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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. [ABSTRACT FROM AUTHOR]

Abstract: X-ray Absorption Spectroscopy (XAS), X-Ray Diffraction (XRD), Thermo-Gravimetric Analysis (TGA) and Scanning Electron Microscopy–Energy Dispersive Spectroscopy (SEM–EDS) techniques were used to determine the composition and the speciation of Fe and Mn in road dust samples collected in the Traforo del San Bernardo highway tunnel. Principal Component Analysis and Least Square Fitting on the XANES region of the absorption spectra and structural refinements on the EXAFS part of the spectra were applied to obtain complementary information on the speciation, average oxidation state, and local structure of Fe and Mn. XRD indicated the presence of silica, calcite, gypsum, and of various phyllosilicates. TGA analysis confirmed the presence of phyllosilicates and also detected a significant amount of organic phases. These findings indicate the co-presence of particles of natural origin along with the organic phases related to vehicular gas exhausts emission. On the other hand, XAS analysis showed that iron is mainly present in the Fe3O4 and FeCl3 forms, which can be considered to have both anthropic origin, i.e., exhaust emission and salt used to prevent ice formation, respectively. [Copyright &y& Elsevier]

Abstract: Acid waters and sediments of the Tinto Santa Rosa acid stream (Iberian Pyritic Belt; SW, Spain) were analysed to determine the role of sedimentary phases in the behaviour of arsenic. Aqueous arsenic and iron concentrations decreased markedly from the adit mouth to 300m downstream indicating iron minerals precipitation as well as arsenic sorption onto these newly-formed phases. This was confirmed by the high arsenic concentrations observed in bed-stream precipitates, which play a major role in controlling arsenic mobility. To unravel the complex nature of the AMD sediments a combination of techniques including X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), total solid digestions, X-Ray Fluorescence (XRF) and X-Ray Absorption Spectroscopy (XAS) were employed. Results showed that (1) arsenic was present predominantly in its pentavalent state; (2) upstream arsenic was sorbed onto the main phase, schwertmannite, whereas downstream it was chiefly associated with goethite and jarosite; and (3) changes in arsenic speciation with depth were observed in the consolidated terrace sediments, where arsenic appeared primarily associated with schwertmannite in the upper part of the terraces, but with goethite at depth. Arsenic mobilization was controlled by sorption onto newly formed precipitates (schwertmannite, goethite and jarosite), causing natural arsenic attenuation. [Copyright &y& Elsevier]