Michelle M. Lorah

Natural attenuation of chlorinated volatile organic compounds in a freshwater tidal wetland: Field evidence of anaerobic biodegradation

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 m 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.

Biogeochemical Evolution of a Landfill Leachate Plume, Norman, Oklahoma

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 aquifers geologic and hydrodynamic framework.

Biogeochemistry at a wetland sediment–alluvial aquifer interface in a landfill leachate plume

The biogeochemistry at the interface between sediments in a seasonally ponded wetland (slough) and an alluvial aquifer contaminated with landfill leachate was investigated to evaluate factors that can effect natural attenuation of landfill leachate contaminants in areas of groundwater/surface-water interaction. The biogeochemistry at the wetland-alluvial aquifer interface differed greatly between dry and wet conditions. During dry conditions (low water table), vertically upward discharge was focused at the center of the slough from the fringe of a landfill-derived ammonium plume in the underlying aquifer, resulting in transport of relatively low concentrations of ammonium to the slough sediments with dilution and dispersion as the primary attenuation mechanism. In contrast, during wet conditions (high water table), leachate-contaminated groundwater discharged upward near the upgradient slough bank, where ammonium concentrations in the aquifer where high. Relatively high concentrations of ammonium and other leachate constituents also were transported laterally through the slough porewater to the downgradient bank in wet conditions. Concentrations of the leachate-associated constituents chloride, ammonium, non-volatile dissolved organic carbon, alkalinity, and ferrous iron more than doubled in the slough porewater on the upgradient bank during wet conditions. Chloride, non-volatile dissolved organic carbon (DOC), and bicarbonate acted conservatively during lateral transport in the aquifer and slough porewater, whereas ammonium and potassium were strongly attenuated. Nitrogen isotope variations in ammonium and the distribution of ammonium compared to other cations indicated that sorption was the primary attenuation mechanism for ammonium during lateral transport in the aquifer and the slough porewater. Ammonium attenuation was less efficient, however, in the slough porewater than in the aquifer and possibly occurred by a different sorption mechanism. A stoichiometrically balanced increase in magnesium concentration with decreasing ammonium and potassium concentrations indicated that cation exchange was the sorption mechanism in the slough porewater. Only a partial mass balance could be determined for cations exchanged for ammonium and potassium in the aquifer, indicating that some irreversible sorption may be occurring. Although wetlands commonly are expected to decrease fluxes of contaminants in riparian environments, enhanced attenuation of the leachate contaminants in the slough sediment porewater compared to the aquifer was not observed in this study. The lack of enhanced attenuation can be attributed to the fact that the anoxic plume, comprised largely of recalcitrant DOC and reduced inorganic constituents, interacted with anoxic slough sediments and porewaters, rather than encountering a change in redox conditions that could cause transformation reactions. Nevertheless, the attenuation processes in the narrow zone of groundwater/surface-water interaction were effective in reducing ammonium concentrations by a factor of about 3 during lateral transport across the slough and by a factor of 2 to 10 before release to the surface water. Slough porewater geochemistry also indicated that the slough could be a source of sulfate in dry conditions, potentially providing a terminal electron acceptor for natural attenuation of organic compounds in the leachate plume.

Characterization of a microbial consortium capable of rapid and simultaneous dechlorination of 1,1,2,2-tetrachloroethane and chlorinated ethane and ethene intermediates

ABSTRACT Mixed cultures capable of dechlorinating chlorinated ethanes and ethenes were enriched from contaminated wetland sediment at Aberdeen Proving Ground (APG) Maryland. The “West Branch Consortium” (WBC-2) was capable of degrading 1,1,2,2-tetrachloroethane (TeCA), trichloroethene (TCE), cis and trans 1,2-dichloroethene (DCE), 1,1,2-trichloroethane (TCA), 1,2-dichloroethane, and vinyl chloride to nonchlorinated end products ethene and ethane. WBC-2 dechlorinated TeCA, TCA, and cisDCE rapidly and simultaneously. A Clostridium sp. phylogenetically closely related to an uncultured member of a TCE-degrading consortium was numerically dominant in the WBC-2 clone library after 11 months of enrichment in culture. Clostridiales, including Acetobacteria, comprised 65% of the bacterial clones in WBC-2, with Bacteroides (14%), and epsilon Proteobacteria (14%) also numerically important. Methanogens identified in the consortium were members of the class Methanomicrobia, which includes acetoclastic methanogens. Dehalococcoides did not become dominant in the culture, although it was present at about 1% in the microbial population. The WBC-2 consortium provides opportunities for the in situ bioremediation of sites contaminated with mixtures of chlorinated ethenes and ethanes.

