UO2 dissolution in bicarbonate solution with H2O2: the effect of temperature.

Upon nuclear waste canister failure and contact of spent nuclear fuel with groundwater, the UO2 matrix of spent fuel will interact with oxidants in the groundwater generated by water radiolysis. Bicarbonate (HCO3-) is often found in groundwater, and the H2O2 induced oxidative dissolution of UO2 in bicarbonate solution has previously been studied under various conditions. Temperatures in the repository at the time of canister failure will differ depending on the location, yet the effect of temperature on oxidative dissolution is unknown. To investigate, the decomposition rate of H2O2 at the UO2 surface and dissolution of UVI in bicarbonate solution (0.1, 1, 10 and 50 mM) was analysed at various temperatures (10, 25, 45 and 60 °C). At [HCO3-] ≥ 1 mM, the concentration of dissolved UVI decreased with increasing temperature. This was attributed to the formation of UVI-bicarbonate species at the surface and a change in the mechanism of H2O2 decomposition from oxidative to catalytic. At 0.1 mM, no obvious correlation between temperature and U dissolution was observed, and thermodynamic calculations indicated this was due to a change in the surface species. A pathway to explain the observed dissolution behaviour of UO2 in bicarbonate solution as a function of temperature was proposed.

Application of High-Energy-Resolution X-ray Absorption Spectroscopy at the U L3-Edge to Assess the U(V) Electronic Structure in FeUO4.

FeUO4 was studied to clarify the electronic structure of U(V) in a metal monouranate compound. We obtained the peak splitting of spectra utilizing high-energy-resolution fluorescence detection-X-ray absorption near-edge structure (HERFD-XANES) spectroscopy at the U L3-edge, which is a novel technique in uranium(V) monouranate compounds. Theoretical calculations revealed that the peak splitting was caused by splitting of the 6d orbital of U(V) in FeUO4, which would be used to detect minor U(V) species. Such distinctive electronic states are of major interest to researchers and engineers working in various fields, from fundamental physics to the nuclear industry and environmental sciences for actinide elements.

Speciation of chromium aqua and chloro complexes in hydrochloric acid solutions at 298 K.

The distribution of metal aqua and chloro complexes is fundamental information for analysis of a chemical reaction involving these complexes. The present study investigated the speciation and structures of chromium aqua and chloro complexes using the thermodynamic model fitting analysis of UV-vis/X-ray absorption spectra. The existence of a negatively charged species was examined by adsorbability of chromium species on a strong base anion exchanger. In the results, a planar square [CrIII(H2O)4]3+, a planar square or distorted tetrahedral [CrIIICl(H2O)3]2+, a trigonal bipyramidal [CrIIICl3(H2O)2]0, and a distorted octahedral [CrIIICl4(H2O)2]- were confirmed and the thermodynamic parameters of complexation reactions were quantitatively determined. Investigation of the evolution of speciation of chromium aqua and chloro complexes in a pH 1 solution suggested the existence of [CrIIICl2(H2O) m ]+ (m = 2 or 3) during the hydration process, which diminished in the equilibrium state. The kinetic analysis deserves further investigation to understand the speciation process quantitatively.

Competencies That Japanese Collegiate Sports Coaches Require for Dual-Career Support for Student Athletes.

The purpose of this study was to clarify coaches' competencies (COM) regarding dual-career (DC) support for student athletes in Japan. The questionnaire survey was conducted at 31 universities with an online survey URL that was distributed to 300 collegiate athletic coaches. In total, there were 152 respondents (female, 19; male, 133; mean age, 43.15 ± 12.07 years; coaching experience, 12.83 ± 9.72 years). The online survey adopted a Japanese-translated version of the Dual-Career Competency Questionnaire (DCCQ), which has been translated into nine languages and is widely used in European counties. The scale consists of six factors and 33 items, each rated on a five-point scale of importance (IM) and possession (PO). The Japanese version of the DCCQ was validated through a confirmatory factor analysis, and the internal consistency of the items was confirmed by calculating the Cronbach's alpha coefficient. In addition, we examined differences between the IM and PO for DC support by t-tests and by calculating effect sizes. The validity and reliability of the Japanese version of the DCCQ were confirmed based on the goodness-of-fit index and Cronbach's alpha coefficients, respectively. Our examination of the differences between IM and PO in DC support revealed that coaches perceived the importance of DC support but did not possess the necessary COM to offer DC support. That finding was similar to those of previous European studies. In particular, the Japanese coaches who participated in our online survey recognized the importance of COM in terms of "collaboration with various stakeholders and departments" for DC support but did not feel as though they held sufficient COM in that regard. In other words, the improvement of DC support requires the development of a coaching program that fosters COM to work with various stakeholders. This key insight provides a direction and specific focus for programs to improve coaches' DC support for student athletes.

