We have previously defined in situ biogeochemical transformation as the biogenic formation of reactive minerals that are capable of abiotically degrading chlorinated solvents such as trichloroethene without accumulation of degradation products such as vinyl chloride (AFCEE et al. ). This process has been implemented in biowalls used to intercept contaminated groundwater. Abiotic patterns of contaminant degradation were observed at Altus Air Force Base (AFB) and in an associated column study, but not at other sites including Dover AFB. These abiotic patterns were associated with biogenic formation of reactive iron sulfide minerals. Iron sulfides in the form of small individual grains, coatings on magnetite, and sulfur‐deficient pyrite framboids were observed in samples collected from the Altus AFB biowalls and one of the EPA columns. Larger iron sulfide grains coated with oxide layers were observed in samples collected from Dover AFB. Altus AFB and the EPA column differed from Dover AFB in that groundwater flow at Dover AFB was relatively slow and potentially reversing. High volumetric sulfate consumption rates, an abiotic pattern of trichloroethene (TCE) degradation, and the formation of small, high surface area iron sulfide particles were associated with relatively high rates of TCE removal via an abiotic pattern. Geochemical modeling demonstrated that iron monosulfides such as mackinawite were near saturation, and iron disulfides such as pyrite were supersaturated at all sites. This environmental condition can be supportive of nucleation of small particles rather than crystal growth leading to larger particles. When nucleation is dominant, small, high surface area, and reactive particles result. When crystal growth dominates the crystals are larger and have lower specific surface area and reactivity. These results taken together suggest that creation of a dynamic environment can promote biogeochemical transformation based on generation of reactive iron sulfides.

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A pilot-scale permeable reactive barrier filled with plant mulch was installed at Altus Air Force Base in Oklahoma, USA to treat trichloroethylene (TCE) contamination in groundwater emanating from a landfill. The barrier was constructed in June 2002. It was 139 meters long, 7 meters deep, and 0.5 meters wide. The barrier is also called a Biowall because one of the mechanisms for removal of TCE is anaerobic biodegradation. This study aimed at evaluating the performance of the pilot-scale Biowall after its installation. Data from over four years' monitoring indicated that the Biowall greatly changed geochemistry in the study area and stimulated TCE removal. The concentration of TCE in the Biowall and downgradient of the Biowall was greatly reduced as compared to that in ground water upgradient of the Biowall, while the concentration of cis-DCE in the Biowall and downgradient of the Biowall was much higher than that observed upgradient of the Biowall. Over time, the concentration of vinyl chloride in the Biowall and downgradient of the Biowall increased. Dehalococcoides DNA was detected within and downgradient of the Biowall, corresponding to the observation that vinyl chloride was produced at these locations. Results from a tracer study indicated that the regional groundwater flow pattern ultimately determined the flow direction in the area around the Biowall. The natural groundwater velocity was estimated at an average of 0.060 +/- 0.015 m/d.