Field biostimulation experiments at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, have demonstrated that uranium concentrations in groundwater can be decreased to levels below the U.S. Environmental Protection Agency's (EPA) drinking water standard (0.126 µM).During successive summer experiments -referred to as "Winchester" (2007) and "Big Rusty" (2008) -acetate was added to the aquifer to stimulate the activity of indigenous dissimilatory metalreducing bacteria capable of reductively immobilizing uranium. The two experiments differed in the length of injection (31 vs. 110 days), the maximum concentration of acetate (5 vs. 30 mM), and the extent to which iron reduction ("Winchester") or sulfate reduction ("Big Rusty") was the predominant metabolic process. In both cases, rapid removal of U(VI) from groundwater occurred at calcium concentrations (6 mM) and carbonate alkalinities (8 meq/L) where Ca-UO 2 -CO 3 ternary complexes constitute >90% of uranyl species in groundwater. Complete consumption of acetate and increased alkalinity (>30 meq/L) accompanying the onset of sulfate reduction corresponded to temporary increases in U(VI); however, by increasing acetate concentrations in excess of available sulfate (10 mM), low U(VI) concentrations (0.1-0.05 µM) were achieved for extended periods of time (>140 days). Uniform delivery of acetate during "Big Rusty" was impeded due to decreases in injection well permeability, likely resulting from biomass accumulation and carbonate and sulfide mineral precipitation. Such decreases were not observed during the short-duration "Winchester" experiment. Terminal restriction fragment length polymorphism (TRFLP) analysis of 16S rRNA genes demonstrated that Geobacter sp. and Geobacter-like strains dominated the groundwater community profile during iron reduction, with 13 C stable isotope probing (SIP) results confirming these strains were actively utilizing acetate to replicate their genome during the period of optimal U(VI) removal. Gene transcript levels during "Big Rusty" were quantified for Geobacter-specific citrate synthase (gltA), with ongoing transcription during sulfate reduction indicating that members of the Geobacteraceae were still active and likely contributing to U(VI) removal. The persistence of reducible Fe(III) in sediments recovered from an area of prolonged (110-day) sulfate reduction is consistent with this conclusion. These results indicate that acetate availability and its ability to sustain the activity of iron-and uranyl-respiring Geobacter strains during sulfate reduction exerts a primary control on optimized U(VI) removal from groundwater at the Rifle IFRC site over extended time scales (>50 days).

Executive SummaryAdditional data needed for development of a Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) Phase III Feasibility Study to address a persistent uranium plume in 300 Area groundwater provided the stimulus for the limited field investigation (LFI) described in this report. The focus of the LFI was to determine the location and geochemical nature of the source for the uranium plume. These objectives were accomplished by drilling four new groundwater monitoring wells in the 300-FF-5 Operable Unit (OU) in fiscal year 2006 as defined in the Operable Unit Limited Field Investigation Plan (DOE 2006a). Wells 399-3-18 (C4999), 399-3-19 (C5001), 399-3-20 (C5002), and 399-1-23 (C5000) were drilled to characterize the uranium distribution in sediments in the vadose zone and the unconfined aquifer. In addition to uranium, the presence of other contaminants of concern were also evaluated.Uranium contamination in groundwater beneath the Hanford Site's 300 Area has persisted longer than predicted by modeling that was conducted during the 1990s as part of the initial remedial investigation for the 300-FF-5 Operable Unit. Even though discharge of uranium-bearing effluent to infiltration ponds and trenches ended by the mid-1980s, and removal of contaminated soil from former waste sites was accomplished in the late 1990s, the groundwater plume today continues to occupy a relatively constant area, with concentrations remaining within a fairly fixed range. Because portions of the plume exceed the drinking water standard for uranium (30 µg/L), the U.S. Department of Energy is supporting renewed remedial investigation activities and remedial action feasibility studies. The goal of this renewed effort is to find a remedy that will reduce uranium concentrations in the aquifer such that the aquifer is restored to its maximum beneficial use, i.e., as a potential supplier of drinking water.To provide the information necessary to proceed with the remedial action feasibility study and possible field treatability tests, a limited field investigation (LFI) has been conducted. The focus of the LFI was to determine the location and mobility characteristics for contaminant uranium that continues to re-supply the groundwater plume. Presumed sources include uranium remaining in the vadose zone and/or sequestered in the aquifer sediments, which interact with the fluctuating groundwater-river water. This information is fundamental for evaluating remedial action alternatives to reduce the concentration of uranium in groundwater to meet regulatory standards. New results provided by the LFI will be used in developing computer simulations of groundwater flow and uranium transport, in designing treatability field tests, and when implementing remedial action decisions.The four LFI borehole locations were chosen to represent various combinations of proximity to former waste disposal sites, proximity to the Columbia River, and wide ranging hydrogeologic features. Highly detailed descriptions of geologic features ...

Water level elevation measurements in wells are commonly used as a basis to delineate groundwater flow patterns (i.e., flow direction and hydraulic gradient). Barometric pressure fluctuations, however, can have a discernible impact on well water levels. These barometric effects may lead to erroneous indications of hydraulic head within the aquifer. Total hydraulic head within the aquifer, not well water level elevation, is the hydrologic parameter for determining groundwater flow direction and hydraulic gradient conditions. For low‐gradient, unconfined aquifer sites exhibiting variable vadose zone characteristics (e.g., thickness, pneumatic diffusivity), barometric pressure fluctuations can cause temporal changes in lateral flow direction and flow velocity. Discrete water level measurements used to determine the average or long‐term groundwater flow conditions, therefore, may provide nonrepresentative results. Calculation of the barometric response characteristics for individual wells provides the basis to account for the temporal effects of barometric pressure fluctuations from monitor well measurements, so that average, long‐term groundwater flow pattern behavior can be determined.

Continued global use of fossil fuels places a premium on developing technology solutions to minimize increases in atmospheric CO 2 levels. CO 2 storage in reactive basalts might be one of these solutions by permanently converting injected gaseous CO 2 into solid carbonates. Herein, we report results from a field demonstration in which ∼1000 metric tons of CO 2 was injected into a natural basalt formation in eastern Washington state. Following post-injection monitoring for 2 years, cores were obtained from within the injection zone and subjected to detailed physical and chemical analysis. Nodules found in vesicles throughout the cores were identified as the carbonate mineral, ankerite Ca[Fe,Mg,Mn](CO 3 ) 2 . Carbon isotope analysis showed the nodules are chemically distinct compared with natural carbonates present in the basalt and in clear correlation with the isotopic signature of the injected CO 2 . These findings provide field validation of rapid mineralization rates observed from years of laboratory testing with basalts.

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