Effect of diffusive transport limitations on UO2 dissolution.

The effects of diffusive transport limitations on the dissolution of UO(2) were investigated using an artificial groundwater prepared to simulate the conditions at the Old Rifle aquifer site in Colorado, USA. Controlled batch, continuously-stirred tank (CSTR), and plug flow reactors were used to study UO(2) dissolution in the absence and presence of diffusive limitations exerted by permeable sample cells. The net rate of uranium release following oxidative UO(2) dissolution obtained from diffusion-limited batch experiments was ten times lower than that obtained for UO(2) dissolution with no permeable sample cells. The release rate of uranium to bulk solution from UO(2) contained in permeable sample cells under advective flow conditions was more than 100 times lower than that obtained from CSTR experiments without diffusive limitations. A 1-dimensional transport model was developed that could successfully simulate diffusion-limited release of U following oxidative UO(2) dissolution with the dominant rate-limiting process being the transport of U(VI) out of the cells. Scanning electron microscopy, X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS) characterization of the UO(2) solids recovered from batch experiments suggest that oxidative dissolution was more evident in the absence of diffusive limitations. Ca-EXAFS spectra indicate the presence of Ca in the reacted UO(2) solids with a coordination environment similar to that of a Ca-O-Si mineral. The findings from this study advance our overall understanding of the coupling of geochemical and transport processes that can lead to differences in dissolution rates measured in the field and in laboratory experiments.

Molecular-scale structure of uranium(VI) immobilized with goethite and phosphate.

The molecular-scale immobilization mechanisms of uranium uptake in the presence of phosphate and goethite were examined by extended X-ray absorption fine structure (EXAFS) spectroscopy. Wet chemistry data from U(VI)-equilibrated goethite suspensions at pH 4-7 in the presence of ~100 µM total phosphate indicated changes in U(VI) uptake mechanisms from adsorption to precipitation with increasing total uranium concentrations and with increasing pH. EXAFS analysis revealed that the precipitated U(VI) had a structure consistent with the meta-autunite group of solids. The adsorbed U(VI), in the absence of phosphate at pH 4-7, formed bidentate edge-sharing, ≡ Fe(OH)(2)UO(2), and bidentate corner-sharing, (≡ FeOH)(2)UO(2), surface complexes with respective U-Fe coordination distances of ~3.45 and ~4.3 Å. In the presence of phosphate and goethite, the relative amounts of precipitated and adsorbed U(VI) were quantified using linear combinations of the EXAFS spectra of precipitated U(VI) and phosphate-free adsorbed U(VI). A U(VI)-phosphate-Fe(III) oxide ternary surface complex is suggested as the dominant species at pH 4 and total U(VI) of 10 µM or less on the basis of the linear combination fitting, a P shell indicated by EXAFS, and the simultaneous enhancement of U(VI) and phosphate uptake on goethite. A structural model for the ternary surface complex was proposed that included a single phosphate shell at ~3.6 Å (U-P) and a single iron shell at ~4.3 Å (U-Fe). While the data can be explained by a U-bridging ternary surface complex, (≡ FeO)(2)UO(2)PO(4), it is not possible to statistically distinguish this scenario from one with P-bridging complexes also present.

Oxidative Dissolution of Biogenic Uraninite in Groundwater at Old Rifle, CO.

Reductive bioremediation is currently being explored as a possible strategy for uranium-contaminated aquifers such as the Old Rifle site (Colorado). The stability of U(IV) phases under oxidizing conditions is key to the performance of this procedure. An in situ method was developed to study oxidative dissolution of biogenic uraninite (UO2), a desirable U(VI) bioreduction product, in the Old Rifle, CO, aquifer under different variable oxygen conditions. Overall uranium loss rates were 50-100 times slower than laboratory rates. After accounting for molecular diffusion through the sample holders, a reactive transport model using laboratory dissolution rates was able to predict overall uranium loss. The presence of biomass further retarded diffusion and oxidation rates. These results confirm the importance of diffusion in controlling in-aquifer U(IV) oxidation rates. Upon retrieval, uraninite was found to be free of U(VI), indicating dissolution occurred via oxidation and removal of surface atoms. Interaction of groundwater solutes such as Ca²âº or silicate with uraninite surfaces also may retard in-aquifer U loss rates. These results indicate that the prolonged stability of U(IV) species in aquifers is strongly influenced by permeability, the presence of bacterial cells and cell exudates, and groundwater geochemistry.

Effect of Mn(II) on the structure and reactivity of biogenic uraninite.

