Analysis of the U L3-edge X-ray absorption spectra in UO2 using molecular dynamics simulations

This work was supported by a grant from the Swiss National Supercomputing Centre (CSCS) under the project ID s444. The resource allocation within the PSI share at CSCS and on the PSI compute cluster Merlin4 is also acknowledged. D. B. is grateful for a fellowship within the Sciex-NMS programme. A. K. was supported by Latvian Science Council Grant no. 187/2012.Uranium L3-edge X-ray absorption spectroscopy was used to study the atomic structure of uranium dioxide (UO2). The extended X-ray absorption fine structure (EXAFS) was interpreted within the ab initio multiple-scattering approach combined with classical molecular dynamics to account for thermal disorder effects. Nine force-field models were validated, and the role of multiple-scattering contributions was evaluated.Swiss National Supercomputing Centre project ID s444; Latvian Science Council grant no. 187/2012; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Analysis of the U L3-edge X-ray absorption spectra in UO2 using molecular dynamics simulations

This work was supported by a grant from the Swiss National Supercomputing Centre (CSCS) under the project ID s444. The resource allocation within the PSI share at CSCS and on the PSI compute cluster Merlin4 is also acknowledged. D. B. is grateful for a fellowship within the Sciex-NMS programme. A. K. was supported by Latvian Science Council Grant no. 187/2012.Uranium L3-edge X-ray absorption spectroscopy was used to study the atomic structure of uranium dioxide (UO2). The extended X-ray absorption fine structure (EXAFS) was interpreted within the ab initio multiple-scattering approach combined with classical molecular dynamics to account for thermal disorder effects. Nine force-field models were validated, and the role of multiple-scattering contributions was evaluated.Swiss National Supercomputing Centre project ID s444; Latvian Science Council grant no. 187/2012; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Kinetics of phase transition in the terrestrial mantle

L’évolution des assemblages pétrologiques avec l’augmentation de pression et de température est couramment perçue à l’équilibre et figée dans le temps. Le développement des sources synchrotron de rayons X permet à présent de mesurer in situ et en temps résolu les vitesses de transformations minéralogiques à haute pression (HP), haute température (HT). Cette thèse présente l’utilisation de cette technologie dans 2 contextes géologiques. (i) Le potentiel sismogène de la déstabilisation des minéraux hydratés dans les plaques en subduction est vérifié. Les cinétiques de déshydratation du talc, de la phase à 10Å et de l’antigorite ont été mesurées à HP-HT en système clos. Nous avons identifié que l’antigorite se déshydrate en passant par un stade intermédiaire. Toutes les vitesses de libération de fluides associées sont plus rapides que la déformation visqueuse des roches et sont donc compatibles avec le déclenchement de rupture. (ii) Les cinétiques de transition olivine-ringwoodite ont été déterminées dans la loupe de costabilité pour des compositions riches en Fe. Elles mettent en évidence une amorphisation partielle de l'olivine en début de transformation. Cela pourrait perturber de manière significative la vitesse des ondes sismiques lors de leur passage au niveau de la zone de transition mantellique. Par ailleurs, les temps caractéristiques de réaction et la réduction conséquente de la taille des grains, indiquent qu’une telle transition de phase induit une atténuation sismique importante. Ces résultats expérimentaux in situ HP-HT révèlent des mécanismes originaux de transition de phase et contribuent ainsi à une meilleure compréhension des modèles géodynamiquesThe evolution of petrological assemblies with increasing pressure and temperature is commonly perceived at equilibrium and fixed within time. The development of X-ray synchrotron sources now enable to measure in situ, time-resolved rates of mineralogical transformations at high pressure (HP), high temperature (HT). This thesis presents the application of this technology in two geological settings. (i) The seismogenic ability of breakdown of hydrated minerals within the subducting slab is checked. The dehydration kinetics of talc, 10Å phase and antigorite were measured at HP-HT in a closed system. We have found that antigorite dehydrates through an intermediate stage. All associated rates of released fluids are faster than the viscous deformation of rocks and are therefore compatible with the trigger of rupture. (ii) The kinetics of olivineringwoodite transition were determined within the co-stability loop for Fe-rich compositions. They show a partial amorphization of olivine at the beginning of the transformation. This could significantly affect the velocities of seismic waves when crossing the mantle transition zone. Moreover, the characteristic times of this reaction and the substantial reduction in grain size, indicate that such a phase transition may induce a significant seismic attenuation. These in situ HP-HT experimental results reveal novel mechanisms of phase transition and thus contribute to a better understanding of geodynamic model

