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'Contamination of soils and groundwaters with chlorinated aliphatic hydrocarbons (CAHs) is one of the most serious environmental problems in the DOE system and in the nation at large. These compounds are designated as priority pollutants by the US Environmental Protection Agency (EPA) and are known or suspected to be carcinogenic or mutagenic in humans. These compounds are readily transported by groundwater and are not reduced to acceptable concentrations for human consumption by most municipal water supply treatments; thus the compounds represent a significant hazard to a large portion of the human population. In situ bioremediation is an emerging technology that shows great promise for mitigation of CAH contamination at many sites. One of the most severe limitations of in-situ bioremediation is the difficulty of proving when it is working at a given site. The concentrations of CAHs and their degradation products in plumes may be difficult to relate to the efficiency of the remediation process because of dilution effects, but this problem is mitigated to a large extent by measuring isotope ratios. If there is a significant isotopic fractionation between CAHs and derivative chlorine-bearing products, then the fraction of CAH that is dechlorinated can be inferred from the {sup 37}Cl/{sup 35}Cl and {sup 13}C/{sup 12}C isotope ratios of the residual CAH. It is important to point out that there is currently no published information available on the magnitude of chlorine and carbon isotopic fractionation associated with biological degradation of CAHs. The authors plan to help eliminate this important gap in the knowledge with the work being performed here. This work is relevant to EMSP goals because it will provide a new and cost-effective means of evaluating and monitoring the effectiveness of in-situ bioremediation. It will employ newly developed techniques to characterize isotopic fractionation (of chlorine and carbon) associated with biotic and abiotic degradation of CAHs in laboratory microcosms. These techniques and the data acquired by using them in laboratory studies will form the fundamental basis for quantitative assessment of the mechanisms, rates, and efficiencies of various in-situ bioremediation schemes for CAHs. This report summarizes work as of 21 months into a 36-month project. First, the author has developed methods for precise measurement of stable carbon and chlorine isotope ratios of micromolar amounts of CAHs. He has also developed methods for quantitative extraction of CAHs from water and air. He has applied these methods in laboratory experiments, to investigate isotopic fractionation caused by microbial degradation and by abiotic processes such as evaporation and chemical reduction. He has also applied these methods to field investigations of contaminated groundwater aquifers at the Paducah Gaseous Diffusion Plant, Kentucky and at several manufacturing plants in the Chicago and Kansas City metropolitan areas. Results of much of this work have already been incorporated into four manuscripts that have been published, accepted for publication, or are in review.

Stable isotopic investigations of in-situ bioremediation of chlorinated organic solvents. 1998 annual progress report