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Metals dissolved in natural waters often become sorbed onto oxide or clay minerals, so that prediction of their chemical behaviour and transport properties requires knowledge of the structure and bonding of metal species at the solid/water interface. For many sorption systems, X-ray absorption spectroscopy (XAS) can be used to determine the identity and number of nearest-neighbour atoms and interatomic distances in aqueous complexes on solid surfaces, and thus to identify the dominant type of surface complex and the partitioning mechanism. Here we describe an XAS study of divalent cobalt (Co(II)) complexes sorbed on three different solids, gamma-Al2O3, rutile (TiO2) and kaolinite (Al2Si2O5(OH)4). We find direct evidence for the presence of multinuclear sorption complexes at surface coverages below one monolayer of Co(II) atoms. Our spectroscopic data reveal distinct differences in the number of coordinating atoms and interatomic distances in the surface complexes formed on each of the solids at the same sorption density. These results suggest that different oxide and clay surfaces influence the structure and properties of aqueous surface complexes, and therefore must be accounted for in models of metal-ion sorption.

We have investigated the effect of changes in solution chemistry on the nature of uranyl sorption complexes on montmorillonite (SAz-1) at different surface coverages (1.43-53.6 µmol/g). Uranyl uptake onto SAz-1 between pH 3 and 7 was determined in both titration and batch-mode experiments. These pH values result in solutions that contain a range of monomeric and oligomeric aqueous uranyl species. Continuous-wave and time-resolved emission spectroscopies were used to investigate the nature of U(VI) sorbed to SAz-1. A discrete set of uranyl surface complexes has been identified over a wide range of pH values at these low to moderate coverages. For all samples, two surface complexes are detected with spectral characteristics commensurate with an inner-sphere complex and an exchange-site complex; the relative abundance of these two species is similar over these pH values at low coverage (1.43-2.00 µmol/g). In addition, surface species having spectra consistent with polymeric hydroxide-like sorption complexes form at the moderate coverages ( approximately 34-54 µmol/g), increasing in abundance as the capacity of the amphoteric surface sites is exceeded. Furthermore, a species with spectral characteristics anticipated for an outer-sphere surface complex is observed for wet paste samples at low pH (3.7-4.4) and both low ( approximately 2 µmol/g) and moderate ( approximately 40 µmol/g) coverage. There are only subtle differences in the nature of sorption complexes formed at different pH values but similar coverages, despite markedly different uranyl speciation in solution. These results indicate that the speciation in the solution has minimal influence on the nature of the sorption complex under these experimental conditions. The primary control on the nature and abundance of the different uranyl sorption complexes appears to be the relative abundance and reactivity of the different sorption sites. Copyright 2001 Academic Press.

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Uranium (U) was successfully removed from contaminated soils from the Fernald Environmental Management Project (FEMP) site near Fernald, Ohio. The laboratory column leach process, referred to as the simulated heap leach process, using 0.5 M sodium bicarbonate as the dominant reagent, was able to achieve uranium removals of 75-90%, corresponding approximately to the percentage of uranium in the oxidized state. Parametric optimization studies are reported. The dissolution of uranium took place in two stages: a rapid desorption associated with soil surfaces and a slow step associated with diffusion of uranium toward solid surfaces. In addition, use of the oxidizing agent, sodium peroxide, improved uranium removal due to oxidation of U(IV), enhancing the solubility of the uranium. The results suggest that the process will be effective for field scale remediation of uranium-contaminated soils because of the efficiency, mild complexing agent employed, lack of prescreening of the soil and the simple equipment necessary. Two relevant companion studies have recently been completed. The first, a scale-up demonstration [Turney, W.

ES950745IX Abstract published in Advance ACS Abstracts, May 15, 1996.

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