Hydration of α-UO3 following storage under controlled conditions of temperature and relative humidity.

Changes in chemical speciation of uranium oxides following storage under varied conditions of temperature and relative humidity are valuable for characterizing material provenance. In this study, subsamples of high purity α-UO3 were stored under four sets of controlled conditions of temperature and relative humidity over several years, and then measured periodically for chemical speciation. Powder X-ray diffraction (XRD) analysis and extended X-ray absorption fine structure spectroscopy confirm hydration of α-UO3 to a schoepite-like end product following storage under each of the varied storage conditions, but the species formed during exposure to the lower relative humidity and lower temperature condition follows different trends from those formed under the other three storage conditions (high relative humidity with high or low temperatures, and low relative humidity with a high temperature). Thermogravimetry coupled with XRD analysis was carried out to distinguish desorption pathways of water from the hydrated end products. Density functional theory calculations discern changes in the structure of α-UO3 following incorporation of 1, 2 or 3 H2O molecules or 1, 2 or 3 OH groups into the orthorhombic lattice, revealing differences in lattice constants, U-O bond lengths, and U-U distances. The collective results from this analysis are in contrast to analogous studies that report that U3O8 is oxidized and hydrated in air during storage under high relative humidity conditions.

Induction of Short-Term Sensitization by an Aversive Chemical Stimulus in Zebrafish Larvae.

Larval zebrafish possess a number of molecular and genetic advantages for rigorous biological analyses of learning and memory. These advantages have motivated the search for novel forms of memory in these animals that can be exploited for understanding the cellular and molecular bases of vertebrate memory formation and consolidation. Here, we report a new form of behavioral sensitization in zebrafish larvae that is elicited by an aversive chemical stimulus [allyl isothiocyanate (AITC)] and that persists for ≥30 min. This form of sensitization is expressed as enhanced locomotion and thigmotaxis, as well as elevated heart rate. To characterize the neural basis of this nonassociative memory, we used transgenic zebrafish expressing the fluorescent calcium indicator GCaMP6 (Chen et al., 2013); because of the transparency of larval zebrafish, we could optically monitor neural activity in the brain of intact transgenic zebrafish before and after the induction of sensitization. We found a distinct brain area, previously linked to locomotion, that exhibited persistently enhanced neural activity following washout of AITC; this enhanced neural activity correlated with the behavioral sensitization. These results establish a novel form of memory in larval zebrafish and begin to unravel the neural basis of this memory.

Ab initio study of gallium stabilized δ-plutonium alloys and hydrogen-vacancy complexes.

All-electron density functional theory was used to investigate δ-plutonium (δ-Pu) alloyed with gallium (Ga) impurities at 3.125, 6.25, 9.375 atomic (at)% Ga concentrations. The results indicated that the lowest energy structure is anti-ferromagnetic, independent of the Ga concentration. At higher Ga concentrations (>3.125 at%), the position of the Ga atoms are separated by four nearest neighbor Pu-Pu shells. The results also showed that the lattice constant contracts with increasing Ga concentration, which is in agreement with experimental data. Furthermore with increasing Ga concentration, the face-centered-cubic structure becomes more stably coupled with increasing short-range disorder. The formation energies show that the alloying process is exothermic, with an energy range of -0.028 to -0.099 eV/atom. The analyses of the partial density of states indicated that the Pu-Ga interactions are dominated by Pu 6d and Ga 4p hybridizations, as well as Ga 4s-4p hybridizations. Finally, the computed formation energies for vacancy and hydrogen-vacancy complexes within the 3.125 at% Ga cell were 1.12 eV (endothermic) and -3.88 eV (exothermic), respectively. In addition, the hydrogen atom prefers to interact much more strongly to the Pu atom than the Ga atom in the hydrogen-vacancy complex.

Hydrogen trapping in δ-Pu: insights from electronic structure calculations.

Density functional theory calculations have been performed to provide details of the structural and charge-transfer details related to the solid solution of hydrogen in (δ)-plutonium. We follow the Flanagan model that outlines the process by which hydrogen interacts with a metal to produce hydride phases, via a sequence of surface, interstitial and defect-bound (trapped) states. Due to the complexities of the electronic structure in plutonium solid-state systems, we take the pragmatic approach of adopting the 'special quasirandom structure' to disperse the atomic magnetic moments. We find that this approach produces sound structural and thermodynamic properties in agreement with the available experimental data. In δ-Pu, hydrogen has an exothermic binding energy to all of the states relevant in the Flanagan model, and, furthermore, is anionic in all these states. The charge transfer is maximized (i.e. most negative for hydrogen) in the hydride phase. The pathway from surface to hydride is sequentially exothermic, in the order surface < interstitial < grain boundary < vacancy < hydride (hydride being the most exothermic state). Thus, we find that there is no intermediate state that involves an endothermic increase in energy, consistent with the general experimental observations that the hydriding reaction in plutonium metal can proceed with zero apparent activation barrier.