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Abstract: Fourier-transform infrared (FTIR) spectroscopy is a widespread and highly sensitive analytical method for the identification and characterization of a wide range of materials via their infrared (IR) absorption bands. Until now, the potential of IR microspectroscopy and imaging for the characterization of works of art or other objects of cultural heritage significance has been only partially exploited; in particular the use of the synchrotron radiation (SR) IR microprobe to study, at the micron scale, materials of interest for archaeological and cultural heritage studies has become popular only in the past decade. One of the main requirements imposed on the studies of ancient and/or valuable materials is that the techniques applied must be non-destructive. In this scenario, SRbased FTIR methods are perfectly suitable. Moreover, IR spectroscopy and imaging are emerging techniques that combine the assets of IR in terms of molecular specificity with the unique properties of synchrotron light. SR-FTIR micro-spectroscopy offers great advantages over conventional methods because it provides a broader spectrum (down to THz) and higher spectral quality (signal/noise ratio) at the highest spatial resolution (diffraction limited). This is due to the high brilliance and collimation of SR-IR, while still being non-damaging to the investigated system. The unique SR-IR parameters are essential for the compositional analysis of the tiny, sub-millimetric samples characteristic of ancient materials, which are heterogeneous by nature, and with complex molecular distributions at extremely variable concentrations. SR-FTIR spectroscopy and imaging can be applied successfully to the characterization of organic and inorganic materials via so-called IR fingerprinting, as well as for their compositional quantification. The range of materials investigated is very broad and encompasses painting materials, stones, glasses, ceramics, coatings on metals, paper and wooden materials, canvas or other textiles, organic colourants, resins, varnishes, cosmetics, and binding media such as glues, waxes, oils, etc. SR-IR-based methods can also be used to understand the historical technologies and to identify the raw materials used to produce archaeological artefacts and art objects, and to improve stabilization, conservation and restoration practices. Selected applications of SR-FTIR methods are discussed with a special emphasis on the chemical and mineralogical characterization of ancient paintings, on the study of alteration and corrosion layers, and the separation and identification of pigments. New perspectives offered by existing facilities and new developments in IR imaging and advanced vibrational spectroscopy that may broaden the variety of archaeological and historical materials that may be studied are outlined.

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Abstract: Structural changes of MoO3 thin films deposited on thick copper substrates upon annealing at different temperatures were investigated via ex situ X-Ray Absorption Spectroscopy (XAS). From the analysis of the X-ray Absorption Near-Edge Structure (XANES) pre-edge and Extended X-ray Absorption Fine Structure (EXAFS), we show the dynamics of the structural order and of the valence state. As-deposited films were mainly disordered, and ordering phenomena did not occur for annealing temperatures up to 300 °C. At ~350 °C, a dominant α-MoO3 crystalline phase started to emerge, and XAS spectra ruled out the formation of a molybdenum dioxide phase. A further increase of the annealing temperature to ~500 °C resulted in a complex phase transformation with a concurrent reduction of Mo6+ ions to Mo4+. These original results suggest the possibility of using MoO3 as a hard, protective, transparent, and conductive material in different technologies, such as accelerating copper-based devices, to reduce damage at high gradients.

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Abstract: X-ray absorption near edge structure (XANES) measurements at the Fe K-edge were performed on aeolian dust in the TALos Dome Ice CorE drilling project (TALDICE) ice core drilled in the peripheral East Antarctic plateau, as well as on Southern Hemisphere potential source area samples. While South American sources show, as expected, a progressive increase in Fe oxidation with decreasing latitude, Antarctic sources show Fe oxidation levels higher than expected in such a cold polar environment, probably because of their very high exposure ages. Results from the TALDICE dust samples are compatible with a South American influence at the site during MIS2 (marine isotopic stage 2, the last and coldest phase of the last glacial period), in particular from Patagonia and Tierra del Fuego. However, a contribution from Australia and/or local Antarctic sources cannot be ruled out. Finally, important changes also occurred during the deglaciation and in the Holocene, when the influence of Antarctic local sources seems to have become progressively more important in recent times. This research is the first successful attempt to extract temporal climatic information from X-ray absorption spectroscopic data of the insoluble mineral dust particles contained in an ice core and shows the high potential of this technique.

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Abstract: In this work, we will report applications of the total external X-ray fluorescence (TXRF) station, a prototype assembled at the XLab Frascati laboratory (XlabF) at the INFN National Laboratories of Frascati (INFN LNF). XlabF has been established as a facility to study, design and develop X-ray optics, in particular, polycapillary lenses, as well as to perform X-ray experiments for both elemental analysis and tomography. The combination of low-power conventional sources and policapillary optics allows assembling a prototype that can provide a quasi-parallel intense beam for detailed X-ray spectroscopic analysis of extremely low concentrated samples, down to ng/g. We present elemental analysis results of elements contained in tree rings and of dust stored in deep ice cores. In addition to performing challenging environmental research studies, other experiments aim to characterize novel optics and to evaluate original experimental schemes for X-ray diffraction (XRD), X-ray fluorescence (XRF and TXRF) and X-ray imaging.

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Abstract: We investigated the oxidation behaviour of a synthetic potassic-ferro-richterite up to 750 °C by using simultaneous X-ray absorption spectroscopy and X-ray diffraction experiments with synchrotron radiation. From the X-ray diffraction results, we observed an abrupt decrease of cell dimensions at ∼335 °C accompanied by an anomalous increase in the monoclinic cell angle β. From the analysis of the XANES spectra at the iron K-edge, we observed that the structural shrinkage is due to the iron oxidation process, coupled to hydrogen loss, occurring at ∼315 °C, slightly before the cell contraction. Combining these results with previous studies performed on similar samples by single-crystal structure refinement, Mössbauer, high temperature-Fourier transform IR and Raman spectroscopies, we show that the temperature evolution in Fe-amphiboles is a multi-step process. Following the iron oxidation driven by temperature, the structural dynamics in this double-chain silicate is ruled by local strains in the ribbon of iron-filled octahedra, mainly due to the contraction of the M(1) site.