Dehydration kinetics of talc and 10 Å phase: Consequences for subduction zone seismicity

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New Insights into the Thermal Expansion of Neptunium Dioxide up to 2000K

AbstractWe report for the first time the thermal expansion of NpO2 up to 2000K and compare it to the one of UO2 and PuO2. Lattice parameters were measured as a function of temperature by in situ X-ray diffraction with neutral, reducing and oxidizing atmospheres. Data for NpO2 under neutral and reducing conditions perfectly superpose. Up to 1550K, thermal expansion varies linearly with increasing temperature. Above, thermal expansion presents a curvature towards higher lattice parameters. No bibliographic data were available for this temperature range for comparison. As for the thermal expansion of UO2, we propose this curvature is certainly inferred by the formation of lattice defects in the oxygen sub-lattice. Expression of thermal expansion and coefficients of thermal expansion at given temperatures for NpO2, are presented

Kinetics and mechanism of antigorite dehydration: Implications for subduction zone seismicity

International audienceProperties of serpentine minerals are thought to influence the occurrence and location of intermediate‐depth seismicity in subduction zones, which is often characterized by two dipping planes separated by ∼30 km defining a double seismic zone. The seismicity of the lower plane is believed to be provoked by the dehydration of serpentine since the experimentally determined stability limit for antigorite matches hypocenter locations. This requires that the fluid produced by dehydration is released much faster than the typical time scale of ductile deformation mechanisms. Here we measured the kinetics of antigorite dehydration in situ at high pressure and high temperature by time‐resolved synchrotron X‐ray diffraction in a closed system. Antigorite dehydrates in two steps. During step 1 it partially breaks down into olivine and a hydrous phyllosilicate closely related to the 10 Å phase. The modal abundance of the intermediate assemblage is described by 66 wt % antigorite, 19 wt % olivine, 12 wt % 10 Å phase. During step 2 at higher temperature, the remaining antigorite and the 10 Å phase fully dehydrate. From the analysis of reaction progress data, we determined that the major release of aqueous fluid occurs during step 2 at a fast rate of 10−4 mfluid 3 mrock −3 s−1. This exceeds by orders of magnitude the typical time scale of deformation by ductile mechanisms of any mineral or rock in the subducting slab or in the overlying mantle wedge. These results suggest that the fast dehydration of antigorite may well trigger the seismicity of the lower plane of the double seismic zone

Comparative analysis of Vibrio splendidus-related strains isolated during Crassostrea gigas mortality events

International audienceFrench mollusc production is based mainly on the Pacific cupped oyster, Crassostrea gigas. Since 1991, annual mass mortality of juveniles has been reported during summer months. These recurring episodes concern professionals who fear that like Portugese oyster, C. angulata, C. gigas could in turn disappear following one of these epizooties. Previously, bacteriological analysis of moribund oyster juveniles yielded an isolate of a Vibrio splendidus biovar II strain, named TNEMF6. This isolate was demonstrated to be pathogenic to Crassostrea gigas spat by experimental challenge. To study the association between summer oyster mortality and presence of TNEMF6 cluster strains, Vibrionaceae fauna were isolated from infected spat along the French Atlantic coast between 1997-1998. Strains related to V. splendidus biovar II were selected. Comparison with TNEMF6 was performed by classical biochemical tests and polymerase chain reaction - restriction fragment length polymorphism (PCR-RFLP) of SSU rDNA, rpoD, and gyrB genes. Genomic similarities were confirmed by DNA/DNA hybridization. Only one strain out of 14, TNNIII7, was found to be closely related to the pathogenic bacteria. Neither the phenotypic nor the genotypic markers used in this study were able to distinguish pathogenic from non-pathogenic strains of the widespread V. splendidus. However, future genetic comparisons of TNEMF6 and TNNIII7 is likely to reveal genes involved in pathogenicity