Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

Genesis of a mottled horizon by Fe-depletion within a laterite cover in the Amazon BasinGenèse d'un horizon tacheté par déferruginisation dans une couverture à latérite du Bassin amazonien

A mottled horizon in a laterite cover (without any duricrust) was studied by microscopy and quantitative chemical microanalysis. Apart from the voids, light red spots consisting of Fe-rich particles (≈2 μm) are set in clayey plasma. Dark red spots consisted of concentrations of Fe-rich particles. These patterns are inherited. On the border of structural or biological voids, where Fe-depletion features are systematic, gray or yellow spots result from dissolution of the Fe-rich particles and impregnation of the plasma by iron, respectively. The present Fe-depletion is the dominant process that explains the mottled differentiation and the absence of lateritic duricrust. To cite this article: V. Rosolen et al., C. R. Geoscience 334 (2002) 187–195.     

X-ray Spectromicroscopy of Mineral Intergrowths in the Santa Catharina Meteorite

This work describes the application of microfocus X-ray absorption spectroscopy (XAS) and X-ray photo-emission electron microscopy (XPEEM) to the study of the complex mineralogical intergrowths within the Santa Catharina meteorite. The Santa Catharina meteorite of this study (BM52283 from the meteorite collection of the Natural History Museum, London, UK) primarily comprises a taenite bulk host phase (Fe:Ni ratio = 70.9 ± 0.8%:29.1 ± 0.8%) with a set of oxide-bearing cloudy zone textured regions (Fe:Ni:O ratio = 40.4 ± 0.3%:49.0 ± 0.7%:10.6 ± 0.8% at the core and Fe:Ni:O ratio = 34.4 ± 1.5%:42.7 ± 0.6%:22.9 ± 1.8% towards the rims) and numerous schreibersite (Fe:Ni:P ratio = 38.6 ± 1.6%:38.4 ± 0.9%:23.0 ± 0.5%) inclusions. Between the schreibersite and the taenite are rims up to 50 μm across of Ni-rich kamacite (Fe:Ni ratio = 93.4 ± 0.4%:6.6 ± 0.5%). No chemical zoning or spatial variations in the Fe and Ni speciation was observed within either the schreibersite or the kamacite phases. The oxide-bearing cloudy zone textured regions mostly comprise metallic Fe–Ni alloy, predominantly tetrataenite. Within the oxide phases, the Fe is predominantly, but not entirely, tetrahedrally co-ordinated Fe³⁺ and the Ni is octahedrally co-ordinated Ni²⁺. Structural analysis supports the suggestion that non-stoichiometric Fe₂NiO₄ trevorite is the oxide phase. The trevorite:tetrataenite ratio increases at the edges of the oxide-bearing cloudy zone textured regions indicating increased oxidation at the edges of these zones. The spatial resolution of the XPEEM achieved was between 110 and 150 nm, which precluded the study of either the previously reported ∼ 10 nm precipitates of tetrataenite within the bulk taenite or any antitaenite.