Andrea Ceglia

Iron speciation in soda-lime-silica glass: a comparison of XANES and UV-vis-NIR spectroscopy

Scientific analyses of ancient glasses have been carried out for many years using elemental chemical analysis. However, it is known that the control of the redox conditions in the glass melt has a strong implication on the final hue of glass because it affects Fe2+/ΣFe. Therefore an increasing number of studies on the redox conditions have been published in recent years by means of synchrotron based X-ray absorption spectroscopy. This is a technique which is not easily accessible and requires dedicated facilities. In this paper we describe an alternative approach by means of optical absorption spectroscopy. We synthesised 10 soda-lime-silica glasses with known redox conditions and iron concentration to calibrate the absorption at 1100 nm as a function of Fe2+ concentration. The linear extinction coefficient was also determined. These glasses were also studied by means of X-ray Absorption Near Edge Structure (XANES) spectroscopy. Electron paramagnetic resonance spectroscopy was additionally used as an ancillary method to verify the quality of our data. Furthermore 28 samples from real archaeological samples were analysed by XANES and optical spectroscopy as a case study. The Fe2+/ΣFe values obtained were compared and demonstrated that the two techniques were in good agreement with each other. Optical spectroscopy can be applied in situ with moderate sample preparation to determine the concentration of Fe2+. To investigate the redox conditions, especially as a first screening approach, this methodology is an important tool to take into consideration before applying more sophisticated techniques such as XANES, which is more elaborate and requires high-tech resources.

A XANES study of chromophores: the case of black glass

We studied the Fe K-edge X-ray absorption near edge (XANES) spectra of several Roman black glass fragments in order to determine the Fe3+/ΣFe ratio of these materials. The selected archaeological glass samples cover the period 1st–5th century AD in nine different sites of the North Western provinces of the Roman Empire. The fragments belong to two different compositional groups demonstrating a diachronic evolution: early Roman HMG (High Magnesia Glass) and Roman Imperial LMG (Low Magnesia Glass). The first group contains natural Fe levels (below 2 wt% as Fe2O3), while the LMG has concentrations above 5 wt%. This difference is also reflected by Fe3+/ΣFe values. Low iron glass was produced under strongly reducing conditions in order to obtain the black colour, with average Fe3+/ΣFe values ≈ 0.17. LMG glass is somewhat more oxidised (Fe3+/ΣFe ≈ 0.4–0.5). While HMG glass required active control of the furnace environment, LMG was made under ambient atmosphere and its higher oxidation degree is mainly determined by the chemistry of the raw glass.

Unravelling provenance and recycling of late antique glass from Cyprus with trace elements

Earlier research has shown that several common late antique glass types circulate in Cyprus between the fifth and the seventh century AD, specifically Levantine 1, HLIMT, HIMTa, HIMTb and Egypt 1, HIT, Roman and a plant ash glass. By investigating the glass material from Yeroskipou-Agioi Pente, Maroni-Petrera, and Kalavasos-Kopetra, we aimed to refine the chemical groups present within three late antique Cypriot sites and define the relations between trace elements obtained from LA-ICP-MS. Our data demonstrate compositional patterns that can be exploited to provenance late antique glass by investigating the REE-bearing mineral fractions, the amount of zircon and the carbonaceous fraction of the sand. In addition, Nb and Ti display a strong linear relation which depends on the glass type. Finally, the paper discusses the occurrence of glass recycling on the island and how this activity influenced the concentration levels of specific trace elements. Our study thus sets out an analytical framework to identify recycling events tailored on each compositional type.

