Effect of U(VI) aqueous speciation on the binding of uranium by the cell surface of Rhodotorula mucilaginosa, a natural yeast isolate from bentonites.

This study presents the effect of aqueous uranium speciation (U-hydroxides and U-hydroxo-carbonates) on the interaction of this radionuclide with the cells of the yeast Rhodotorula mucigilanosa BII-R8. This strain was isolated from Spanish bentonites considered as reference materials for the engineered barrier components of the future deep geological repository of radioactive waste. X-ray absorption and infrared spectroscopy showed that the aqueous uranium speciation has no effect on the uranium binding process by this yeast strain. The cells bind mobile uranium species (U-hydroxides and U-hydroxo-carbonates) from solution via a time-dependent process initiated by the adsorption of uranium species to carboxyl groups. This leads to the subsequent involvement of organic phosphate groups forming uranium complexes with a local coordination similar to that of the uranyl mineral phase meta-autunite. Scanning transmission electron microscopy with high angle annular dark field analysis showed uranium accumulations at the cell surface associated with phosphorus containing ligands. Moreover, the effect of uranium mobile species on the cell viability and metabolic activity was examined by means of flow cytometry techniques, revealing that the cell metabolism is more affected by higher concentrations of uranium than the cell viability. The results obtained in this work provide new insights on the interaction of uranium with bentonite natural yeast from genus Rhodotorula under deep geological repository relevant conditions.

On the sequential separation and quantification of 237Np, 241Am, thorium, plutonium, and uranium isotopes in environmental and urine samples.

The implementation of the one-pass-through separation technique using two stacked chromatography columns of TEVA - TRU resins for the separation of 237Np, 241Am, thorium, plutonium and uranium from environmental and urine samples was investigated. The sequential separation technique proved to be successful and gave similar results to those obtained when using individual separations. The analysis time was considerably improved. The amount of chemical waste was also reduced by 50% and the use of HClO4 was avoided. The technique of ICP-MS was also investigated as a complementary technique to alpha-spectrometry.

Redox behavior of uranium at the nanoporous aluminum oxide-water interface: implications for uranium remediation.

Sorption-desorption experiments show that the majority (ca. 80-90%) of U(VI) presorbed to mesoporous and nanoporous alumina could not be released by extended (2 week) extraction with 50 mM NaHCO(3) in contrast with non-nanoporous α alumina. The extent of reduction of U(VI) presorbed to aluminum oxides was semiquantitatively estimated by comparing the percentages of uranium desorbed by anoxic sodium bicarbonate between AH(2)DS-reacted and unreacted control samples. X-ray absorption spectroscopy confirmed that U(VI) presorbed to non-nanoporous alumina was rapidly and completely reduced to nanoparticulate uraninite by AH(2)DS, whereas reduction of U(VI) presorbed to nanoporous alumina was slow and incomplete (<5% reduction after 1 week). The observed nanopore size-dependent redox behavior of U has important implications in developing efficient remediation techniques for the subsurface uranium contamination because the efficiency of in situ bioremediation depends on how effectively and rapidly U(VI) bound to sediment or soil can be converted to an immobile phase.

Long-term leaching of uranium from different waste matrices.

A semi-dynamic leaching test was carried out for metallurgical wastes and ore samples from the uranium and copper mining industry over a 142 day period using distilled water and 0.1N NaNO(3) as solvents. Laser fluorimetry was used as the analytical technique to determine the total uranium content in the leachates. The cumulative leach fraction (CLF) of uranium release from the samples was calculated to be 0.22, 0.22, 0.07 and 0.39% for rock, uranium tailings, copper kinker ash samples and copper tailings respectively using distilled water as solvent and 0.31, 0.27, 0.05 and 0.59% for the same matrices using 0.1N NaNO(3). The release of mobile uranium fraction was very slow, being faster in the initial stage and then attained a near steady state condition. The diffusion coefficient and bulk release of uranium from the samples have been calculated. The processes governing the release of uranium from these matrices have been identified to be surface wash-off and diffusion. Hence the use of weak solvents (leach out the mobile/exchangeable fraction of uranium) under semi-dynamic conditions aids the determination of leaching parameters and identification of the leaching mechanism for mobile uranium fraction from different matrices by slow leaching processes.

