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Natural Attenuation of Chlorinated Volatile Organic Compounds in a Freshwater Tidal Wetland, Aberdeen Proving Ground, Maryland

By Michelle M. Lorah, Lisa D. Olsen, Barrett L. Smith, Mark A. Johnson, and William B. Fleck

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Groundwater contaminant plumes that are flowing toward or currently discharging to wetland areas present unique remediation problems because of the hydrologic connections between Groundwater and surface water and the sensitive habitats in wetlands. Because wetlands typically have a large diversity of microorganisms and redox conditions that could enhance biodegradation, they are ideal environments for natural attenuation of organic contaminants, which is a treatment method that would leave the ecosystem largely undisturbed and be cost effective. During 1992-97, the U.S. Geological Survey investigated the natural attenuation of chlorinated volatile organic compounds (VOC's) in a contaminant plume that discharges from a sand aquifer to a freshwater tidal wetland along the West Branch Canal Creek at Aberdeen Proving Ground, Maryland. Characterization of the hydrogeology and geochemistry along flowpaths in the wetland area and determination of the occurrence and rates of biodegradation and sorption show that natural attenuation could be a feasible remediation method for the contaminant plume that extends along the West Branch Canal Creek.

The aquifer, which received contaminants in the past from sources that were located upgradient of the current eastern boundary of the wetland, is about 40 to 45 feet thick in the study area. The overlying wetland sediments consist of two distinct layers that have a combined thickness of about 6 to 12 feet--an upper unit of peat and a lower unit of silty to sandy clay or clayey sand. Head distributions show strong vertical gradients, and flow directions are predominantly upward through the wetland sediments.

Tidal fluctuations, however, cause some reversals in Groundwater-flow directions and changes in discharge locations, which affect the distribution and transport of contaminants. The average linear velocity of Groundwater is estimated to be about 2 to 3 feet per year along vertical flow lines in the wetland area, and the total Groundwater discharge along a 1-foot-wide strip of the wetland extending from the eastern wetland boundary to the creek is in the range of 0.13 to 0.25 feet squared per day.

The major parent contaminants in the aquifer were trichloroethylene (TCE); 1,1,2,2-tetrachloroethane (PCA); carbon tetrachloride (CT); and chloroform (CF). The aquifer was typically aerobic, but Groundwater in the wetland sediments became increasingly anaerobic along the upward flow direction. Iron-reducing conditions were predominant in the lower wetland sediment unit composed of clayey sand and silt, and methanogenesis was predominant in an upper unit composed of peat. Total concentrations of VOC's and the relative proportions of parent compounds to anaerobic daughter products changed substantially as the contaminants were transported upward through these changing redox environments. Concentrations of the parent compounds TCE and PCA ranged from about 100 to 2,000 micrograms per liter in the aquifer beneath the wetland, whereas concentrations of daughter products were low or undetectable. In contrast, the parent compounds commonly were not detected in Groundwater in the wetland sediments, but the daughter compounds 1,2- dichloroethylene (12DCE), vinyl chloride (VC), 1,1,2-trichloroethane (112TCA), and 1,2-dichloroethane (12DCA) were observed. 12DCE and VC were the dominant daughter products in the wetland sediments, even where PCA was the primary parent contaminant discharging to the wetland. The presence of these daughter products in water in the wetland sediments indicates that TCE and PCA are degraded by reductive dechlorination reactions in the naturally anaerobic wetland sediments.

Although production of daughter products was observed, total concentrations of the VOC's decreased upward through the 6- to 12-feet-thick wetland sediments and were less than 5 micrograms per liter near the surface. The daughter products are apparently further degraded by these anaerobic processes to non-chlorinated, non-toxic endproducts, or are removed by other attenuation processes such as aerobic degradation or volatilization.

Several sets of anaerobic microcosms, some amended with TCE concentrations of 400 or 990 micrograms per liter (3.0 or 7.5 micromoles per liter) and one amended with PCA concentration of 480 micrograms per liter (2.9 micromoles per liter), were constructed in the laboratory using wetland sediment and Groundwater from the study area. These microcosm experiments confirmed field observations that 12DCE and VC are the dominant daughter products from anaerobic biodegradation of both TCE and PCA. Production of 112TCA and 12DCA also was observed in the PCA-amended microcosms, but concentrations were lower than those of 12DCE and VC. These results indicate that degradation of PCA occurs through both hydrogenolysis and dichloroelimination pathways under anaerobic conditions. Daughter products were not observed in sterile controls, except for relatively low concentrations of 12DCE in the PCA-amended controls, suggesting that the reactions were predominantly microbially mediated. Parent and daughter concentrations in the microcosms decreased to less than 5 micrograms per liter in less than 34 days under methanogenic conditions, thus showing extremely rapid biodegradation rates in these organic-rich wetland sediments.

Maximum potential rate constants for biodegradation of TCE and PCA, which were calculated from the microcosm experiments assuming first-order degradation rates, ranged from 0.10 to 0.31 per day under methanogenic conditions, corresponding to half-lives of 2 to 7 days. The rate constant for TCE biodegradation under sulfate-reducing conditions was 0.045 per day (half-life of 15 days), which is lower than under methanogenic conditions. These estimated rate constants for the wetland sediments are two to three orders of magnitude higher than those reported in the literature for TCE biodegradation in microcosms constructed with sandy aquifer sediments.

Aerobic biodegradation rates for cis-12DCE, trans-12DCE, and VC were in the same range as those measured for TCE and PCA under anaerobic conditions in microcosm experiments. Thus, production of these daughter products by anaerobic biodegradation of TCE and PCA could be balanced by their consumption where oxygen is available in the wetland sediment, such as near roots and land surface. In the aerobic microcosm experiments, biodegradation of cis-12DCE, trans-12DCE, and VC occurred only if methane consumption occurred, indicating that methanotrophs were involved in the process. Aerobic biodegradation was fastest for vinyl chloride and slowest for TCE in the microcosm experiments. These results agree with other laboratory and field studies that have shown faster degradation by methane-utilizing cultures when the compounds are less halogenated.

Equilibrium sorption isotherms were measured in 24-hour batch tests and used to estimate distribution coefficients (Kd's) to describe the ratios of sorbed to aqueous concentrations of PCA and the daughter products cis-12DCE, trans-12DCE, and VC. The estimated Kd's for PCA, cis-12DCE, trans-12DCE, and VC were about 2.3, 1.8, 2.4, and 1.3 liters per kilogram of sediment, respectively. Sorbed concentrations of PCA, cis-12DCE, and trans-12DCE in the wetland sediments, therefore, would be expected to be about twice the concentration measured in the water, whereas sorbed concentrations of VC would not be much greater than the aqueous concentrations. Coefficients of retardation, which were calculated using the Kd's and an advective flow velocity of about 2 feet per year, indicate that sorption alone would cause the movement of the contaminants in the wetland sediments to be 6 to 10 times slower than the advective Groundwater flow.

Biodegradation and sorption, therefore, are significant natural attenuation mechanisms for chlorinated hydrocarbons in these wetland sediments. The relatively thin layers of wetland sediments are critical in reducing contaminant concentrations and toxicity of the Groundwater before it discharges to the wetland surface and the creek, and natural attenuation in the wetland sediments could be an effective remediation method for the Groundwater contaminants.

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