Laboratory experiments were performed using minimally disturbed sedimentary rocks to measure the coupled diffusion and abiotic reaction of trichloroethene (TCE) through rock core samples. Results showed that, for all rock types studied, TCE dechlorination occurred, as evidenced by generation of acetylene, ethene, and/or ethane daughter products. First-order bulk reaction rate constants for TCE degradation ranged from 8.3 × 10(-10) to 4.2 × 10(-8) s(-1). Observed reaction rate constants showed a general correlation to the available ferrous iron content of the rock, which was determined by evaluating the spatial distribution of ferrous iron relative to that of the rock porosity. For some rock types, exposure to TCE resulted in a decrease in the effective diffusivity. Scanning electron microscopy (SEM) indicated that the decrease in the effective diffusivity was due to a decrease in the porosity that occurred after exposure to TCE. Overall, these coupled diffusion and reaction results suggest that diffusion of TCE into rock matrices as well as the rate and extent of back-diffusion may be substantially mitigated in rocks that contain ferrous iron or other naturally occurring reactive metals, thereby lessening the impacts of matrix diffusion on sustaining dissolved contaminant plumes in bedrock aquifers.

Laboratory experiments were performed in discretely fractured sandstone blocks to evaluate the use of bioaugmentation to treat residual dense non-aqueous phase liquid (DNAPL) tetrachloroethene (PCE). Significant dechlorination of PCE and growth of Dehalococcoides spp. (DHC) occurred within the fractures. DNAPL dissolution was enhanced during bioaugmentation by up to a factor of approximately 3.5, with dissolved PCE concentrations at or near aqueous solubility. The extent of dechlorination and DNAPL dissolution enhancement were dependent upon the fracture characteristics, residence time in the fractures, and dissolved concentration of PCE. No relationship was observed between planktonic DHC concentrations exiting the fracture and the observed extents of PCE dechlorination and DNAPL dissolution. Measured planktonic DHC concentrations exiting the fracture increased with increasing flow rate and bioaugmentation dosage, suggesting that these parameters may be important for distribution of DHC to treat dissolved chlorinated ethenes migrating downgradient of the DNAPL source. Bioaugmentation dosage, for the DHC dosages and conditions studied, did not have a measurable impact on DNAPL dissolution or dechlorination within the fractures themselves. Overall, these results indicate that bioaugmentation may be a viable remedial option for treating DNAPL sources in bedrock.

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