Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO 2 (CO 3 ) 3 2À and Ca 2 UO 2 (CO 3 ) 3 0 (aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO 3 solutions equilibrated with either ambient air (430 ppm CO 2 ) or 2% CO 2 in the presence of 0, 1.8, or 8.9 mM Ca 2+ . Under conditions where the Ca 2 UO 2 (CO 3 ) 3 0 (aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca 2 UO 2 (CO 3 ) 3 0 (aq) accurately simulated the effect of Ca 2+ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca 2+ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers.

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To understand how redox processes influence carbon, nitrogen, and iron cycling within the intrameander hyporheic zone, we developed a biotic and abiotic reaction network and incorporated it into the reactive transport simulator PFLOTRAN. Two‐dimensional reactive flow and transport simulations were performed (1) to evaluate how transient hydrological conditions control the lateral redox zonation within an intrameander region of the East River in Colorado and (2) to quantify the impact of a single meander on subsurface exports of carbon and other geochemical species to the river. The meander's overall contribution to the river was quantified by integrating geochemical outfluxes along the outside of the meander bend. The model was able to capture the field‐observed trends of dissolved oxygen, nitrate, iron, pH, and total inorganic carbon along a 2‐D transect. Consistent with field observations, simulated dissolved oxygen and nitrate decreased along the intrameander flow paths while iron (Fe2+) concentration increased. The simulation results further demonstrated that the reductive potential of the lateral redox zonation was controlled by groundwater velocities resulting from river stage fluctuations, with low‐water conditions promoting reducing conditions. The sensitivity analysis results showed that permeability had a more significant impact on biogeochemical zonation compared to the reaction pathways under transient hydrologic conditions. The simulation results further indicated that the meander acted as a sink for organic and inorganic carbon as well as iron during the extended baseflow and high‐water conditions; however, these geochemical species were released into the river during the falling limb of the hydrograph.

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al. 2003, Williams et al. 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated ratelimited U(VI) desorption (Fox et al. 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggested the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer sediments desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranylcarbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ~3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetatebicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction in the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers. * Concentration/enrichment within the injection tank. ** Tank #2 injection was initially started on 9-Sept-10; however, a closed injection valve prevented flow from the tank; injection was restarted on 13-Sept-10, as indicated.

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans.

[1] A tracer test was performed at the Rifle Integrated Field Research Challenge site to assess the effect of addition of bicarbonate on U(VI) desorption from contaminated sediments in the aquifer and to compare equilibrium and rate-limited reactive transport model descriptions of mass transfer limitations on desorption. The tracer test consisted of injection of a 37 mM NaHCO 3 solution containing conservative tracers followed by downgradient sampling of groundwater at various elevations and distances from the point of injection. Breakthrough curves show that dissolved U(VI) concentrations increased 1.2-2.6-fold above background levels, resulting from increases in bicarbonate alkalinity (from injectate solution) and Ca concentrations (from cation exchange). In general, more U(VI) was mobilized in shallower zones of the aquifer, where finer-grained sediments and higher solid phase U content were found compared to deeper zones. An equilibrium-based reactive transport model incorporating a laboratory-based surface complexation model derived from the same location predicted the general trends in dissolved U(VI) during the tracer test but greatly overpredicted the concentrations of U(VI), indicating that the system was not at equilibrium. Inclusion of a multirate mass transfer model successfully simulated the nonequilibrium desorption behavior of U(VI). Local sediment properties such as sediment texture (weight percent <2 mm), surface area, cation exchange capacity, and adsorbed U(VI) were heterogeneous at the meter scale, and it was important to incorporate these values into model parameters in order to produce accurate simulations.

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A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2 mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 x 10(-8) to 10(-5) M in [U(VI)](tot), 7.2 to 8.0 in pH, 3.0 x 10(-3) to 6.0 x 10(-3) M in [Ca(2+)], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption K(d) values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters.