RESUMO
U isotope fractionation may serve as an accurate proxy for U(VI) reduction in both modern and ancient environments, if the systematic controls on the magnitude of fractionation (ε) are known. We model the effect of U(VI) reduction kinetics on U isotopic fractionation during U(VI) reduction by a novel Shewanella isolate, Shewanella sp. (NR), in batch incubations. The measured ε values range from 0.96 ± 0.16 to 0.36 ± 0.07 and are strongly dependent on the U(VI) reduction rate. The ε decreases with increasing reduction rate constants normalized by cell density and initial U(VI). Reactive transport simulations suggest that the rate dependence of ε is due to a two-step process, where diffusive transport of U(VI) from the bulk solution across a boundary layer is followed by enzymatic reduction. Our results imply that the spatial decoupling of bulk U(VI) solution and enzymatic reduction should be taken into account for interpreting U isotope data from the environment.
Assuntos
Fracionamento Químico , Cromo , Isótopos , Cinética , OxirreduçãoRESUMO
In this study, porewater chloride data from Yucca Mountain, NV are analyzed and modeled by three-dimensional chemical transport simulation and analytical methods. The simulation modeling approach is based on a continuum formulation of coupled multiphase fluid flow and tracer transport processes through fractured porous rock using a dual-continuum concept. Infiltration rate calibrations were performed using the porewater chloride data. Model results of chloride distributions were improved in matching the observed data with the calibrated infiltration rates. Statistical analyses of the frequency distribution for overall percolation fluxes and chloride concentration in the unsaturated zone system demonstrate that the use of the calibrated infiltration rates had an insignificant effect on the distribution of simulated percolation fluxes but significantly changed the predicted distribution of simulated chloride concentrations. An analytical method was also applied to model transient chloride transport. The method was verified by three-dimensional simulation results to be capable of capturing major chemical transient behavior and trends. Effects of lateral flow in the Paintbrush nonwelded unit on percolation fluxes and chloride distribution were studied by three-dimensional simulations with increased horizontal permeability. The combined results from these model calibrations furnish important information for the UZ model studies, contributing to performance assessment of the potential repository.
Assuntos
Cloretos/análise , Modelos Teóricos , Movimentos da Água , Calibragem , Filtração , Fenômenos Geológicos , Geologia , Nevada , Porosidade , Resíduos Radioativos , Eliminação de ResíduosRESUMO
Plugging of flow paths caused by mineral precipitation in fractures above the potential repository at Yucca Mountain, Nevada could reduce the probability of water seeping into the repository. As part of an ongoing effort to evaluate thermal-hydrological-chemical (THC) effects on flow in fractured media, we performed a laboratory experiment and numerical simulations to investigate mineral dissolution and precipitation under anticipated temperature and pressure conditions in the repository. To replicate mineral dissolution by vapor condensate in fractured tuff, water was flowed through crushed Yucca Mountain tuff at 94 degrees C. The resulting steady-state fluid composition had a total dissolved solids content of about 140 mg/l; silica was the dominant dissolved constituent. A portion of the steady-state mineralized water was flowed into a vertically oriented planar fracture in a block of welded Topopah Spring Tuff that was maintained at 80 degrees C at the top and 130 degrees C at the bottom. The fracture began to seal with amorphous silica within 5 days.A 1-D plug-flow numerical model was used to simulate mineral dissolution, and a similar model was developed to simulate the flow of mineralized water through a planar fracture, where boiling conditions led to mineral precipitation. Predicted concentrations of the major dissolved constituents for the tuff dissolution were within a factor of 2 of the measured average steady-state compositions. The mineral precipitation simulations predicted the precipitation of amorphous silica at the base of the boiling front, leading to a greater than 50-fold decrease in fracture permeability in 5 days, consistent with the laboratory experiment.These results help validate the use of a numerical model to simulate THC processes at Yucca Mountain. The experiment and simulations indicated that boiling and concomitant precipitation of amorphous silica could cause significant reductions in fracture porosity and permeability on a local scale. However, differences in fluid flow rates and thermal gradients between the experimental setup and anticipated conditions at Yucca Mountain need to be factored into scaling the results of the dissolution/precipitation experiments and associated simulations to THC models for the potential Yucca Mountain repository.
Assuntos
Geologia , Modelos Teóricos , Movimentos da Água , Precipitação Química , Previsões , Fenômenos Geológicos , Minerais/química , Nevada , Resíduos Radioativos , Eliminação de Resíduos , Dióxido de Silício/química , SolubilidadeRESUMO
The biological effects and expected fate of the vast amount of oil in the Gulf of Mexico from the Deepwater Horizon blowout are unknown owing to the depth and magnitude of this event. Here, we report that the dispersed hydrocarbon plume stimulated deep-sea indigenous γ-Proteobacteria that are closely related to known petroleum degraders. Hydrocarbon-degrading genes coincided with the concentration of various oil contaminants. Changes in hydrocarbon composition with distance from the source and incubation experiments with environmental isolates demonstrated faster-than-expected hydrocarbon biodegradation rates at 5°C. Based on these results, the potential exists for intrinsic bioremediation of the oil plume in the deep-water column without substantial oxygen drawdown.