For more than 10 years, electron donor has been injected into the Snake River aquifer beneath the Test Area North site of the Idaho National Laboratory for the purpose of stimulating microbial reductive dechlorination of trichloroethene (TCE) in groundwater. This has resulted in significant TCE removal from the source area of the contaminant plume and elevated dissolved CH4 in the groundwater extending 250 m from the injection well. The delta13C of the CH4 increases from 56o/oo in the source area to -13 o/oo with distance from the injection well, whereas the delta13C of dissolved inorganic carbon decreases from 8 o/oo to -13 o/oo, indicating a shift from methanogenesis to methane oxidation. This change in microbial activity along the plume axis is confirmed by PhyloChip microarray analyses of 16S rRNA genes obtained from groundwater microbial communities, which indicate decreasing abundances of reductive dechlorinating microorganisms (e.g., Dehalococcoides ethenogenes) and increasing CH4-oxidizing microorganisms capable of aerobic co-metabolism of TCE (e.g., Methylosinus trichosporium). Incubation experiments with 13C-labeled TCE introduced into microcosms containing basalt and groundwater from the aquifer confirm that TCE co-metabolism is possible. The results of these studies indicate that electron donor amendment designed to stimulate reductive dechlorination of TCE may also stimulate co-metabolism of TCE.

Water and chemical transport from a point source within vadose zone sediments at Hanford were examined with a leak test consisting of five 3800-liter aliquots of water released at 4.5 m depth every week over a 4-week period. The third aliquot contained bromide, D2O and 87Sr. Movement of the tracers was monitored for 9 months by measuring pore water compositions of samples from boreholes drilled 2-8 m from the injection point. Graded sedimentary layers acting as natural capillary barriers caused significant lateral spreading of the leak water. D2O concentrations >50 percent of the concentration in the tracer aliquot were detected at 9-11 m depth. However, increased water contents, lower d18O values, and geophysical monitoring of moisture changes at other depths signified high concentrations of leak fluids were added where D2O concentrations were <3 percent above background, suggesting limited mixing between different aliquots of the leak fluids. Initially high bromide concentrations decreased more rapidly over time than D2O, suggesting enhanced transport of bromide due to anion exclusion. No significant increase in 87Sr was detected in the sampled pore water, indicating strong retardation of Sr by the sediments. These results highlight some of the processes strongly affecting chemical transport in the vadose zone and demonstrate the significant separation of contaminant plumes that can occur.

Strontium isotope compositions (87Sr/86Sr) measured in groundwater samples from 273 wells in the Pasco Basin unconfined aquifer below the Hanford Site show large and systematic variations that provide constraints on groundwater recharge, weathering rates of the aquifer host rocks, communication between unconfined and deeper confined aquifers, and vadose zone-groundwater interaction. The impact of millions of cubic meters of wastewater discharged to the vadose zone (103-105 times higher than ambient drainage) shows up strikingly on maps of groundwater 87Sr/86Sr. Extensive access through the many groundwater monitoring wells at the site allows for an unprecedented opportunity to evaluate the strontium geochemistry of a major aquifer, hosted primarily in unconsolidated sediments, and relate it to both long term properties and recent disturbances. Groundwater 87Sr/86Sr increases systematically from 0.707 to 0.712 from west to east across the Hanford Site, in the general direction of groundwater flow, as a result of addition of Sr from the weathering of aquifer sediments and from diffuse drainage through the vadose zone. The lower 87Sr/86Sr groundwater reflects recharge waters that have acquired Sr from Columbia River Basalts. Based on a steady-state model of Sr reactive transport and drainage, there is an average natural drainage flux of 0-1.4 mm/yr near the western margin of the Hanford Site, and ambient drainage may be up to 30 mm/yr in the center of the site assuming an average bulk rock weathering rate of 10-7.5 g/g/yr.