ABSTRACT-In oxidizing environments, the toxic and radioactive element uranium (U) is most soluble and mobile in the hexavalent oxidation state. Sorption of U(VI) on Fe-oxides minerals [such as hematite (α-Fe 2 O 3 ) and goethite (α-FeOOH)] and occlusion of U(VI) by Feoxide coatings are processes that can retard U transport in environments. In aged Ucontaminated geologic materials, the transport and the biological availability of U toward reduction may be limited by co-precipitation with Fe-oxide minerals. These processes also affect the biological availability of U(VI) species toward reduction and precipitation as the less soluble U(IV) species by metal-reducing bacteria.To examine the dynamics of interactions between U(VI) and Fe oxides during crystallization, indicated that almost all of the Fe in these solids was crystalline and that most of the U was associated with these crystalline Fe oxides. X-ray diffraction and Fourier-transform infrared (FT-IR) spectroscopic studies indicate that hematite formation is preferred over that of goethite when the amount of U in the Fe-oxides exceeds 1 mol % U (~4 wt % U). FT-IR and room temperature continuous wave luminescence spectroscopic studies with unleached U/Fe solids indicate a relationship between the mol % U in the Fe oxide and the intensity or existence of the spectra features that can be assigned to UO 2 2+ species (such as the IR asymmetric υ 3 stretch for O=U=O for uranyl). These spectral features were undetectable in carbonate-or oxalate-leached Molecular modeling studies reveal that U 6+ species could bond with O atoms from distorted Fe octahedra in the hematite structure with an environment that is consistent with the results of the XAFS. The results provide compelling evidence of U incorporation within the hematite structure.

Quantitative information on the uptake and distribution of Al at the cellular level is required to understand mechanisms of Al toxicity, but direct measurement of uptake across the plasma membrane has remained elusive. We measured rates of Al transport across membranes in single cells of Chara corallina using the rare 26 Al isotope, an emerging technology (accelerator mass spectrometry), and a surgical technique for isolating subcellular compartments. Accumulation of Al in the cell wall dominated total uptake (71-318 g m Ϫ2 min Ϫ1 ), although transport across the plasma membrane was detectable (71-540 ng m Ϫ2 min Ϫ1 ) within 30 min of exposure. Transport across the tonoplast was initially negligible, but accelerated to rates approximating uptake across the plasma membrane. The avacuolate protoplasm showed signs of saturation after 60 min, but continued movement across the plasma membrane was supported by sequestration in the vacuole. Saturation of all compartments was observed after 12 to 24 h. Accumulation of Al in the cell wall reflected variation in {Al 3ϩ } induced by changes in Al supply or complexing ligands, but was unaffected by pH. In contrast, transport across the plasma membrane peaked at pH 4.3 and increased when {Al 3ϩ } was reduced by complexing ligands. Cold temperature (4°C) reduced accumulation in the cell wall and protoplasm, whereas 2,4-dinitrophenol and m-chlorocarbonylcyanidephenyl hydrazone increased membrane transport by 12-to 13-fold. Our data suggest that the cell wall is the major site of Al accumulation. Nonetheless, membrane transport occurs within minutes of exposure and is supported by subsequent sequestration in the vacuole. The rapid delivery of Al to the protoplasm suggests that intracellular lesions may be possible.

Influence of Mn oxides on the reduction of uranium(VI) by the Influence of Mn oxides on the reduction of uranium(VI) by the metal-reducing bacterium

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