NMR as a new tool for cultural heritage application: The provenance of ancient white marbles

Identifying the origin of marble used in antiquity brings back to light details of the economic, social and political organization of classical societies, and characterizing in depth the chemistry of marble is key to discovering its provenance. Beyond X‐ray diffraction, which could reveal the presence of discriminant secondary crystalline phases and the quantification of accessory minerals combined with a multivariate analysis approach, solid‐state nuclear magnetic resonance (NMR) enables one to recognize the local structure arrangement of both crystalline and amorphous materials by looking at one or more selected atoms. In present paper targets the ¹³C nuclide, and thus the major component of marble, calcium carbonate. Whatever their geological origin, marbles ¹³C‐NMR spectra present only one resonance corresponding to the carboxyl function whose intensity and line width vary from one marble to another. If the variation of the NMR signal intensity observed is the result of great T1 variations (from 220 to 5300 s) and is linked to iron content, the line width reflects defects in the calcite crystal in which calcium has been replaced by another element such as magnesium, aluminium or strontium. The specific profile of the NMR signal has been used successfully to help determine the origin of some archaeological items.     

The Faragola Ceramic Collection: Ceramic Production,Consumption and Exchange in Seventh‐Century Apulia

A collection of 30 ceramic samples, 16 of coarse wares and 14 of fine painted wares, have been investigated by optical microscopy, scanning electron microscopy, inductively coupled plasma optical emission spectrometry, inductively coupled plasma mass spectrometry and neutron activation analysis. Further samples of clayey sediments, both locally outcropping and found within the settling tank, have been submitted to the same analytical techniques for comparison with the ceramic collection. The results demonstrated that local clayey sediments were used as received for the production of coarse wares. The same raw materials were sieved and/or refined by decantation for the production of fine painted wares, which, in fact, provided results that were perfectly comparable with those for the clayey raw materials found within the settling tank. The Faragola productions were distinguished from the neighbouring Apulian productions according to petrographic features (the presence of leucite‐bearing volcanic rocks and Mn‐rich wads) and their bulk chemical composition.     

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.     

Non-ferrous metallurgy from the Phoenician site of La Fonteta (Alicante, Spain): a study of provenance

The lead isotope composition of 22 samples from the excavation of the Phoenician site of La Fonteta (Guardamar del Segura, Alicante, Spain) has been analysed in a preliminary study of their provenance. These materials span chronologically from the first half of the 8th century BC to the middle of the 6th century BC.The samples have been selected to include materials used in lead and silver production, as well as in copper-based metallurgy. Therefore, lead droplets, galena nodules and fragments of litharge have been analysed, together with a fragment of a copper ingot, an object, a melting waste composed of a Cu–Pb alloy, and two fragments of a material that we have provisionally labelled ‘Pb–Cu cupellation debris’.All these materials have been initially analysed by X-Ray Fluorescence-Spectrometry to identify their bulk compositions. Some of them have been also analysed by SEM–EDX and ICP–OES. Subsequently, lead isotope analyses (LIA) have been performed using Thermal Ionization Mass Spectrometry (TIMS). The new LIA data obtained has been compared with published lead isotope data from the Mediterranean area. The identification of different groups suggests a significant complexity of the internal and external trade routes during the Orientalising period. For this reason, the provenance study of these materials is especially important in shedding light on the commercial dynamics that the Phoenicians established with native people to control the raw materials and to commercialise finished products.     

Black Gloss Pottery: Production Sites and Technology in Northern Etruria,Part I: Provenance Studies

The object of the present study is an assemblage of 149 black gloss pottery samples found in northern Etruria (Tuscany, Italy), at Arezzo, Volterra, Chiusi and Populonia. Complete chemical analyses have been performed for the whole set of samples, whereas mineralogical characterization has been provided for most of the Volterra, Chiusi and Populonia samples. The Chiusi‐Marcianella production site has been the further object of a detailed study aimed at the creation of a complete reference group. Moreover, several trade routes have been reconstructed, shedding light on the import and export of these ceramics from inland Etruria to the coast and vice versa.     

THE BLUE ENAMELS IN THE BAROQUE DECORATIONS OF THE CHURCHES OF PALERMO,SICILY: FE2+‐COLOURED GLASSES FROM LIME KILNS*

Deep blue glasses coloured by octahedral Fe²⁺ cations are often reported as textbook examples of blue pigmentation. However, despite the possibility of laboratory synthesis under reducing conditions, to date there are no well‐reported occurrences of their production and use in the past. A thorough historical, ethnographic, mineralogical, and chemico‐physical investigation of the ‘smaltini di calcara’ from several baroque churches in Palermo, Sicily, has revealed that the blue enamels widely used for altar decorations in the 17th and 18th centuries are actually a unique case of ancient blue glasses pigmented by divalent iron cations in distorted octahedral coordination. This mixed‐alkali glass was accidentally produced under severely reducing conditions in the local kilns during production of lime.     

AN ELEMENTAL AND LEAD‐ISOTOPIC STUDY ON BRONZE HELMETS FROM ROYAL TOMB NO. 1004 IN YIN RUINS

Lead isotope and element composition analyses were performed by thermal ionization mass spectrometry (TIMS) and inductively coupled plasma optical emission spectroscopy (ICP–OES) on bronze helmets from royal tomb No. 1004 at Yin Ruins, the last capital of China's Shang Dynasty (17th to 11th centuries bc ). The data show that the copper‐based alloy helmets can be divided into two categories: tin bronze and leaded tin bronze; and the lead isotope ratios for both categories are in the range of highly radiogenic lead (HRL). This result offers some important clues to answering questions concerning the provenance of raw metal materials, as well as the chronology of this famous royal tomb.