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Anaerobic degradation of 1,1,2,2-tetrachloroethane and association with microbial communities in a freshwater tidal wetland, Aberdeen Proving Ground, Maryland: Laboratory experiments and comparisons to field data

Defining biodegradation rates and processes is a critical part of assessing the feasibility of monitored natural attenuation as a remediation method for ground water containing organic contaminants. During 1998–2001, the U.S. Geological Survey conducted a microbial study at a freshwater tidal wetland along the West Branch Canal Creek, Aberdeen Proving Ground, Maryland, as part of an investigation of natural attenuation of chlorinated volatile organic compounds (VOCs) in the wetland sediments. Geochemical analyses and molecular biology techniques were used to investigate factors controlling anaerobic degradation of 1,1,2,2-tetrachloroethane (TeCA), and to characterize the microbial communities that potentially are important in its degradation. Rapid TeCA and daughter product degradation observed in laboratory experiments and estimated with field data confirm that natural attenuation is a feasible remediation method at this site. The diverse microbial community that seems to be involved in TeCA degradation in the wetland sediments varies with changing spatial and seasonal conditions, allowing continued effective natural attenuation throughout the year. Rates of TeCA degradation in anaerobic microcosm experiments conducted with wetland sediment collected from two different sites (WB23 and WB30) and during three different seasons (March–April 1999, July–August 1999, and October–November 2000) showed little spatial variability but high seasonal variability. Initial first-order degradation rate constants for TeCA ranged from 0.10±0.01 to 0.16±0.05 per day (halflives of 4.3 to 6.9 days) for March–April 1999 and October–November 2000 microcosms incubated at 19 degrees Celsius, whereas lower rate constants of 0±0.03 and 0.06±0.03 per day were obtained in July–August 1999 microcosms incubated at 19 degrees Celsius. Microbial community profiles showed that low microbial biomass and microbial diversity in the summer, possibly due to competition for nutrients by the wetland vegetation, could account for these unexpectedly low degradation rates. In microcosms incubated at 5 degrees Celsius, about 50 percent of the initial TeCA in solution was converted to daughter products within a 35-day incubation period, indicating that biodegradation in the wetland sediments can continue during cold winter temperatures. Initial pathways of TeCA degradation were the same in the wetland sediment microcosms regardless of the season or sediment collection site, the reduction-oxidation conditions, and the previous exposure of the sediment to contamination. Immediate and simultaneous dichloroelimination and hydrogenolysis, producing 1,2-dichloroethene (12DCE) and 1,1,2-trichloroethane (112TCA), respectively, were the initial TeCA degradation pathways in all live microcosm experiments. The production and degradation of vinyl chloride (VC), which is the most toxic of the TeCA daughter compounds, was affected by spatial and seasonal variability, reduction-oxidation condition, and pre-exposure of the wetland sediment. TeCA-amended microcosms constructed with WB30 sediment showed approximately twice as much VC production as those constructed with WB23 sediment. Results of 112TCA-amended microcosms indicated that the greater production of VC in the WB30 sediment resulted from a greater predominance of the 112TCA dichloro elimination pathway in these sediments. VC degradation also was substantially higher in microcosms constructed with WB30 sediment than those constructed with WB23 sediment, resulting in lower VC concentrations at the end of WB30 microcosms. Enrichment experiments in which microcosm slurry was amended with high initial VC concentrations showed that the spatial difference in VC degradation was negligible after prolonged incubation under methanogenic conditions. Inhibition of methanogenic activity in microcosms by addition of sulfate or of 2-bromoethanesulfonic acid inhibited production and degradation of VC. Inhibition of methanogenesis by addition of ferric iron or of 2-bromoethanesulfonic acid also completely inhibited VC degradation in VC-amended enrichment experiments. Pre-exposure to VC substantially increased degradation in VC-amended enrichment experiments. A microbial consortium, rather than one microbial species or group, likely is involved in the degradation of TeCA, as indicated by the occurrence of multiple degradation pathways and the variability in VC production and degradation. A bacterial peak at 90 base pair (bp) fragment length in terminal- restriction fragment length polymorphism (TRFLP) profiles was associated with TeCA hydrogenolysis to 112TCA, and bacterial species represented by 198 and 170 bp fragment lengths were associated with TeCA dichloroelimination to 12DCE. Dichloroelimination of 112TCA to VC was associated with increasing dominance of the 198 bp bacterial peak in March–April 1999 and October–November 2000 microcosms, whereas an 86 bp or the 170 bp bacterial peak was associated with 112TCA dichloroelimination in the summer experiment. Hydrogenolysis of 12DCE to VC was associated with a carbon dioxide-utilizing methanogen at 307 bp in the March–April 1999 and October–November 2000 microcosm experiments, whereas production of VC occurred despite low methanogen biomass and methane production in the July–August 1999 experiments. Production of VC in the absence of methane production also occurred in 12DCE-amended enrichment cultures. The exponential production of VC in the 12DCE-amended enrichment cultures after an initial lag indicated growth of a microbial species or group, possibly one of the known dehalorespiring bacteria. Molecular analyses using specific primers targeting dehalorespiring bacteria of the Dehalococcoides group (Dehalococcoides ethenogenes and Dehalococcoides sp. strain FL2) and of the acetate-oxidizing Desulfuromonas group (Desulfuromonas sp. strain BB1 and Desulfuromonas chloroethenica) showed the presence of these bacteria in microcosm slurry from site WB30 but not from site WB23. Addition of hydrogen, which is the favored substrate of Dehalococcoides, tripled VC production in 12DCE-amended enrichment cultures. VC degradation showed a marked association with an increase in the relative proportion of Methanosarcinaceae, a family of methanogens that includes all those capable of utilizing acetate as a substrate, in the total methanogen community. Half-lives for TeCA and TCE estimated from field data were in the range of 60 to 100 days, which agrees well with laboratory estimates of degradation rates considering the inherent differences in the laboratory and field systems. Both laboratory microcosm experiments and field data showed that 12DCE and VC are the predominant, persistent daughter compounds from TeCA degradation. In addition, porewater chemistry showed higher accumulation of VC in the wetland sediment at site WB30 than at site WB23, as was observed in the microcosm experiments. Molecular analyses of grab samples of surficial wetland sediment showed that all the microbial species or groups linked to TeCA degradation in the microcosm experiments were present in all sediment samples. Microbial biomass and diversity were lowest in an area of the wetland (transect C-C') where porewater VOC concentrations are highest, indicating that the higher VOC concentrations could result from lower degradation rates. The lower microbial biomass and diversity in this area could be caused by toxic effects of the contaminants, or possibly from differences in frequency and duration of tidal inundation.