Biodegradation of Trichloroethylene and Its Anaerobic Daughter Products in Freshwater Wetland Sediments

The wide range of redox conditions and diversity of microbial populations in organic-rich wetland sediments could enhance biodegradation of chlorinated solvents. To evaluate potential biodegradation rates of trichloroethylene (TCE) and its anaerobic daughter products (cis-1,2-dichloroethylene; trans-1,2-dichloroethylene; and vinyl chloride), laboratory microcosms were prepared under methanogenic, sulfate-reducing, and aerobic conditions using sediment and groundwater from a freshwater wetland that is a discharge area for a TCE contaminant plume. Under methanogenic conditions, biodegradation rates of TCE were extremely rapid at 0.30 to 0.37 d−1 (half-life of about 2 days). Although the TCE biodegradation rate was slower under sulfate-reducing conditions (0.032 d−1) than under methanogenic conditions, the rate was still two orders of magnitude higher than those reported in the literature for microcosms constructed with sandy aquifer sediments. In the aerobic microcosm experiments, biodegradation occurred only if methane consumption occurred, indicating that methanotrophs were involved. Comparison of laboratory-measured rates indicates that production of the 1,2-dichloroethylene isomers and vinyl chloride by anaerobic TCE biodegradation could be balanced by their consumption through aerobic degradation where methanotrophs are active in wetland sediment. TCE degradation rates estimated using field data (0.009 to 0.016 d−1) agree with the laboratory-measured rates within a factor of 3 to 22, supporting the feasibility of natural attenuation as a remediation method for contaminated groundwater discharging in this wetland and other similar environments.

Anaerobic biodegradation and hydrogeochemical controls on natural attenuation of trichloroethene in an inland forested wetland

ABSTRACT A field and laboratory investigation of natural attenuation, focusing on anaerobic biodegradation, was conducted in a forested wetland where a plume of trichloroethene discharges from a sand aquifer through organic-rich wetland and stream-bottom sediments. The rapid response of the wetland hydrology to precipitation events altered groundwater flow and geochemistry during wet conditions in the spring compared to the drier conditions in the summer and fall. During dry conditions, partial reductive dechlorination of trichloroethene to cis-1,2-dichloroethene occurred in methanogenic wetland porewater. Influx of oxygenated recharge during wet conditions resulted in a change from methanogenic to iron-reducing conditions and a lack of 1,2-dichloroethene production in the wet spring conditions. During these wet conditions, dilution was the primary attenuation mechanism evident for trichloroethene in the wetland porewater. Trichloroethene degradation was insignificant in anaerobic microcosms constructed with the shallow wetland sediment, and microbiological analyses showed a low microbial biomass and absence of known dehalorespiring microorganisms. Despite the typically organic-rich characteristic of wetland sediments, natural attenuation by anaerobic degradation may not be an effective groundwater remediation for chlorinated solvents at all sites.

Effect of Fe(III) on 1,1,2,2-Tetrachloroethane Degradation and Vinyl Chloride Accumulation in Wetland Sediments of the Aberdeen Proving Ground

1,1,2,2-Tetrachloroethane (TeCA) contaminated groundwater at the Aberdeen Proving Ground discharges through an anaerobic wetland in West Branch Canal Creek (MD), where dechlorination occurs. Two microbially mediated pathways, dichloroelimination and hydrogenolysis, account for most of the TeCA degradation at this site. The dichloroelimination pathways lead to the formation of vinyl chloride (VC), a recalcitrant carcinogen of great concern. The goal of this investigation was to determine whether microbially-available Fe(III) in the wetland surface sediment influenced the fate of TeCA and its daughter products. Differences were identified in the TeCA degradation pathway between microcosms treated with amorphous ferric oxyhydroxide (AFO-treated) and untreated (no AFO) microcosms. TeCA degradation was accompanied by a lower accumulation of VC in AFO-treated microcosms than untreated microcosms. The microcosm incubations and subsequent experiments with the microcosm materials showed that AFO treatment resulted in lower production of VC by (1) shifting TeCA degradation from dichloroelimination pathways to production of a greater proportion of chlorinated ethane products, and (2) decreasing the microbial capability to produce VC from 1,2-dichloroethene (DCE). VC degradation was not stimulated in the presence of Fe(III). Rather, VC degradation occurred readily under methanogenic conditions and was inhibited under Fe(III)-reducing conditions.

