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Abstract: The analysis of reference materials is a fundamental part of the data analysis process, in particular for XAS experiments. The beamline users and more generally the XAS community can greatly benefit from the availability of a reliable and wide base of reference sample spectra, acquired in standard and well-characterized experimental conditions. On B18, the Core EXAFS beamline at the Diamond Light Source, in the past years we have collected a series of XAS data on well characterized compounds. This work constitutes the base for a reference sample database, available as a data analysis tool to the general XAS community. This data repository aims to complement the bare spectroscopic information with characterisation, preparation, provenance, analysis and bibliographic references, so improving the traceability of the deposited information. This integrated approach is the base of success and wide distribution of data repositories in other fields, and we hope it will provide on one side a precious facility for the training of students and researchers new to the technique, and at the same time encourage the discussion of best practices in the data analysis process. The database will be open to the contribution of experimental data from the user community, and will provide bibliographic reference information and access control.

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Abstract: Purportedly originating from the late Predynastic–Early Dynastic period of ancient Egyptian civilisation (about 3100 BC), the statuette known as “MacGregor Man” was acquired near the site of Naqada in southern Egypt by the Reverend William MacGregor at the end of the 19th century. The Ashmolean Museum (University of Oxford) subsequently purchased the statuette at the sale of MacGregor’s collection in 1922, and it remains one of the most important items in the museum’s Egyptology collection. However, the authenticity of the statuette has been the focus of fierce scholarly debate since it first came to light. At that time there was little with which the object could be compared and a forger would have little source material to copy: some of its features are consistent with securely provenanced statuettes and figurines that were discovered some time after the appearance of MacGregor Man. Several other aspects have caused others to question whether MacGregor Man is genuine. It is carved from what is widely believed to be a basaltic rock; rare in ancient Egypt and its hardness would have made sculpting such a detailed statue exceedingly difficult with the tools available to ancient stonemasons. Also, there are strong indications that MacGregor Man may have been deliberately damaged, possibly in an effort to artificially “antiquate” the statuette (though other explanations are feasible). Despite the sustained interest in MacGregor Man, no mineralogical analysis of the stone it is sculpted from has been carried out to date. Though it has been visually identified as being most likely a basalt, it has so far been impossible to ascertain even this basic information without removing a sample from and thus damaging the statue. Even a basic understanding of the mineralogy of the sample could prove informative since basaltic composition can be diagnostic for determining the region of its origin. Using energy-dispersive X-ray diffraction (EDXRD) in a back-reflection geometry, a non-destructive technique, high-resolution powder diffraction data from several regions were collected at Diamond Light Source (Didcot, Oxfordshire, U.K.) in February 2019. From these data, despite poor powder averaging (resulting from the large crystallite size), we plan to extract crystallographic information such as the minerals present and unit cell dimensions. This will be compared to published data from known Egyptian basalt samples in an attempt to ascertain whether it is Egyptian in origin. The results of this crystallographic analysis will be presented.

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Abstract: Airborne dust extracted from deep ice core perforations can provide chemical and mineralogical insight into the history of the climate and atmospheric conditions, with unrivalled temporal resolution, time span and richness of information. The availability of material for research and the natural complexity of the particulate, however, pose significant challenges to analytical methods. We present the developments undertaken to optimize the experimental techniques, materials and protocols for synchrotron radiation-based analysis, in particular for the acquisition of combined Synchrotron Radiation X-Ray Fluorescence and X-ray Absorption Spectroscopy data.

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Abstract: K0.5Bi0.5TiO3 (KBT) – one of the few perovskite-like ferroelectric compounds with room-temperature tetragonal symmetry – differs from other members of this family (BaTiO3 and PbTiO3) by the presence of a disordered mixture of K and Bi on cuboctahedral sites. This disorder is expected to affect local atomic displacements and their response to an applied electric field. We have derived nanoscale atomistic models of KBT by refining atomic coordinates to simultaneously fit neutron/X-ray total-scattering and extended X-ray absorption fine-structure data. Both Bi and Ti ions were found to be offset relative to their respective oxygen cages in the high-temperature cubic phase; in contrast, the coordination environment of K remained relatively undistorted. In the cubic structure, Bi displacements prefer the <100> directions and the probability-density distribution of Bi features six well-separated sites; a similar preference exists for the much smaller Ti displacements although the split sites for Ti could not be resolved. The cation displacements are correlated, yielding polar nanoregions, while on average the structure appears as cubic. The cubic<->tetragonal phase transition involves both order-disorder and displacive mechanisms. A qualitative change in the form of the Bi probability-density distribution occurs in the tetragonal phase on cooling to room temperature because Bi displacements “branch off” to <111> directions. This change, which preserves the average symmetry, is accompanied by the development of nanoscale polar heterogeneities that exhibit significant deviations of their polarization vectors from the average polar axis.

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Abstract: In this work, the authors investigated MoO3 films with thickness between 30 nm and 1 μm grown at room temperature by solid phase deposition on polycrystalline Cu substrates. Atomic force microscopy, scanning electron microscopy, and scanning tunneling microscopy revealed the presence of a homogenous MoO3 film with a “grainlike” morphology, while Raman spectroscopy showed an amorphous character of the film. Nanoindentation measurements evidenced a coating hardness and stiffness comparable with the copper substrate ones, while Auger electron spectroscopy, x-ray absorption spectroscopy, and secondary electron spectroscopy displayed a pure MoO3 stoichiometry and a work function ΦMoO3 = 6.5 eV, 1.8 eV higher than that of the Cu substrate. MoO3 films of thickness between 30 and 300 nm evidenced a metallic behavior, whereas for higher thickness, the resistance–temperature curves showed a semiconducting character.