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Optimization of ground-water withdrawal at the old O-Field area, Aberdeen Proving Ground, Maryland

The U.S. Army disposed of chemical agents, laboratory materials, and unexploded ordnance at the Old O-Field landfill at Aberdeen Proving Ground, Maryland, beginning prior to World War II and continuing until at least the 1950's. Soil, ground water, surface water, and wetland sediments in the Old O-Field area were contaminated by the disposal of these materials. The site is in the Atlantic Coastal Plain, and is characterized by a complex series of Pleistocene and Holocene sediments formed in various fluvial, estuarine, and marine-marginal hydrogeologic environments. A previously constructed transient finite-difference ground-water-flow model was used to simulate ground-water flow and the effects of a pump-and-treat remediation system designed to prevent contaminated ground water from flowing into Watson Creek (a tidal estuary and a tributary to the Gunpowder River). The remediation system consists of 14 extraction wells located between the Old O-Field landfill and Watson Creek.Linear programming techniques were applied to the results of the flow-model simulations to identify optimal pumping strategies for the remediation system. The optimal management objective is to minimize total withdrawal from the water-table aquifer, while adhering to the following constraints: (1) ground-water flow from the landfill should be prevented from reaching Watson Creek, (2) no extraction pump should be operated at a rate that exceeds its capacity, and (3) no extraction pump should be operated at a rate below its minimum capacity, the minimum rate at which an Old O-Field pump can function. Water withdrawal is minimized by varying the rate and frequency of pumping at each of the 14 extraction wells over time. This minimizes the costs of both pumping and water treatment, thus providing the least-cost remediation alternative while simultaneously meeting all operating constraints. The optimal strategy identified using this objective and constraint set involved operating 13 of the 14 extraction wells at rates ranging from 0.4 to 4.9 gallons per minute.

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Simulation of ground-water flow and transport of chlorinated hydrocarbons at Graces Quarters, Aberdeen Proving Ground, Maryland

Military activity at Graces Quarters, a former open-air chemical-agent facility at Aberdeen Proving Ground, Maryland, has resulted in ground-water contamination by chlorinated hydrocarbons. As part of a ground-water remediation feasibility study, a three-dimensional model was constructed to simulate transport of four chlorinated hydrocarbons (1,1,2,2-tetrachloroethane, trichloroethene, carbon tetrachloride, and chloroform) that are components of a contaminant plume in the surficial and middle aquifers underlying the east-central part of Graces Quarters. The model was calibrated to steady-state hydraulic head at 58 observation wells and to the concentration of 1,1,2,2-tetrachloroethane in 58 observation wells and 101direct-push probe samples from the mid-1990s. Simulations using the same basic model with minor adjustments were then run for each of the other plume constituents. The error statistics between the simulated and measured concentrations of each of the constituents compared favorably to the error statisticst,1,2,2-tetrachloroethane calibration. Model simulations were used in conjunction with contaminant concentration data to examine the sources and degradation of the plume constituents. It was determined from this that mixed contaminant sources with no ambient degradation was the best approach for simulating multi-species solute transport at the site. Forward simulations were run to show potential solute transport 30 years and 100 years into the future with and without source removal. Although forward simulations are subject to uncertainty, they can be useful for illustrating various aspects of the conceptual model and its implementation. The forward simulation with no source removal indicates that contaminants would spread throughout various parts of the surficial and middle aquifers, with the100-year simulation showing potential discharge areas in either the marshes at the end of the Graces Quarters peninsula or just offshore in the estuaries. The simulation with source removal indicates that if the modeling assumptions are reasonable and ground-water cleanup within30 years is important, source removal alone is not a sufficient remedy, and cleanup might not even occur within 100 years.