Sorption profile and chromatographic separation of uranium (VI) ions from aqueous solutions onto date pits solid sorbent.

The retention profile of uranium (VI) as uranyl ions (UO(2)(2+)) from the aqueous media onto the solid sorbent date pits has been investigated. The sorption of UO(2)(2+) ions onto the date pits was achieved quantitatively (98+/-3.4%, n=5) after 15 min of shaking at pH 6-7. The sorption of UO(2)(2+) onto the used sorbent was found fast, followed by a first order rate equation with an overall rate constant, k of 4.8+/-0.05 s(-1). The sorption data were explained in a manner consistent with a "solvent extraction" mechanism. The sorption data were also subjected to Freundlich isotherm model over a wide range of equilibrium concentration (1-20 microgmL(-1)) of UO(2)(2+). The results revealed that, a "dual-mode" of sorption mechanism involving absorption related to "solvent extraction" and an added component for "surface adsorption" is most likely operated simultaneously for uranyl ions uptaking the solid sorbent. The thermodynamic parameters (-DeltaH, DeltaS and DeltaG) of the uranyl ions uptake onto the date pits indicated that, the process is endothermic and proceeds spontaneously. The interference of some diverse ions on the sorption UO(2)(2+) from the aqueous media onto the date pits packed column was critically investigated and the data revealed quantitative collection of UO(2)(2+) at 5 mLmin(-1) flow rate. The retained UO(2)(2+) was recovered quantitatively with HCl (3.0 molL(-1)) from the column at 5 mLmin(-1) flow rate. The mode of binding of the date pits with UO(2)(2+) was determined from the IR spectral date bits before and after extraction of uranium (VI). The height equivalent (HETP) and the number (N) of theoretical plates of the date pits packed column were determined from the chromatograms. Complete retention and recovery of UO(2)(2+) spiked to wastewater samples by the date pits packed column was successfully achieved. The capacity of the used sorbent towards retention of uranium (VI) from aqueous solutions was much better than the most common sorbents.

Sorption of uranyl ions on titanium oxide studied by ATR-IR spectroscopy.

ATR-IR spectroscopy was used to study the sorption of uranyl ions (10(-4) M) onto titanium oxide (mixture of rutile and anatase). A circulation setup, filled with a solution in D(2)O, allowed recording of the evolution of the antisymmetric O=U=O stretching of uranyl species onto titanium oxide particles deposited on the ATR crystal. The band centered at 915 cm(-1) has been decomposed in two Gaussian peaks at 920 and 905 cm(-1). From these values, and the observation that the ratio of the areas of the two peaks vs pH was constant, we have proposed that uranyl sorption on titanium oxide in the pH range 4-7 leads to the formation of one surface complex where uranium atoms have two different chemical environments. A trimer surface complex linked by two uranium atoms to the titanium oxide surface would be consistent with this interpretation.

[Determination of 235U/238U isotope ratios in camphor tree bark samples by MC-ICP-MS after separation of uranium from matrix elements].

Twelve camphor (cinnamomum camphora) tree bark samples were collected from Hiroshima and Kyoto, and the matrix element composition and morphology of the outer surface of these camphor tree bark samples were studied by EDXS and SEM respectively. After a dry decomposition, DOWEX 1-X8 anion exchange resin was used to separate uranium from matrix elements in these camphor tree bark samples. Finally, 235U/238 U isotope ratios in purified uranium solutions were determined by MC-ICP-MS. It was demonstrated that the outer surface of these camphor tree bark samples is porous and rough, with Al, Ca, Fe, K, Mg, Si, C, O and S as its matrix element composition. Uranium in these camphor tree bark samples can be efficiently separated and quantitatively recovered from the matrix element composition. Compared with those collected from Kyoto, the camphor tree bark samples collected from Hiroshima have significantly higher uranium contents, which may be due to the increased aerosol mass concentration during the city reconstruction. Moreover, the 235 U/23.U isotope ratios in a few camphor tree bark samples collected from Hiroshima are slightly higher than 0.007 25.