Chloroethene dechlorination in acidic groundwater: Implications for combining fenton's treatment with natural attenuation

A sulfuric acid leak in 1988 at a chloroethene‐contaminated groundwater site at the Naval Air Station Pensacola has resulted in a long‐term record of the behavior of chloroethene contaminants at low pH and a unique opportunity to assess the potential impact of source area treatment technologies, which involve acidification of the groundwater environment (e.g., Fenton's‐based in situ chemical oxidation), on downgradient natural attenuation processes. The greater than 75 percent decrease in trichloroethene (TCE) concentrations and the shift in contaminant composition toward predominantly reduced daughter products (dichloroethene [DCE] and vinyl chloride [VC]) that were observed along a 30‐m groundwater flow path characterized by highly acidic conditions (pH = 3.5 ± 0.4) demonstrated that chloroethene reductive dechlorination can continue to be efficient under persistent acidic conditions. The detection of Dehalococcoides‐type bacteria within the sulfuric acid/chloroethene co‐contaminant plume was consistent with biotic chloroethene reductive dechlorination. Microcosm studies conducted with ¹⁴C‐TCE and ¹⁴C‐VC confirmed biotic reductive dechlorination in sediment collected from within the sulfuric acid/chloroethene co‐contaminant plume. Microcosms prepared with sediment from two other locations within the acid plume, however, demonstrated only a limited mineralization to ¹⁴CO₂ and ¹⁴CO, which was attributed to abiotic degradation because no significant differences were observed between experimental and autoclaved control treatments. These results indicated that biotic and abiotic mechanisms contributed to chloroethene attenuation in the acid plume at NAS Pensacola and that remediation techniques involving acidification of the groundwater environment (e.g., Fenton's‐based source area treatment) do not necessarily preclude efficient chloroethene degradation. © 2007 Wiley Periodicals, Inc.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/ aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally atteuated by a combination of active anaerobic and aerobic biotransformation processes.     

Accumulation of dechlorination daughter products: A valid metric of chloroethene biodegradation

In situ reductive dechlorination of perchloroethene (PCE) and trichloroethene (TCE) generates characteristic chlorinated (cis‐dichloroethene [cis‐DCE] and vinyl chloride [VC]) and nonchlorinated (ethene and ethane) products. The accumulation of these daughter products is commonly used as a metric for ongoing biodegradation at field sites. However, this interpretation assumes that reductive dechlorination is the only chloroethene degradation process of any significance in situ and that the characteristic daughter products of chloroethene reductive dechlorination persist in the environment. Laboratory microcosms, prepared with aquifer and surface‐water sediments from hydrologically diverse sites throughout the United States and amended with [1,2‐¹⁴C] TCE, [1,2‐¹⁴C] DCE, [1,2‐¹⁴C] DCA, or [1,2‐¹⁴C] VC, demonstrated widely variable patterns of intermediate and final product accumulation. In predominantly methanogenic sediment treatments, accumulation of ¹⁴C‐DCE, ¹⁴C‐VC, ¹⁴C‐ethene, and ¹⁴C‐ethane predominated. Treatments characterized by significant Fe(III) and/or Mn(IV) reduction, on the other hand, demonstrated substantial, and in some cases exclusive, accumulation of ¹⁴CO₂ and ¹⁴CH₄. These results suggest that relying on the accumulation of cis‐DCE, VC, ethene, and ethane may substantially underestimate overall chloroethene biodegradation at many sites. © 2007 Wiley Periodicals, Inc. *

1 This article is a U.S. government work and, as such, is in the public domain in the United States of America.

     

Threshold amounts of organic carbon needed to initiate reductive dechlorination in groundwater systems

Aquifer sediment and groundwater chemistry data from 15 Department of Defense facilities located throughout the United States were collected and analyzed with the goal of estimating the amount of natural organic carbon needed to initiate reductive dechlorination in groundwater systems. Aquifer sediments were analyzed for hydroxylamine and NaOH‐extractable organic carbon, yielding a probable underestimate of potentially bioavailable organic carbon (PBOC). Aquifer sediments were also analyzed for total organic carbon (TOC) using an elemental combustion analyzer, yielding a probable overestimate of bioavailable carbon. Concentrations of PBOC correlated linearly with TOC with a slope near one. However, concentrations of PBOC were consistently five to ten times lower than TOC. When mean concentrations of dissolved oxygen observed at each site were plotted versus PBOC, it showed that anoxic conditions were initiated at approximately 200 mg/kg of PBOC. Similarly, the accumulation of reductive dechlorination daughter products relative to parent compounds increased at a PBOC concentration of approximately 200 mg/kg. Concentrations of total hydrolysable amino acids (THAA) in sediments also increased at approximately 200 mg/kg, and bioassays showed that sediment CO₂ production correlated positively with THAA. The results of this study provide an estimate for threshold amounts of bioavailable carbon present in aquifer sediments (approximately 200 mg/kg of PBOC; approximately 1,000 to 2,000 mg/kg of TOC) needed to support reductive dechlorination in groundwater systems. © 2012 Wiley Periodicals, Inc.     