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Natural attenuation of chlorinated volatile organic compounds in a freshwater tidal wetland, Aberdeen Proving Ground, Maryland

Ground-water contaminant plumes that are flowing toward or currently discharging to wetland areas present unique remediation problems because of the hydrologic connections between ground water 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 ground-water-flow directions and changes in discharge locations, which affect the distribution and transport of contaminants. The average linear velocity of ground water is estimated to be about 2 to 3 feet per year along vertical flow lines in the wetland area, and the total ground-water 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 ground water 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 ground water in the wetland sediments, but the daughter compounds 1,2- dichloro-ethylene (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 ground water 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 exper-iments 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 West Branch, Aberdeen Proving Ground, Maryland 3 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 ( K d 's) to describe the ratios of sorbed to aqueous concentrations of PCA and the daughter products cis-12DCE, trans-12DCE, and VC. The estimated K d'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 K d '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 ground-water 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 ground water 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 ground-water contaminants.

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Contamination of ground water, surface water, and soil, and evaluation of selected ground-water pumping alternatives in the Canal Creek area of Aberdeen Proving Ground, Maryland

Chemical manufacturing, munitions filling, and other military-support activities have resulted in the contamination of ground water, surface water, and soil in the Canal Creek area of Aberdeen Proving Ground, Maryland. Chlorinated volatile organic compounds, including 1,1,2,2-tetrachloroethane and trichloroethylene, are widespread ground-water contaminants in two aquifers that are composed of unconsolidated sand and gravel. Distribution and fate of chlorinated organic compounds in the ground water has been affected by the movement and dissolution of solvents in their dense immiscible phase and by microbial degradation under anaerobic conditions. Detection of volatile organic contaminants in adjacent surface water indicates that shallow contaminated ground water discharges to surface water. Semivolatile organic compounds, especially polycyclic aromatic hydrocarbons, are the most prevalent organic contaminants in soils. Various trace elements, such as arsenic, cadmium, lead, and zinc, were found in elevated concentrations in ground water, surface water, and soil. Simulations with a ground-water-flow model and particle tracker postprocessor show that, without remedial pumpage, the contaminants will eventually migrate to Canal Creek and Gunpowder River. Simulations indicate that remedial pumpage of 2.0 million gallons per day from existing wells is needed to capture all particles originating in the contaminant plumes. Simulated pumpage from offsite wells screened in a lower confined aquifer does not affect the flow of contaminated ground water in the Canal Creek area.

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Hydrogeologic setting, hydraulic properties, and ground-water flow at the O-Field area of Aberdeen Proving Ground, Maryland

The U.S. Army disposed chemical agents, laboratory materials, and unexploded ordnance at O-Field in the Edgewood Area of Aberdeen Proving Ground, Maryland, from before World War II until at least the 1950's. Soil, ground water, surface water, and wetland sediments in the O-Field area were contaminated from the disposal activity. A ground-water-flow model of the O-Field area was constructed by the U.S. Geological Survey (USGS) in 1989 to simulate flow in the central and southern part of Gunpowder Neck. The USGS began an additional study of the contamination in the O-Field area in cooperation with the U.S. Army in 1990 to (1) further define the hydrogeologic framework of the O-Field area, (2) characterize the hydraulic properties of the aquifers and confining unit, and (3) define ground-water flow paths at O-Field on the basis of the current data and simulations of ground-water flow. A water-table aquifer, an upper confining unit, and an upper confined aquifer comprise the shallow ground-water system of the O-Field area. A lower confining unit, through which ground-water movement is negligible, is considered a lower boundary to the shallow system. These units are all part of the Pleistocene Talbot Formation. The model developed in the previous study was redesigned using the data collected during this study and emphasized New O-Field. The current steady-state model was calibrated to water levels of June 1993. The rate of ground-water flow calculated by the model was approximately 0.48 feet per day and the rate determined from chlorofluorocarbon dates was approximately 0.39 feet per day.

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