Speciation of Uranium in Sediments before and after In situ Biostimulation

The success of sequestration-based remediation strategies will depend on detailed information, including the predominant U species present as sources before biostimulation and the products produced during and after in situ biostimulation. We used X-ray absorption spectroscopy to determine the valence state and chemical speciation of U in sediment samples collected at a variety of depths through the contaminant plume at the Field Research Center at Oak Ridge, TN, before and after approximately 400 days of in situ biostimulation, as well as in duplicate bioreduced sediments after 363 days of resting conditions. The results indicate that U(VI) in subsurface sediments was partially reduced to 10–40% U(IV) during biostimulation. After biostimulation, U was no longer bound to carbon ligands and was adsorbed to Fe/Mn minerals. Reduction of U(VI) to U(IV) continued in sediment samples stored under anaerobic condition at <4 °C for 12 months, with the fraction of U(IV) in sediments more than doubling and U concentrations in the aqueous phase decreasing from 0.5-0.74 to <0.1 µM. A shift of uranyl species from uranyl bound to phosphorus ligands to uranyl bound to carbon ligands and the formation of nanoparticulate uraninite occurred in the sediment samples during storage.

Deposition of Uranium Precipitates in Dolomitic Gravel Fill

Uranium-containing precipitates have been observed in a dolomitic gravel fill near the Department of Energy (DOE) S-3 Ponds former waste disposal site as a result of exposure to acidic (pH 3.4) groundwater contaminated with U (33 mg L-1), Al3+ (900 mg L-1), and NO3- (14?000 mg L-1). The U containing precipitates fluoresce a bright green under ultraviolet (UV) short-wave light which identify U-rich coatings on the gravel. Scanning electron microscopy (SEM) microprobe analysis show U concentration ranges from 1.6-19.8% (average of 7%) within the coatings with higher concentrations at the interface of the dolomite fragments. X-ray absorption near edge structure spectroscopy (XANES) indicate that the U is hexavalent and extended X-ray absorption fine structure spectroscopy (EXAFS) shows that the uranyl is coordinated by carbonate. The exact nature of the uranyl carbonates are difficult to determine, but some are best described by a split K+-like shell similar to grimselite [K4Na(UO2)(CO3)3·H2O] and other regions are better described by a single Ca2+-like shell similar to liebigite [Ca2(UO2)(CO3)3·11(H2O)] or andersonite [Na2CaUO2(CO3)3 · 6H2O]. The U precipitates are found in the form of white to light yellow cracked-formations as coatings on the dolomite gravel and as detached individual precipitates, and are associated with amorphous basalumnite [Al4(SO4)(OH)10·4H2O].

First dielectronic recombination measurements with H-like uranium

In this report we show first results on dielectronic recombination (DR) measurements with H-like uranium U91+. The experiments were conducted at the heavy ion storage ring ESR of GSI. The electron cooler of the ESR was used as a target for free electrons. Stochastic pre-cooling of the stored ion beam was employed in order to accomplish high-energy resolution at the necessary high electron-ion collision energies of more than 64 keV. For the DR of U91+ this novel technique enabled us to measure for the first time the KLL-DR process and even to resolve the individual j-j' fine structure components of the KLjLj' resonances. The experimental data are compared with fully relativistic Multi-Configuration Dirac-Fock (DR-MCDF) calculations. (c) 2006 Elsevier Ltd. All rights reserved.

Polarization studies of radiative electron capture into highly-charged uranium ions

Recent advances in the development of 2D microstrip detectors open up new possibilities for hard x-ray spectroscopy, in particular for polarization studies. These detectors make ideal Compton polarimeters, which enable us to study precisely the polarization of hard x-rays. Here, we present recent results from measurements of Radiative Electron Capture into the K-shell of highly-charged uranium ions. The experiments were performed with a novel 2D Si(Li) Compton polarimeter at the Experimental Storage Ring at GSI. Stored and cooled beams of U91+ and U92+ ions, with kinetic energies of 43 MeV/u and 96 MeV/u respectively, were crossed with a hydrogen gasjet. The preliminary data analysis shows x-rays from the K-REC process, emitted perpendicularly to the ion beam, to be strongly linearly polarized.