Kai-Uwe Ulrich

Natural inactivation of phosphorus by aluminum in atmospherically acidified water bodies

Atmospheric acidification of catchment-lake ecosystems may provide natural conditions for the in-lake control of P cycling. This process is based on the elevated transport of aluminum from acidified soils and its subsequent precipitation in the water body and is described for strongly acidified forest lakes, acidified and circumneutral reservoirs, and a moderately acidified alpine lake. In water bodies with episodically or permanently acidified inflows a pH gradient develops between lake water and tributaries due to: (i) neutralization of acidic inflows after mixing with waters with undepleted carbonate buffering system, and/or (ii) the in-lake alkalinity generation dominated by biochemical removal of NO3- and SO4(2-). With the pH increasing towards neutrality, ionic Al species hydrolyze and form colloidal Al hydroxides (Al(part)) with large specific surfaces and strong ability to bind orthophosphate from the liquid phase. Moreover, Alpart settles and increases the P sorption capacity of the sediment. The presence of Al(part) on the bottom reduces orthophosphate release from sediments after its liberation from ferric oxyhydroxides during anoxia because Al(part) is not sensitive to redox changes. Consequently, the natural in-lake P inactivation may be expected in any water body with elevated Al input and a pH gradient between its inlet and outlet.

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 Ca²⁺ 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.

Speciation-Dependent Kinetics of Uranium(VI) Bioreduction

The kinetics of uranium(VI) reduction by Shewanella oneidensis strain MR-1 was studied for varied pH and concentrations of dissolved inorganic carbon (DIC) and calcium. These are key variables affecting U(VI) speciation in aqueous systems. For all conditions studied, a nearly log-linear decrease of [U(VI)] suggested pseudo–first-order kinetics with respect to U(VI). The reduction rate constants (k) decreased with increasing DIC and calcium concentration, and were sensitive to pH. A positive correlation was found between k and the logarithm of the total concentration of U(VI)-hydroxyl and U(VI)-organic complexes. Linear correlations of the rate constant with the redox potential (EH) of U(VI) reduction and the associated Gibbs free energy of reaction (ΔGr) were found for both Ca-free and Ca-containing systems. Both EH and ΔGr are strong functions of aqueous U(VI) speciation. Because the range in ΔGr among the experimental conditions was small, the differences in k are more likely to be due to differences in EH or to differences in individual rate constants of U(VI) species. Calculation of conditional reduction rate constants for the major groups of U(VI) complexes revealed highest constants for the combined groups of U(VI)-hydroxyl and U(VI)-organic species, lower rate constants for the U(VI)-carbonate group, and much lower constants for the Ca-U(VI)-carbonate group. Mechanistic explanations for these findings are discussed.

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.

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

Reference EPFL-ARTICLE-184448doi:10.1021/es302732dView record in Web of Science Record created on 2013-02-27, modified on 2016-08-09

Speciation of Colloid-borne Uranium by EXAFS and ATR-FTIR spectroscopy

De-acidification of acid mine waters transfers dissolved uranium into a colloidal form. Spectroscopic studies on colloid-borne uranium obtained by simulation of mine flooding in the laboratory showed that matrix ions such as sulfate and silicate are not involved in inner-sphere surface sorption complexes of UO22+ on ferrihydrite. At ambient air atmosphere, the data suggest the formation of ternary U(VI) carbonato surface complexes with either monodentate or bidentate coordination of carbonate and uranyl even at moderately acidic conditions. A revised model is proposed for UO22+ sorption on ferrihydrite in the absence of carbonate.