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Abstract: Here we report the results of multiple analytical techniques on sub-mm particulate material derived from Unit 1 of the Fukushima Daiichi Nuclear Power Plant to provide a better understanding of the events that occurred and the environmental legacy. Through combined x-ray fluorescence and absorption contrast micro-focused x-ray tomography, entrapped U particulate are observed to exist around the exterior circumference of the highly porous Si-based particle. Further synchrotron radiation analysis of a number of these entrapped particles shows them to exist as UO2—identical to reactor fuel, with confirmation of their nuclear origin shown via mass spectrometry analysis. While unlikely to represent an environmental or health hazard, such assertions would likely change should break-up of the Si-containing bulk particle occur. However, more important to the long-term decommissioning of the reactors at the FDNPP (and environmental clean-upon), is the knowledge that core integrity of reactor Unit 1 was compromised with nuclear material existing outside of the reactors primary containment.

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Abstract: Bulk studies have revealed a first-order valence phase transition in Ba 2 PrRu 1 − x Ir x O 6 ( 0.10 ≤ x ≤ 0.25 ), which is absent in the parent compounds with x = 0 ( Pr 3 + ) and x = 1 ( Pr 4 + ), which exhibit antiferromagnetic order with transition temperatures T N = 120 and 72 K, respectively. In the present study, we have used magnetization, heat capacity, neutron diffraction, inelastic neutron scattering, and x-ray absorption measurements to investigate the nature of the Pr ion in x = 0.1 . The magnetic susceptibility and heat capacity of x = 0.1 show a clear sign of the first-order valence phase transition below 175 K, where the Pr valence changes from 3+ to 4+. Neutron diffraction analysis reveals that x = 0.1 crystallizes in a monoclinic structure with space group P 2 1 / n at 300 K, but below 175 K two phases coexist, the monoclinic having the Pr ion in a 3+ valence state and a cubic one ( F m ¯ 3 m ) having the Pr ion in a 4+ valence state. Clear evidence of an antiferromagnetic ordering of the Pr and Ru moments is found in the monoclinic phase of the x = 0.1 compound below 110 K in the neutron diffraction measurements. Meanwhile, the cubic phase remains paramagnetic down to 2 K, a temperature below which heat capacity and susceptibility measurements reveal a ferromagnetic ordering. High energy inelastic neutron scattering data reveal well-defined high-energy magnetic excitations near 264 meV at temperatures below the valence transition. Low energy INS data show a broad magnetic excitation centered at 50 meV above the valence transition, but four well-defined magnetic excitations at 7 K. The high energy excitations are assigned to the Pr 4 + ions in the cubic phase and the low energy excitations to the Pr 3 + ions in the monoclinic phase. Further direct evidence of the Pr valence transition has been obtained from the x-ray absorption spectroscopy. The results on the x = 0.1 compound are compared with those for x = 0 and 1.

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Abstract: A detailed understanding of the mechanisms and effects of radiation damage in phyllosilicate minerals is a necessary component of the evaluation of the safety case for a deep geological disposal facility (GDF) for radioactive waste. Structural and chemical changes induced by α-particle damage will affect these mineral’s performance as a reactive barrier material (both in the near and far-field) over timescales relevant to GDF integrity. In this study, two examples of chlorite group minerals have been irradiated at α-particle doses comparable to those predicted to be experienced by the clay buffer material surrounding high level radioactive waste canisters. Crystallographic aberrations induced by the focused 4He2+ ion beam are revealed via high-resolution, microfocus X-ray diffraction mapping. Interlayer collapse by up to 0.5 Å is prevalent across both macro- and micro-crystalline samples, with the macro-crystalline specimen displaying a breakdown of the phyllosilicate structure into loosely-connected, multi-oriented crystallites displaying variable lattice parameters. The damaged lattice parameters suggest a localised breakdown and collapse of the OH- rich, ‘brucite-like’ interlayer. Microfocus Fe K-edge X-ray absorption spectroscopy illustrates this defect accumulation, manifest as a severe damping of the X-ray absorption edge. Subtle Fe2+/Fe3+ speciation changes are apparent across the damaged structures. A trend towards Fe reduction is evident at depth in the damaged structures at certain doses (8.76 x 1015 alpha particles/ cm2). Interestingly, this reductive trend does not increase with radiation dose, indeed at the maximum dose (1.26 x 1016 alpha particles/ cm2) administered in this study, there is evidence for a slight increase in Fe binding energy, suggesting the development of a depth-dependant redox gradient concurrent with light ion damage. At the doses examined here, these damaged structures are likely highly reactive, as sorption capacity will, to an extent, be largely enhanced by lattice disruption and an increase in available ‘edge’ sites.

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Abstract: Fe(II) bearing iron (oxyhydr)oxides were directly co-precipitated with Np(V)O2+ under anaerobic conditions to form Np doped magnetite and green rust. These environmentally relevant mineral phases were then characterised using geochemical and spectroscopic analyses. The Np doped mineral phases were then oxidised in air over 224 days with solution chemistry and end-point oxidation solid samples collected for further characterisation. Analysis using chemical extractions and X-ray absorption spectroscopy (XAS) techniques confirmed that Np(V) was initially reduced to Np(IV) during co-precipitation of both magnetite and green rust. Extended X-Ray Absorption Fine Structure (EXAFS) modelling suggested the Np(IV) formed a bidentate binuclear sorption complex to both minerals. Furthermore, following oxidation in air over several months, the sorbed Np(IV) was partially oxidised to Np(V), but very little remobilisation to solution occurred during oxidation. Here, linear combination fitting of the X-Ray Absorption Near Edge Structure (XANES) for the end-point oxidation samples for both mineral phases suggested approximately 50% oxidation to Np(V) had occurred over 7 months of oxidation in air. Both the reduction of Np(V) to Np(IV) and inner sphere sorption in association with iron (oxyhydr)oxides, and the strong retention of Np(IV) and Np(V) species with these phases under robust oxidation conditions, have important implications in understanding the mobility of neptunium in a range of engineered and natural environments.

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Abstract: Synchrotron radiation X-ray fluorescence microscopy is frequently used to investigate the spatial distribution of elements within a wide range of samples. Interrogation of heterogeneous samples that contain large concentration ranges has the potential to produce image artefacts due to the profile of the X-ray beam. The presence of these artefacts and the distribution of flux within the beam profile can significantly affect qualitative and quantitative analyses. Two distinct correction methods have been generated by referencing the beam profile itself or by employing an adaptive-thresholding procedure. Both methods significantly improve qualitative imaging by removing the artefacts without compromising the low-intensity features. The beam-profile correction method improves quantitative results but requires accurate two-dimensional characterization of the X-ray beam profile.