Deep groundwater physicochemical components affecting actinide migration.

To better understand the migration behavior of actinides in deep groundwater (GW), the interactions between doped tracers and deep GW components were investigated. La, Sm, Ho, and U tracers (10 or 100 ppb) were doped into sedimentary rock GW samples collected from 250 to 350 m deep boreholes in the experimental gallery of the Horonobe Underground Research Laboratory (URL), Hokkaido, Japan. To evaluate the effect of GW composition on the chemical speciation of actinides, the same tracers were doped into crystalline rock GW samples collected from 300 to 500 m deep boreholes in the experimental gallery at the Mizunami URL, Gifu Prefecture, Japan. Each GW sample was sequentially filtered through a micro-pore filter (0.2 µm) and ultrafilters with a 10 kDa nominal molecular weight limit. Next, the filtrate solutions were analyzed using inductively coupled plasma-mass spectrometry to determine the concentration of tracers retained in solution during each filtration step, and the used filters were analyzed using time-of-flight secondary ion mass spectrometry element mapping and X-ray absorption fine structure spectroscopy to determine the chemical species of the tracers trapped on each filter. It was determined that lanthanide migration was controlled by the amount of phosphates in the Horonobe GW. Therefore, it was expected that the solubility of minor actinides (MAs), which exhibit a similar chemical behavior to that of lanthanides, would be controlled by the formation of phosphates in sedimentary rock GW. Moreover, the data on the Mizunami GW indicated that a fraction of lanthanides and MAs formed hydroxides and/or hydroxocarbonates.

Autoimmune glial fibrillary acidic protein astrocytopathy resembling isolated central nervous system lymphomatoid granulomatosis.

We report two patients with meningoencephalomyelitis without evidence of extra central nervous system (CNS) involvement. Brain MRI showed linear perivascular radial gadolinium enhancement patterns and spinal cord MRI showed longitudinal extensive T2-hyperintensity lesions. Pathological findings from brain biopsies were angiocentric T-cell predominant lymphoid infiltrates that lacked Epstein-Barr virus-positive atypical B cells. The patients were initially suspected to have isolated CNS-lymphomatoid granulomatosis (LYG). Thereafter, glial fibrillary acidic protein (GFAP)-immunoglobulin G were detected in their cerebrospinal fluid. This finding suggested autoimmune GFAP astrocytopathy. We speculate there is a link between isolated CNS-LYG and autoimmune GFAP astrocytopathy.

The kinetics and mechanism of H2O2 decomposition at the U3O8 surface in bicarbonate solution.

In the event of nuclear waste canister failure in a deep geological repository, groundwater interaction with spent fuel will lead to dissolution of uranium (U) into the environment. The rate of U dissolution is affected by bicarbonate (HCO3 -) concentrations in the groundwater, as well as H2O2 produced by water radiolysis. To understand the dissolution of U3O8 by H2O2 in bicarbonate solution (0.1-50 mM), dissolved U concentrations were measured upon H2O2 addition (300 µM) to U3O8/bicarbonate mixtures. As the H2O2 decomposition mechanism is integral to the dissolution of U3O8, the kinetics and mechanism of H2O2 decomposition at the U3O8 surface was investigated. The dissolution of U3O8 increased with bicarbonate concentration which was attributed to a change in the H2O2 decomposition mechanism from catalytic at low bicarbonate (≤5 mM HCO3 -) to oxidative at high bicarbonate (≥10 mM HCO3 -). Catalytic decomposition of H2O2 at low bicarbonate was attributed to the formation of an oxidised surface layer. Second-order rate constants for the catalytic and oxidative decomposition of H2O2 at the U3O8 surface were 4.24 × 10-8 m s-1 and 7.66 × 10-9 m s-1 respectively. A pathway to explain both the observed U3O8 dissolution behaviour and H2O2 decomposition as a function of bicarbonate concentration was proposed.

