed to the San Giusto site. Furthermore, the production cycle of this ware can thus be reconstructed: from the diversified supply of raw materials (fluvial and marine sediments), to the relatively complex preparation of the paste, to firing at variable temperatures (600–750°C for cooking ware; 850–1050°C for painted ware).     

A SCIENTIFIC INVESTIGATION ON THE PROVENANCE AND TECHNOLOGY OF A BLACK‐FIGURE AMPHORA ATTRIBUTED TO THE PRIAM GROUP*

The restoration of a Greek black‐figure amphora provided an opportunity to study the provenance and production technology of the vase. The composition of the ceramic body, determined by inductively coupled plasma optical emission spectroscopy (ICP–OES), matches that of Attic products. Investigation by X‐ray diffraction and reflectance spectroscopy suggests a maximum firing temperature around 900°C and a body re‐oxidation temperature around 800°C, respectively. The morphology and composition of black, red and dark red surface areas were studied by scanning electron microscopy and X‐ray energy‐dispersive analysis; the black areas show the features of a typical well‐vitrified black gloss, while the red areas were most probably obtained by simple burnishing of the body; the dark red additions, on the other hand, are the likely result of a partial re‐oxidation of a clay–ochre mixture.     

GEOCHEMICAL ANALYSIS OF VITREOUS ROCKS EXPLOITED DURING THE FORMATIVE PERIOD IN THE ATACAMA REGION,NORTHERN CHILE*

Petrographic analysis and geochemical characterization studies were carried out on vitreous dacite and/or rhyodacite artefacts from Formative period archaeological sites in the upper Salado River Basin in the Atacama Desert, northern Chile. These were compared with samples taken from two source areas located within the subregion, named Linzor and Paniri. Source samples and archaeological specimens were analysed by inductively coupled plasma – mass spectrometry (ICP–MS) combined with optical emission plasma – mass spectrometry (ICP–OES) and atomic absorption spectroscopy (AAS). Results from the limited number of samples analysed indicate that the Linzor source seems to have been the primary source exploited during the Early and Late Formative periods in the Salado River Basin.     

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).