Application of Natural Attenuation to Ground Water Contaminated by Phenoxy Acid Herbicides at an Old Landfill in Sjoelund, Denmark

Investigations of geology, hydrogeology, and ground water chemistry in the aquifer downgradient from Sjoelund Landfill, Denmark, formed the basis for an evaluation of natural attenuation as a remediation technology for phenoxy acid herbicides at the site. Concentrations of phenoxy acids were up to 65 μg/L in the ground water, primarily 4-chlor-2-methylphenoxypropionic acid (MCPP) and 2,4-dichlorophenoxypropionic acid (dichlorprop). Mass removal of the phenoxy acids was shown within 50 to 100 m of the landfill by calculation of contaminant fluxes passing transects at three distances. There was accordance between increasing oxygen concentrations and decreasing phenoxy acid concentrations with distance from the landfill, indicating that aerobic degradation was a major mass removal process. Presence of high concentrations of putative anaerobic phenoxy acid metabolites suggested that anaerobic degradation was also occurring. Laboratory degradation experiments using sediment and ground water from the aquifer supported aerobic and anaerobic degradability of MCPP at the site. It was concluded that natural attenuation may be applicable as a remedy for the phenoxy acids at the Sjoelund Landfill site, although uncertainties related to calculations of chloride and phenoxy acid fluxes at a complex site and identification of specific in situ indicators were encountered. Thus, there is a pronounced need for development and broader experience with evaluation tools for natural attenuation of phenoxy acids, such as specific metabolites, changes in enantiomeric fractions, compound-specific stable carbon isotope ratios, or microbial fingerprints.     

Fate of Point‐Source Pesticide Spill in Clayey Till after 15 Years

This study investigated the development of pesticide pollution two, three, and 17 years after spills of the herbicides dichlorprop, mecoprop (MCPP), MCPA, 2,4‐D (phenoxy acids), simazine, and terbutylazine (triazines) in a former orchard machinery service yard. The spills had occurred over several decades on a 23‐m thick, mainly anaerobic fractured clayey till aquitard. Angled monitoring wells were installed in the aquitard 3 years after the spills ceased in 1989. In 1993, monitoring revealed that high groundwater concentrations of dichlorprop (677 µg/L) and MCPP (139 µg/L) were accumulated as a zone of maximum pollution in anaerobic and largely immobile pore water at 5 to 6 m depth in the aquitard profile. In contrast, 2,4‐D was determined in only one water sample, and MCPA and simazine and terbutylazine were determined only in low concentrations (below10 µg/L), although these pesticides had been handled at the site in greater amounts than dichlorprop and MCPP according to detailed historic information obtained for the site. Repeated monitoring in the same wells after a further 14 years in 2007 revealed that no identifiable degradation of MCPP had occurred, while dichlorprop had degraded by 75% to 80% (estimated half‐life of approximately 5 years). Furthermore, degradation products related to the phenoxy acids had accumulated, especially 4‐CPP with a maximum concentration of 218 µg/L. In the same zone, MCPA and simazine had almost disappeared. As the pollution was mainly accumulated in largely immobile pore water of the aquitard clayey matrix, and the groundwater recharge was low (30 to 60 mm/year), only minor vertical displacement of the zone with maximum pollution zone had occurred during the 15 years of monitoring. However, concentrations of dichlorprop (0.01 to 0.02 µg/L), MCPP (0.1 to 0.2 µg/L), and 4‐CPP (0.6 to 0.7 µg/L) had spread along textural heterogeneities in the aquitard into the underlying sandy aquifer at 23‐m depth.     

Accumulation of Pesticides in Anaerobic Clayey Till‐Controls and Implications for Groundwater

