The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The ULIII-edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate.
Micro-X-ray fluorescence and X-ray absorption fine structure (µ-XRF-XAFS) is one of the most powerful tools to identify the distribution and speciation of trace elements in natural samples with µm spatial resolution. However, conventional µ-XRF-XAFS studies applied to rare earth elements (REEs: lanthanide elements + Y in this study) are mainly limited to their L-edges and L lines (except for Y) that are subject to strong interferences from other elements (mainly transition metals). In this study, we extend µ-XRF-XAFS to the higher energy region (HE-µ-XRF-XAFS) by using an incident X-ray microbeam (size: ca. 1 × 1 µm2) between 38 and 54 keV to realize K-edge excitation lanthanide analysis without interferences from other elements at the BL37XU beamline, SPring-8 (Japan). This method enables us to simultaneously analyze (i) REE patterns (from La to Dy), (ii) XAFS spectra, and (iii) µm-scale distribution of each REE in the natural sample. The proposed method also realizes the simultaneous application of µ-XAFS at low (e.g., Fe K-edge) and high (lanthanide K-edges) energy at the same spot without changing the setup of the µ-XRF-XAFS system using the detuning technique.
Iddingsite in Martian nakhlites contains various secondary minerals that reflect water–rock interaction on Mars. However, the formation processes of secondary Fe minerals in iddingsite are unclear because they include carbonates precipitated under reductive and alkaline conditions and sulfates that are generally precipitated under oxidative and acidic conditions. Mineral types cannot coexist under equilibrium. Herein, we characterize the carbonate phase of meteorite Yamato 000593 as siderite and Mn-bearing siderite via field-emission electron probe microanalyzer (FE-EPMA). Then, we examined the distribution and speciation of trace Cr and S within the carbonates through synchrotron micro-focused X-ray fluorescence-X-ray absorption fine structure and scanning transmission X-ray microscopy (μ-XRF-XAFS/STXM) analysis to estimate the transition history of Eh-pH conditions during siderite formation to explain the coexistence of carbonate and sulfate phases in the nakhlite vein. Specifically, the distribution and speciation of S in the mesostasis and carbonate phases and the heterogeneous distribution of Mn-FeCO3 incorporating Cr(III) in the carbonate constrain the Eh-pH condition. The conditions and transition of the fluid chemistry determined herein based on speciation of various elements provide a new constraint on the physicochemical condition of the water that altered the nakhlite body during the Amazonian epoch.
15 April 2013 in Journal of the Physical Society of Japan
In this study, we measured the Compton scattering spectra of Al, Ag and Au metals changing the harmonic order of X-rays from an undulator. The width of the Compton scattered X-ray spectrum changed depending on the harmonic order of X-rays. This indicates that Compton scattering spectra shape reflects a momentum perpendicular to the traveling direction in Hermite–Gaussian (HG) light.
We present an extensive investigation (magnetic, electric and thermal measurements and X-ray absorption spectroscopy) of the Pr0.5Ca0.5CoO3 and (Pr1-yYy)0.7Ca0.3CoO3 (y=0.0625-0.15) perovskites, in which a peculiar metal-insulator (M-I) transition, accompanied with pronounced structural and magnetic anomalies, occurs at 76 K and 40-132 K, respectively. The inspection of the M-I transition using the XANES data of Pr L3-edge and Co K-edge proofs the presence of Pr4+ ions at low temperatures and indicates simultaneously the intermediate spin to low spin crossover of Co species on lowering the temperature. The study thus definitively confirms the synchronicity of the electron transfer between Pr3+ ions and Co^(3+/4+)O3 subsystem and the transition to the low-spin, less electrically conducting phase. The large extent of the transfer is evidenced by the good quantitative agreement of the determined amount of the Pr4+ species, obtained either from the temperature dependence of the XANES spectra or via integration of the magnetic entropy change over the Pr4+ related Schottky peak in the low-temperature specific heat. These results show that the average valence of Pr3+/Pr4+ ions increases (in concomitance with the decrease of the formal Co valence) below TMI for (Pr0.925Y0.075)0.7Ca0.3CoO3 up to 3.16+ (the doping level of the CoO3 subsystem decreases from 3.30+ to 3.20+), for (Pr0.85Y0.15)0.7Ca0.3CoO3 up to 3.28+ (the decrease of doping level from 3.30+ to 3.13+) and for Pr0.5Ca0.5CoO3 up to 3.46+ (the decrease of doping level from 3.50+ to 3.27+).