The role of different network modifying cations on the speciation of the Co2 + complex in silicates and implication in the investigation of historical glasses

In the last decades the speciation of the cobalt complex in a glass matrix has been extensively studied. Bivalent cobalt ions in glasses of different composition commonly adopt a tetrahedral coordination, though hexa- or penta-coordinated species are also possible. Changes in the absorbance spectrum of Co-doped glasses were attested in previous studies according to the introduction of different modifying cations. A shifting of the first sub-band characterizing the typical triplets of tetrahedral Co2+ ions in both the visible and near infrared regions was observed, but discrepancies in literature suggested a relevant role of glass composition on the definition of the optical signature of cobalt. Co-doped glasses with different composition (soda-lime, potash-lime, mixed alkali and ZnO-Na2O-CaO-SiO2) were studied via Fiber Optic Reflectance Spectroscopy (FORS). Pseudo-Voigt functions were used for the deconvolution of the absorbance spectra and the features of the bands characteristic of each cobalt complex were investigated. The structural role played by each modifying cation and the fundamental implications of glass basicity on the speciation of different Co-complexes were stressed. Changes in glass structure resulted in different equilibria between the three absorbing species whose specific optical signatures in the 480-530nm region interact to determine the resulting absorbance spectrum.

On the making, mixing and trading of glass from the Roman military fort at Oudenburg (Belgium)

This paper presents the analysis of decoloured and naturally coloured glass from well-dated contexts in the southwest corner of the Roman fort at Oudenburg (Belgium) ranging from the late second to the early fifth century AD. The aim is three-fold. First, provide comparative material in the study of glass consumption from the northwestern provinces of the Roman Empire. Secondly, evaluate possible diachronic shifts in the applied decolourizing agent to produce colourless glass as to assess potential correlations between glass production recipes, provenance and chrono-typology. Finally, provide an added value to the research of glass recycling and mixing in the Roman imperial period. Nine subgroups are distinguished based on their chemical composition determined by LA-ICP-MS: Sb-only, two groups of Mn-only, four groups of mixed Mn-Sb, HIMT and one glass without any decolouring agent. The Sb-decoloured glass is used in the earliest phases and can be attributed to an Egyptian provenance. The two subgroups of Mn-glass likely come from different provenances: one from Egypt and the other later one from the Levant. Most of the glass shows high marks of mixing based on high trace elements concentrations and the simultaneous presence of antimony and manganese. Inhomogeneous mixing of manganese and antimony was also detected through μXRF. One Mn-Sb subgroup likely comes from mixing antimony glass with HIMT. The obtained results help better recognise the shifts in applied glass recipes throughout the Roman imperial period and improve our understanding about the mixing and recycling of glass to supply a Roman military camp.

The use of vitrum obsianum in the Roman Empire: some new insights and future prospects

The research on the use of obsidian in the Mediterranean is extensive but this concerns almost exclusively the exploitation of volcanic glass from prehistoric and Bronze Age contexts. The consumption of obsidian during the Roman imperial period in contrast has only occasionally received attention. Never a comprehensive account on what the Romans made in vitrum obsianum has been set up, nor have the sources exploited by them been examined. The aim of the present paper is to provide a concise overview on the current knowledge regarding the use of obsidian during the Roman imperial period and to offer an introductory outline on potential research. The ancient writers inform us about the use of volcanic glass to create exclusive vessels, gemstones, mirrors and sculpture, but also about the creation of black appearing man-made glass initiated as a cheap and easier workable substitute. The archaeological data however propose a more complex story with the occurrence of obsidian chunks in early Roman secondary glass workshops, and the bulky use of obsidian in late Antiquity to produce tesserae for the creation of wall and vault mosaics. Within the Mediterranean three source areas have been recognized that have been responsible for the supply of obsidian in Antiquity: various Italian and Greek islands (Pantelleria, Lipari, Sardinia, Melos, Giali…) and eastern Turkey (Cappadocia, Lake Van district). For a more detailed research to establish the specific obsidian sources used by the Romans and define their distribution networks, the characterization of the obsidian architectural material offers many opportunities. Obsidian can be clearly discriminated from man-made glass by means of non-destructive chemico-physical analyses. A simple device such as portable X-ray fluorescence (XRF) can be used to determine the chemical obsidian of an object enabling a comparison with known glass/obsidian compositions. Raman spectroscopy is another useful technique to distictively seperate glass from obsidian and is applicable for in-situ measurements in museums and archaeological sites by means of a portable Raman spectrometer.