Estimated trichloroethene transformation rates due to naturally occurring biodegradation in a fractured rock aquifer

Rates of trichloroethene (TCE) mass transformed by naturally occurring biodegradation processes in a fractured rock aquifer underlying a former Naval Air Warfare Center (NAWC) site in West Trenton, New Jersey, were estimated. The methodology included (1) dividing the site into eight elements of equal size and vertically integrating observed concentrations of two daughter products of TCE biodegradation—cis‐dichloroethene (cis‐DCE) and chloride—using water chemistry data from a network of 88 observation wells; (2) summing the molar mass of cis‐DCE, the first biodegradation product of TCE, to provide a probable underestimate of reductive biodegradation of TCE, (3) summing the molar mass of chloride, the final product of chlorinated ethene degradation, to provide a probable overestimate of overall biodegradation. Finally, lower and higher estimates of aquifer porosities and groundwater residence times were used to estimate a range of overall transformation rates. The highest TCE transformation rates estimated using this procedure for the combined overburden and bedrock aquifers was 945 kg/yr, and the lowest was 37 kg/yr. However, hydrologic considerations suggest that approximately 100 to 500 kg/yr is the probable range for overall TCE transformation rates in this system. Estimated rates of TCE transformation were much higher in shallow overburden sediments (approximately 100 to 500 kg/yr) than in the deeper bedrock aquifer (approximately 20 to 0.15 kg/yr), which reflects the higher porosity and higher contaminant mass present in the overburden. By way of comparison, pump‐and‐treat operations at the NAWC site are estimated to have removed between 1,073 and 1,565 kg/yr of TCE between 1996 and 2009. © 2012 Wiley Periodicals, Inc.*     

Enhanced dichloroethene biodegradation in fractured rock under biostimulated and bioaugmented conditions

Significant microbial reductive dechlorination of [1,2 ¹⁴C] cis‐dichloroethene (DCE) was observed in anoxic microcosms prepared with unamended, fractured rock aquifer materials, which were colonized in situ at multiple depths in two boreholes at the Naval Air Warfare Center (NAWC) in West Trenton, New Jersey. The lack of significant reductive dechlorination in corresponding water‐only treatments indicated that chlororespiration activity in unamended, fractured rock treatments was primarily associated with colonized core material. In these unamended fractured rock microcosms, activity was highest in the shallow zones and generally decreased with increasing depth. Electron‐donor amendment (biostimulation) enhanced chlororespiration in some but not all treatments. In contrast, combining electron‐donor amendment with KB1 amendment (bioaugmentation) enhanced chlororespiration in all treatments and substantially reduced the variability in chlororespiration activity both within and between treatments. These results indicate (1) that a potential for chlororespiration‐based bioremediation exists at NAWC Trenton but is limited under nonengineered conditions, (2) that the limitation on chlororespiration activity is not entirely due to electron‐donor availability, and (3) that a bioaugmentation approach can substantially enhance in situ bioremediation if the requisite amendments can be adequately distributed throughout the fractured rock matrix. © 2012 Wiley Periodicals, Inc.*     

A preliminary model of nutrient cycling in sediments of a Mediterranean lagoon

A model of nitrogen and phosphorus cycles in the sediment of a lagoon has been developed. This model was applied to the Thau lagoon (southern France). Sediment was sliced in three layers to reproduce the oxygen profile, which is simulated within the model. Following an equilibrium hypothesis, the model was calibrated against field data. State variables and fluxes were estimated in the sediment and across the sediment-water interface. A Monte Carlo sensitivity analysis was performed to determine the most sensitive parameters and sediment state variables. A dynamic simulation with varying oxygen concentrations then showed the influence of anoxia on the phosphorus and nitrogen fluxes between water and sediment.