Pesticide residuals after point‐source pesticide spills in clay‐rich aquitards may potentially affect underlying groundwater for many decades due to slow release of accumulated pollution in the clayey matrix material of the aquitard. In this study, we evaluated factors behind different degrees of accumulation of phenoxy acids (MCPP, dichlorprop, 2,4‐D MCPA) and triazines (simazine and terbutylazine) observed in an old pesticide pollution described by Jørgensen et al. (2016a, this issue). By using leaching experiments, it was shown that a zone of maximum concentrations of MCPP and dichlorprop (mg/L) observed by Jørgensen et al. (2016a, this issue) represented accumulated potentially mobile pollution in anaerobic, however largely immobile pore water of the clayey matrix in the upper few meters of the unoxidized aquitard zone. By using sorption experiments, we determined 9 to16 times higher mobility by diffusion and flow for the phenoxy acids (R = 1 to 2) than for the triazines (R = 9 to 16) in the clayey matrix material of the aquitard. This indicated that more rapid and greater accumulation could occur for the phenoxy acids in the clayey matrix than for the triazines. In contrast, the relative mobility of the phenoxy acids and triazines was much closer in sand‐filled fractures and thin sand layers/lamina in the clay, suggesting that the migration of the same compounds along these textural preferential flow paths into the underlying aquifer was less different. Despite that a greater mass had originally been spilled of 2,4‐D and MCPA having similar mobility as the accumulated MCPP and dichlorprop, these compounds were not accumulated in the zone of maximum concentrations. It is suggested that the controls, which initially allowed for the observed separate accumulation of MCPP and dichlorprop as a zone of maximum pollution, were due to the combination of high persistence and high mobility for these specific pesticides in the clayey till matrix material of the aquitard. The investigation showed that over time the initial high concentrations of the accumulated phenoxy acids (MCPP, dichlorprop) transformed into high concentrations of related mobile degradation products (e.g., 4‐CPP and 2‐CPP), which extended the total time of groundwater pollution beyond the disappearance of the original phenoxyacids.     

Estimation of Biodegradation Rates Using Respiration Tests During In Situ Bioremediation of Weathered Diesel NAPL

Respiration tests were carried out during a seven month bioremediation field trial to monitor biodegradation rates of weathered diesel non-aqueous phase liquid (NAPL) contaminating a shallow sand aquifer. Multiple depth monitoring of oxygen concentrations and air-filled porosity were carried out in nutrient amended and nonamended locations to assess the variability of degradation rate estimates calculated from respiration tests.
The field trial consisted of periodic addition of nutrients (nitrogen and phosphorus) and aeration of a 100 m² trial plot. During the bioremediation trial, aeration was stopped periodically, and decreases in gaseous oxygen concentrations were logged semi-continuously using data loggers attached to recently developed in situ oxygen probes placed at multiple depths above and within a thin NAPL-contaminated zone. Oxygen usage rate coefficients were determined by fitting zero-and first-order rate equations to the oxygen concentration reduction curves, although only zero-order rates were used to calculate biodegradation rates. Air-filled porosity estimates were found to vary by up to a factor of two between sites and at different times.
NAPL degradation rates calculated from measured air-filled porosity and oxygen usage rate coefficients ranged up to 69 mg kg^-1 day^-1. These rates are comparable to and higher than rates quoted in other studies, despite the high concentrations and weathered state of the NAPL at this test site. For nutrient-amended sites within the trial plot, estimates of NAPL degradation rates were two to three times higher than estimates from nonamended sites. Rates also increased with depth.     

Bioaugmentation and Propane Biosparging for In Situ Biodegradation of 1,4‐Dioxane

Propane biosparging and bioaugmentation were applied to promote in situ biodegradation of 1,4‐dioxane at Site 24, Vandenberg Air Force Base (VAFB), CA. Laboratory microcosm and enrichment culture testing demonstrated that although native propanotrophs appeared abundant in the shallow water‐bearing unit of the aquifer (8 to 23 ft below ground surface [bgs]), they were difficult to be enriched from a deeper water‐bearing unit (82 to 90 feet bgs). Bioaugmentation with the propanotroph Rhodococcus ruber ENV425, however, supported 1,4‐dioxane biodegradation in microcosms constructed with samples from the deep aquifer. For field testing, a propane‐biosparging system consisting of a single sparging well and four performance monitoring wells was constructed in the deep aquifer. 1,4‐dioxane biodegradation began immediately after bioaugmentation with R. ruber ENV425 (36 L; 4 × 10⁹ cells/mL), and apparent first‐order decay rates for 1,4‐dioxane ranged from 0.021 day^?1 to 0.036 day^?1. First‐order propane consumption rates increased from 0.01 to 0.05 min^?1 during treatment. 1,4‐dioxane concentrations in the sparging well and two of the performance monitoring wells were reduced from as high as 1090 µg/L to <2 µg/L, while 1,4‐dioxane concentration was reduced from 135 µg/L to 7.3 µg/L in a more distal third monitoring well. No 1,4‐dioxane degradation was observed in the intermediate aquifer control well even though propane and oxygen were present. The demonstration showed that propane biosparging and bioaugmentation can be used for in situ treatment of 1,4‐dioxane to regulatory levels.     