The efficacy of a site remediation strategy involving the stimulaton of microbial U(VI) reduction hinges in part upon the long-term stability of the product, biogenic uraninite, toward environmental oxidants. Geological sedimentary uraninites (nominal formula UO2) reportedly contain abundant cation impurities that enhance their resistance to oxidation. By analogy, incorporation of common groundwater solutes into biogenic uraninite could also impart stability-enhancing properties. Mn(II) is a common groundwater cation, which has a favorable ionic radiusfor substitution reactions. The structure and reactivity of Mn(II)-reacted biogenic uraninite are investigated in this study. Up to 4.4 weight percent Mn(II) was found to be structurally bound in biogenic uraninite. This Mn(II) incorporation was associated with decreasing uraninite particle size and structural order. Importantly, the equilibrium solubility of Mn-reacted uraninite was halved relative to unreacted uraninite, demonstrating changes in thermodynamic properties, while the dissolution rate was up to 38-fold lower than that of unreacted biogenic uraninite. We conclude that structuralincorporation of Mn(II) into uraninite has an important stabilizing effect leading to the prediction that other groundwater solutes may similarly stabilize biogenic uraninite.

Nanoscale size effects on uranium(VI) adsorption to hematite.

U(VI) adsorption on aerosol-synthesized hematite particles ranging in size from 12 to 125 nm was studied to explore nanoscale size effects on uranium adsorption. Adsorption on 70 nm aqueous-synthesized particles was also investigated to examine the effect of the synthesis method on reactivity. Equilibrium adsorption was measured over pH 3-11 at two U(VI) loadings. Surface complexation modeling, combined with adjustment of adsorption equilibrium constants to be independent of site density and surface area, provided a quantitative reaction-based framework for evaluating adsorption affinity and capacity. Among the aerosol-synthesized particles, the adsorption affinity decreased as the particle size increased from 12 to 125 nm with similar intermediate affinities for 30 and 50 nm particles. X-ray absorption fine structure spectroscopy measurements suggest that the differences in adsorption affinity and capacity are not the result of substantially different coordination environments of adsorbed U(VI).

Identification of uranyl surface complexes on ferrihydrite: Advanced EXAFS data analysis and CD-MUSIC modeling.

Previous spectroscopic research suggested that uranium(VI) adsorption to iron oxides is dominated by ternary uranyl-carbonato surface complexes across an unexpectedly wide pH range. Formation of such complexes would have a significant impact on the sorption behavior and mobility of uranium in aqueous environments. We therefore reinvestigated the identity and structural coordination of uranyl sorption complexes using a combination of U LIII-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and iterative transformation factor analysis, which enhances the resolution in comparison to conventional EXAFS analysis. A range of conditions (pH, CO2 partial pressure, ionic strength) made it possible to quantify the variations in surface speciation. In the resulting set of spectral data (N=11) the variance is explained by only two components, which represent two structurally different types of surface complexes: (1) a binary uranyl surface complexwith a bidentate coordination to edges of Fe(O,OH)6 octahedra and (2) a uranyl triscarbonato surface complex where one carbonate ion bridges uranyl to the surface. This ternary type B complex differs from a type A complex where uranyl is directly attached to surface atoms and carbonate is bridged by uranyl to the surface. Both surface complexes agree qualitatively and quantitatively with predictions by a charge distribution (CD) model. According to this model the edge-sharing uranyl complex has equatorial ligands (-OH2, -OH, or one -CO3 group) that point away from the surface. The monodentate uranyl triscarbonato surface complex (type B) is relevant only at high pH and elevated pC0O. At these conditions, however, it is responsible for significant uranyl sorption, whereas standard models would predict only weak sorption. This paper presents the first spectroscopic evidence of this ternary surface complex, which has significant implications for immobilization of uranyl in carbonate-rich aqueous environments.

Dissolution of biogenic and synthetic UO2 under varied reducing conditions.

The chemical stability of biogenic UO2, a nanoparticulate product of environmental bioremediation, may be impacted by the particles' surface free energy, structural defects, and compositional variability in analogy to abiotic UO(2+x) (0 < or = x < or = 0.25). This study quantifies and compares intrinsic solubility and dissolution rate constants of biogenic nano-UO2 and synthetic bulk UO2.00, taking molecular-scale structure into account. Rates were determined under anoxic conditions as a function of pH and dissolved inorganic carbon in continuous-flow experiments. The dissolution rates of biogenic and synthetic UO2 solids were lowest at near neutral pH and increased with decreasing pH. Similar surface area-normalized rates of biogenic and synthetic UO2 suggest comparable reactive surface site densities. This finding is consistent with the identified structural homology of biogenic UO2 and stoichiometric UO2.00 Compared to carbonate-free anoxic conditions, dissolved inorganic carbon accelerated the dissolution rate of biogenic UO2 by 3 orders of magnitude. This phenomenon suggests continuous surface oxidation of U(IV) to U(VI), with detachment of U(VI) as the rate-determining step in dissolution. Although reducing conditions were maintained throughout the experiments, the UO2 surface can be oxidized by water and radiogenic oxidants. Even in anoxic aquifers, UO2 dissolution may be controlled by surface U(VI) rather than U(IV) phases.