Photo-assisted electrochemical detection (PAED) following HPLC-UV for the determination of nitro explosives and degradation products

Continuous efforts implemented by government agencies such as the United States Geological Survey (USGS) aim to manage and protect the integrity of the environments natural resources. RDX is one of the most frequently utilized nitramine explosives for mining, demolition and munitions purposes in the United States (US). The degradation of RDX in natural environments is of particular importance as a result of the accumulation of consequential degradation products in nature. Specifically, RDX has the potential to be degraded by microorganisms resulting in hazardous levels of harmful degradation products in soil and groundwater. The necessity for the detection of these particular degradation products is emphasized as a consequence of their toxicity as these products are recognized as potential mutagens. Photo-assisted electrochemical detection (PAED) following HPLC-UV is used to develop an analytical method qualified for the assessment of RDX and degradation products. The technique offers unique selectivity possessed by the photochemical reactor coupled to EC detection serving to eliminate the need for repetitive analysis using different column technologies. Furthermore, on-line sample pretreatment is developed and optimized specifically for the preparation of samples consisting of RDX and degradation products. Analytical figures of merit determined for all target analytes using on-line SPE-HPLC-UV-PAED revealed detection limits in the sub part per billion range for RDX and degradation product MEDINA. The effectiveness of the method is exemplified in collaborative studies with the USGS in monitoring the degradation of RDX and formation of degradation products once the nitro explosive is subject to anaerobic microorganisms WBC-2.

Ground-water and surface-water quality data for the West Branch Canal Creek area, Aberdeen Proving Ground, Maryland

................................................................................................................................................................................. ̂ Inffoduction................................................................... Purpose and scope.........................................................................................................................................................2 Site history .....................................................................................................................................................................3 Description of study area...............................................................................................................................................3 Site investigations..........................................................................................................................................................3 Acknowledgments.........................................................................................................................................................3 Methods of investigation........................................................................................................................................................^ Ground-water and surface-water sampling networks....................................................................................................5 Ground-water 1-inch piezometers.........................................................................................................................5 Ground-water 0.75-inch drive-point piezometers.................................................................................................9 Ground-water 0.25-inch piezometers....................................................................................................................9 Ground-water multi-level monitoring system.......................................................................................................9 Ground-water profiler.........................................................................................................................................11 Ground-water porous-membrane sampling devices........................................................................................... 12 Ground-water passive-diffusion-bag samplers................................................................................................... 12 Surface-water network........................................................................................................................................ 12 Ground-water and surface-water sampling methods............................................................................................................ 14 Well and piezometer sampling methods...................................................................................................................... 14 1-inch piezometer sampling methods................................................................................................................. 14 0.75-inch drive-point piezometer sampling methods.......................................................................................... 14 0.25-inch flexible tubing and inverted-screen piezometer sampling methods.................................................... 14 Multi-level monitoring system sampling methods...................................................................................................... 14 Ground-water profiler sampling methods.................................................................................................................... 15 Porous-membrane sampling device sampling methods............................................................................................... 15 Passive-diffusion-bag sampler methods...................................................................................................................... 15 Surface-water sampling methods................................................................................................................................. 15 Ground-water and surface-water analytical methods........................................................................................................... 15 Field measurements..................................................................................................................................................... 15 Redox analyses............................................................................................................................................................ 16 Inorganic analyses .......................................................................................................................................................16 Organic analyses..........................................................................................................................................................17 Quality-assurance methods.................................................................................................................................................. 17 Field replicates and blind samples............................................................................................................................... 17 Blanks ..................................................................................................................................................................... Laboratory quality assurance....................................................................................................................................... 18 Matrix spikes and matrix spike duplicates ..................................................................................................................19 Ground-water data from wells, piezometers, and multi-level monitoring systems .............................................................19 Field measurements andredox constituents for wells, piezometers, and multi-level monitoring systems................. 19 Inorganic constituents for wells, piezometers, and multi-level monitoring systems...................................................20 Organic constituents for wells, piezometers, and multi-level monitoring systems .....................................................20 Ground-water profiler and supplemental piezometer data...................................................................................................24 Field measurements and redox constituents for profiler and supplemental piezometer samples................................24 Inorganic constituents for profiler and supplemental piezometer samples .................................................................24 Organic constituents for profiler and supplemental piezometer samples....................................................................25