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Degradation reactions controlling the fate of 1,1,2,2tetrachloroethane (PCA) in a freshwater tidal wetland that is a discharge area for a contaminated aquifer were investigated by a combined field and laboratory study. Samples from nested piezometers and porous-membrane sampling devices (peepers) showed that PCA concentrations decreased and that less chlorinated daughter products formed as the groundwater became increasingly reducing along upward flow paths through the wetland sediments. The cis and trans isomers of 1,2-dichloroethylene (12DCE) and vinyl chloride (VC) were the predominant daughter products detected from degradation of PCA in the field and in microcosms constructed under methanogenic conditions. Significantly lower ratios of cis-12DCE to trans-12DCE were produced by PCA degradation than by degradation of trichloroethylene, a common co-contaminant with PCA. 1,1,2-Trichloroethane (112TCA) and 1,2-dichloroethane (12DCA) occurred simultaneously with 12DCE, indicating simultaneous hydrogenolysis and dichloroelimination of PCA. From an initial PCA concentration of about 1.5 µmol/L, concentrations of PCA and its daughter products decreased to below detection within a 1.0-m vertical distance in the wetland sediments and within 34 days in the microcosms. The results indicate that natural attenuation of PCA through complete anaerobic biodegradation can occur in wetlands before sensitive surface water receptors are reached.

Abstract. Field evidence collected along two groundwater flow paths shows that anaerobic biodegradation naturally attenuates a plume of chlorinated volatile organic compounds as it discharges from an aerobic sand aquifer through wetland sediments. A decrease in concentrations of two parent contaminants, trichloroethylene (TCE) and 1,1,2,2-tetrachloroethane (PCA), and a concomitant increase in concentrations of anaerobic daughter products occurs along upward flow paths through the wetland sediments. The daughter products 1,2-dichloroethylene, vinyl chloride, 1,1,2-trichloroethane, and 1,2-dichloroethane are produced from hydrogenolysis of TCE and from PCA degradation through hydrogenolysis and dichloroelimination (reductive dechlorination) pathways. Total concentrations of TCE, PCA, and their degradation products, however, decrease to below detection levels within 0.15-0.30 rn of land surface. The enhanced reductive dechlorination of TCE and PCA in the wetland sediments is associated with the naturally higher concentrations of dissolved organic carbon and the lower redox state of the groundwater compared to the aquifer. This field study indicates that wetlands and similar organic-rich environments at groundwater/surface-water interfaces may be important in intercepting groundwater contaminated with chlorinated organics and in naturally reducing concentrations and toxicity before sensitive surface-water receptors are reached. Background on Anaerobic Degradation ProcessesAnaerobic degradation of TCE has been fairly well studied, but few studies of PCA degradation under environmental conditions have been conducted. TCE is biodegraded under anaerobic conditions through hydrogenolysis, a reductive dechlorination process that sequentially produces isomers of 1,2-dichloroethylene ( Materials and Methods Groundwater Sampling SitesWater samples were collected for this study during June to October 1995, mainly from nested drive-point piezometers GROUND-WATER-FLOW [• SULFATE-AND IRON-REDUCING ZONE --Concentrations Groundwater Sampling and Analytical ProceduresSampling and analytical procedures have been described by Lorah et al. [1997] and will be summarized here. Piezometers screened in the aquifer generally were purged and sampled using a peristaltic pump from which TygonT•' tubing was extended to directly above the piezometer screen. Piezometers screened in the wetland sediments, where recovery rates were generally low, were purged and sampled using stainless-steel bailers that had a bottom-discharge device. Peepers were

Leachate from municipal landfills can create groundwater contaminant plumes that may last for decades to centuries. The fate of reactive contaminants in leachate‐affected aquifers depends on the sustainability of biogeochemical processes affecting contaminant transport. Temporal variations in the configuration of redox zones downgradient from the Norman Landfill were studied for more than a decade. The leachate plume contained elevated concentrations of nonvolatile dissolved organic carbon (NVDOC) (up to 300 mg/L), methane (16 mg/L), ammonium (650 mg/L as N), iron (23 mg/L), chloride (1030 mg/L), and bicarbonate (4270 mg/L). Chemical and isotopic investigations along a 2D plume transect revealed consumption of solid and aqueous electron acceptors in the aquifer, depleting the natural attenuation capacity. Despite the relative recalcitrance of NVDOC to biodegradation, the center of the plume was depleted in sulfate, which reduces the long‐term oxidation capacity of the leachate‐affected aquifer. Ammonium and methane were attenuated in the aquifer relative to chloride by different processes: ammonium transport was retarded mainly by physical interaction with aquifer solids, whereas the methane plume was truncated largely by oxidation. Studies near plume boundaries revealed temporal variability in constituent concentrations related in part to hydrologic changes at various time scales. The upper boundary of the plume was a particularly active location where redox reactions responded to recharge events and seasonal water‐table fluctuations. Accurately describing the biogeochemical processes that affect the transport of contaminants in this landfill‐leachate‐affected aquifer required understanding the aquifer's geologic and hydrodynamic framework.