Indirect UO2 oxidation by Mn(II)-oxidizing spores of Bacillus sp. strain SG-1 and the effect of U and Mn concentrations.

Manganese oxides are widespread in the environment and their surface reactivity has the potential to modifythe geochemical behavior of uranium. We have investigated the effect of different concentrations of U and Mn on the coupled biogeochemical oxidation-reduction reactions of U and Mn. Experiments conducted in the presence of Mn(II)-oxidizing spores from Bacillus sp. strain SG-1 and 5% headspace oxygen show that the Mn oxides produced by these spores can rapidly oxidize UO2. Thirty to fifty times more UO2 is oxidized in the presence of Mn oxides compared to Mn oxide free controls. As a consequence of this U02 oxidation, Mn oxides are reduced to soluble Mn(II) that can be reoxidized by SG-1 spores. SG-1 spores cannot directly oxidize U02, but U02 oxidation proceeds rapidly with Mn(II) concentrations of <5 microM. The rate of UO2 oxidation is equal to the rate of MnO2 reduction with UO2 oxidation controlled by the initial concentrations of UO2, dissolved Mn(II) (in systems with spores), or Mn(IV) oxides (in systems containing preformed MnO2). U(VI) and UO2 decrease the Mn(II) oxidation rate in different ways by inhibiting the Mn(II)-oxidizing enzyme or decreasing the available Mn(II). These results emphasize the need to consider the impact of Mn(II)-oxidizing bacteria when predicting the potential for U02 oxidation in the subsurface.

Response of drinking-water reservoir ecosystems to decreased acidic atmospheric deposition in SE Germany: trends of chemical reversal.

This study evaluates chemical trends of seven acidified reservoirs and 22 tributaries in the Erzgebirge from 1993 to 2003. About 85% of these waters showed significantly (p < 0.05) declining concentrations of protons (-69%), nitrate (-41%), sulfate (-27%), and reactive aluminum (-50% on average). This reversal is attributed to the intense reduction of industrial SO2 and NOx emissions from formerly high levels, which declined by 99% and 82% in the German-Czech border region between 1993 and 1999. The deposition rates of protons and sulfur decreased by 70-90%. Since 1993, the dry deposition of total inorganic nitrogen diminished to a minor degree, but the wet deposition remained unchanged. The surface waters reflect a substantial decrease in Al exchange processes, a release of sulfur previously stored in soils, and an uptake of nitrate by forest vegetation. The latter effect may be supported by soil protection liming which contributed to the chemical reversal in almost 20% of the study waters.

Aluminum control of phosphorus sorption by lake sediments.

Release of reactive (phosphate-like) phosphorus (P) from freshwater sediments represents a significant internal P source for many lakes. Hypolimnetic P release occurs under reducing conditions that cause reductive dissolution of ferric hydroxide [Fe(OH)3]. This hypolimnetic P release may be naturally low or artificially reduced by sediment with naturally high or artificially elevated concentrations of aluminum hydroxide [Al(OH)3]. We presentfield and laboratory data for a common extraction analysis of sediments from 43 lakes differing in trophic status, pH regime, climate, and P loading. The results indicate that a simple sequential extraction of sediment may be a useful predictor of sediment's ability to release P. Sequential extractions of sediment P, Al, and Fe by water (H2O), bicarbonate-dithionite (BD), and NaOH (at 25 degrees C) showed that negligible amounts of P would be released from lake sediments during hypolimnetic anoxia if either (1) the molar Al(NaOH-25):Fe(BD) ratio is > 3 or (2) the molar Al(NaOH-25):P(H2O+BD) ratio is > 25. These ratios can be used as operational targets for estimation of sediment P release potential and Al dosing of P-rich sediment to prevent hypolimnetic P release under anoxic conditions.

The origin of aluminum flocs in polluted streams.

About 240,000 square kilometers of Earth's surface is disrupted by mining, which creates watersheds that are polluted by acidity, aluminum, and heavy metals. Mixing of acidic effluent from old mines and acidic soils into waters with a higher pH causes precipitation of amorphous aluminum oxyhydroxide flocs that move in streams as suspended solids and transport adsorbed contaminants. On the basis of samples from nine streams, we show that these flocs probably form from aggregation of the epsilon -Keggin polyoxocation AlO4Al12(OH)24(H2O)12(7+)(aq) (Al13), because all of the flocs contain distinct Al(O)4 centers similar to that of the Al13 nanocluster.