Desorption of radioactive cesium by seawater from the suspended particles in river water.

In 2011, the accident at the Fukushima-Daiichi nuclear power plant dispersed radioactive cesium throughout the environment, contaminating the land, rivers, and sea. Suspended particles containing clay minerals are the transportation medium for radioactive cesium from rivers to the ocean because cesium is strongly adsorbed between the layers of clay minerals, forming inner sphere complexes. In this study, the adsorption and desorption behaviors of radioactive cesium from suspended clay particles in river water have been investigated. The radioactive cesium adsorption and desorption experiments were performed with two kinds of suspended particulate using a batch method with 137Cs tracers. In the cesium adsorption treatment performed before the desorption experiments, simulated river water having a total cesium concentration ([133+137Cs+]total) of 1.3 nM (10-9 mol/L) was used. The desorption experiments were mainly conducted at a solid-to-liquid ratio of 0.17 g/L. The desorption agents were natural seawater collected at 10 km north of the Fukushima-Daiichi nuclear power plant, artificial seawater, solutions of NaCl, KCl, NH4Cl, and 133CsCl, and ultrapure water. The desorption behavior, which depends on the preloaded cesium concentration in the suspended particles, was also investigated. Based on the cesium desorption experiments using suspended particles, which contained about 1000 ng/g loaded cesium, the order of cesium desorption ratios for each desorption agent was determined as 1 M NaCl (80%) > 470 mM NaCl (65%) > 1 M KCl (30%) ≈ seawater (natural seawater and Daigo artificial seawater) > 1 M NH4Cl (20%) > 1 M 133CsCl (15%) ≫ ultrapure water (2%). Moreover, an interesting result was obtained: The desorption ratio in the 470 mM NaCl solution was much higher than that in seawater, even though the Na+ concentrations were identical. These results indicate that the cesium desorption mechanism is not a simple ion exchange reaction but is strongly related to structural changes in the clay minerals in the suspended particles. Hydrated Na+ ions expand the interlayer distance of the clay minerals, resulting in the facile desorption of cesium; in contrast, dehydrated K+ ions reduce the interlayer distance and inhibit the desorption of cesium. In conclusion, the desorption of cesium from the suspended particles is controlled by the presence of sodium and potassium ions and the preloaded cesium concentration in the suspended particles.

Anti-inflammatory and antioxidative effects of a methanol extract from bulbs of Scilla scilloides.

The extract from bulbs of Scilla scilloides exhibited inhibitory effects in lipoxygenase and hyaluronidase assays and various oxidation models in vitro. Incubating the cells in the presence of this extract ameliorated t-butyl hydroperoxide-induced cytotoxicity from 27% to 57% in a macrophage model. The results may indicate the potential role of S. scilloides for its anti-inflammatory and antioxidative effects.

Beam homogenizer for hollow-fiber delivery system of excimer laser light.

A beam homogenizer for a hollow-fiber-based, UV laser delivery system is proposed. A rectangular glass waveguide with an inner aluminum coating that has a 1-mm square cross section is attached at the output end of the circular-core hollow fiber with a 1-mm inner diameter. The rectangular waveguide generates a number of higher-order modes and results in a uniform top-hat profile. The configuration of the waveguide is designed by a ray-tracing technique so that both the low transmission loss and the high uniformity in the output beam are obtained. The fabricated waveguide shows a low loss of 0.4 dB, and the intensity variation coefficient is 7%. The output beam from the rectangular waveguide is expanded by a lens to the size larger than 10-mm square. It is also shown that the profile does not change with the bending condition.