Engineering topics

Williams, K H

Publications and source records attributed to Williams, K H.

6 records

DOE OSTI2012

Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquifer

Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology and redox processes that occur in these zones, several cores from a region of naturally occurring reducing conditions in a U-contaminated aquifer (Rifle, CO) were examined. Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for U and Fe content, oxidation state, and mineralogy; reduced S phases; and solid-phase organic C content using a suite of analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase U concentrations were higher in the naturally reduced zone, with a high proportion of the U present as U(IV). The sediments were also elevated in reduced S phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and SO 4 reduction has occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentrations of solid-phase organic C and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic C concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic C for maintaining reducing conditions and U immobilization.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2011

Composition, stability, and measurement of reduced uranium phases for groundwater bioremediation at Old Rifle, CO

Reductive biostimulation is currently being explored as a possible remediation strategy for uranium (U) contaminated groundwater, and is currently being investigated at a field site in Rifle, CO, USA. The long-term stability of the resulting U(IV) phases is a key component of the overall performance and depends upon a variety of factors, including rate and mechanism of reduction, mineral associations in the subsurface, and propensity for oxidation. To address these factors, several approaches were used to evaluate the redox sensitivity of U: measurement of the rate of oxidative dissolution of biogenic uraninite (UO{sub 2(s)}) deployed in groundwater at Rifle, characterization of a zone of natural bioreduction exhibiting relevant reduced mineral phases, and laboratory studies of the oxidative capacity of Fe(III) and reductive capacity of Fe(II) with regard to U(IV) and U(VI), respectively.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2011

Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH{sub 4}{sup +} production during urea hydrolysis were incorporated in the model and captured critical changes in the major metal species. The electrical phase increases were potentially due to ion exchange processes that modified charge structure at mineral/water interfaces. Our study revealed the potential of geophysical monitoring for geochemical changes during urea hydrolysis and the advantages of combining multiple approaches to understand complex biogeochemical processes in the subsurface.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2011

Molecular analysis of the metabolic rates of discrete subsurface populations of sulfate reducers

Elucidating the in situ metabolic activity of phylogenetically diverse populations of sulfate-reducing microorganisms that populate anoxic sedimentary environments is key to understanding subsurface ecology. Previous pure culture studies have demonstrated that transcript abundance of dissimilatory (bi)sulfite reductase genes is correlated with the sulfate reducing activity of individual cells. To evaluate whether expression of these genes was diagnostic for subsurface communities, dissimilatory (bi)sulfite reductase gene transcript abundance in phylogenetically distinct sulfate-reducing populations was quantified during a field experiment in which acetate was added to uranium-contaminated groundwater. Analysis of dsrAB sequences prior to the addition of acetate indicated that Desulfobacteraceae, Desulfobulbaceae, and Syntrophaceae-related sulfate reducers were the most abundant. Quantifying dsrB transcripts of the individual populations suggested that Desulfobacteraceae initially had higher dsrB transcripts per cell than Desulfobulbaceae or Syntrophaceae populations, and that the activity of Desulfobacteraceae increased further when the metabolism of dissimilatory metal reducers competing for the added acetate declined. In contrast, dsrB transcript abundance in Desulfobulbaceae and Syntrophaceae remained relatively constant, suggesting a lack of stimulation by added acetate. The indication of higher sulfate-reducing activity in the Desulfobacteraceae was consistent with the finding that Desulfobacteraceae became the predominant component of the sulfate-reducing community. Discontinuing acetate additions resulted in a decline in dsrB transcript abundance in the Desulfobacteraceae. These results suggest that monitoring transcripts of dissimilatory (bi)sulfite reductase genes in distinct populations of sulfate reducers can provide insight into the relative rates of metabolism of different components of the sulfate-reducing community and their ability to respond to environmental perturbations.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2011

Using complex resistivity imaging to infer biogeochemical processes associated with bioremediation of a uranium-contaminated aquifer

Experiments at the Department of Energy's Rifle Integrated Field Research Challenge (IFRC) site near Rifle, Colorado (USA) have demonstrated the ability to remove uranium from groundwater by stimulating the growth and activity of Geobacter species through acetate amendment. Prolonging the activity of these strains in order to optimize uranium bioremediation has prompted the development of minimally-invasive and spatially-extensive monitoring methods diagnostic of their in situ activity and the end products of their metabolism. Here we demonstrate the use of complex resistivity imaging for monitoring biogeochemical changes accompanying stimulation of indigenous aquifer microorganisms during and after a prolonged period (100+ days) of acetate injection. A thorough raw-data statistical analysis of discrepancies between normal and reciprocal measurements and incorporation of a new power-law phase-error model in the inversion were used to significantly improve the quality of the resistivity phase images over those obtained during previous monitoring experiments at the Rifle IRFC site. The imaging results reveal spatiotemporal changes in the phase response of aquifer sediments, which correlate with increases in Fe(II) and precipitation of metal sulfides (e.g., FeS) following the iterative stimulation of iron and sulfate reducing microorganism. Only modest changes in resistivity magnitude were observed over the monitoring period. The largest phase anomalies (>40 mrad) were observed hundreds of days after halting acetate injection, in conjunction with accumulation of Fe(II) in the presence of residual FeS minerals, reflecting preservation of geochemically reduced conditions in the aquifer - a prerequisite for ensuring the long-term stability of immobilized, redox-sensitive contaminants, such as uranium.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2011

Three-dimensional induced polarization data inversion for complex resistivity

The conductive and capacitive material properties of the subsurface can be quantified through the frequency-dependent complex resistivity. However, the routine three-dimensional (3D) interpretation of voluminous induced polarization (IP) data sets still poses a challenge due to large computational demands and solution nonuniqueness. We have developed a flexible methodology for 3D (spectral) IP data inversion. Our inversion algorithm is adapted from a frequency-domain electromagnetic (EM) inversion method primarily developed for large-scale hydrocarbon and geothermal energy exploration purposes. The method has proven to be efficient by implementing the nonlinear conjugate gradient method with hierarchical parallelism and by using an optimal finite-difference forward modeling mesh design scheme. The method allows for a large range of survey scales, providing a tool for both exploration and environmental applications. We experimented with an image focusing technique to improve the poor depth resolution of surface data sets with small survey spreads. The algorithm's underlying forward modeling operator properly accounts for EM coupling effects; thus, traditionally used EM coupling correction procedures are not needed. The methodology was applied to both synthetic and field data. We tested the benefit of directly inverting EM coupling contaminated data using a synthetic large-scale exploration data set. Afterward, we further tested the monitoring capability of our method by inverting time-lapse data from an environmental remediation experiment near Rifle, Colorado. Similar trends observed in both our solution and another 2D inversion were in accordance with previous findings about the IP effects due to subsurface microbial activity.

15 GEOTHERMAL ENERGY↗