Diisopropanolamine Biodegradation Potential at Sour Gas Plants

The potential for aerobic and anaerobic biodegradation of a sour gas treatment chemical, diisopropanolamine (DIPA), was studied using contaminated aquifer materials from three sour gas treatment sites in western Canada. DIPA was found to be readily consumed under aerobic conditions at 8°C and 28°C in shake flask cultures incubated with aquifer material from each of the sites, and this removal was characterized by first-order kinetics. In addition, DIPA biodegradation was found to occur under nitrate-, Min(IV)., and Fe(III)-reducing conditions at 28°C, and in some cases at 8°C, in laboratory microcosms, DIPA loss corresponded to consumption of nitrate, and production of Mn(II) and Fe(II) in viable microcosms compared to corresponding sterile controls. A threshold DIPA concentration near 40 mg/L was observed in the anaerobic microcosms. This report provides the first evidence that DIPA is biodegraded under anaerobic conditions, and our data suggest that biodegradation may contribute to DIPA attenuation under aerobic and anaerobic conditions in aquifers contaminated with this sour gas treatment chemical.     

Reinterpreting the Importance of Oxygen‐Based Biodegradation in Chloroethene‐Contaminated Groundwater

Chlororespiration is common in shallow aquifer systems under conditions nominally identified as anoxic. Consequently, chlororespiration is a key component of remediation at many chloroethene‐contaminated sites. In some instances, limited accumulation of reductive dechlorination daughter products is interpreted as evidence that natural attenuation is not adequate for site remediation. This conclusion is justified when evidence for parent compound (tetrachloroethene, PCE, or trichloroethene, TCE) degradation is lacking. For many chloroethene‐contaminated shallow aquifer systems, however, nonconservative losses of the parent compounds are clear but the mass balance between parent compound attenuation and accumulation of reductive dechlorination daughter products is incomplete. Incomplete mass balance indicates a failure to account for important contaminant attenuation mechanisms and is consistent with contaminant degradation to nondiagnostic mineralization products like CO₂. While anoxic mineralization of chloroethene compounds has been proposed previously, recent results suggest that oxygen‐based mineralization of chloroethenes also can be significant at dissolved oxygen concentrations below the currently accepted field standard for nominally anoxic conditions. Thus, reassessment of the role and potential importance of low concentrations of oxygen in chloroethene biodegradation are needed, because mischaracterization of operant biodegradation processes can lead to expensive and ineffective remedial actions. A modified interpretive framework is provided for assessing the potential for chloroethene biodegradation under different redox conditions and the probable role of oxygen in chloroethene biodegradation.     

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 aquifer's geologic and hydrodynamic framework.     

Effect of Biofuels on Biodegradation of Benzene and Toluene at Gasoline Spill Sites

The risk that benzene and toluene from spills of gasoline will impact drinking water wells is largely controlled by the natural anaerobic biodegradation of benzene and toluene. Benzene and toluene, as well as ethanol and other biofuels, are degraded under anaerobic conditions to the same pool of degradation products. Biodegradation of biofuels may produce concentrations of degradation products that make the thermodynamics for degradation of benzene and toluene infeasible under methanogenic conditions and produce larger plumes of benzene and toluene. This study evaluated the concentrations of fuel alcohols that are necessary to inhibit the anaerobic degradation of benzene and toluene under methanogenic conditions. At two ethanol spill sites, concentrations of ethanol greater ≥42 mg/L inhibited the anaerobic degradation of toluene. The pH and concentrations of acetate, dissolved inorganic carbon, and molecular hydrogen were used to calculate the Gibbs free energy for the biodegradation of toluene. In general, the anaerobic biodegradation of toluene was not thermodynamically feasible in water with ≥42 mg/L ethanol. In a microcosm study, when the concentrations of ethanol were ≥14 mg/L or the concentrations of n‐butanol were ≥16 mg/L, the biodegradation of the alcohols consistently produced concentrations of hydrogen, dissolved inorganic carbon, and acetate that would preclude natural anaerobic biodegradation of benzene and toluene by syntrophic organisms. In contrast, iso‐butanol and n‐propanol only occasionally produced conditions that would preclude the biodegradation of benzene and toluene.     

Bioremediation of Phenanthrene by Mycoplana sp. MVMB2 Isolated from Contaminated Soil

The effect of nutrient and surfactant addition on the biodegradation of phenanthrene was studied in a batch scale soil–slurry system using isolated Mycoplana sp. MVMB2strain. The study was conducted using an artificially phenanthrene spiked and as well as contaminated soil from petrochemical industrial site. Maximum phenanthrene degradation and subsequent high microbial growth were observed at optimum pH (pH 6) and C/N/P ratio (100:20:3). To investigate maximum substrate degradation potential of Mycoplana sp. MVMB2, very high concentrations of phenanthrene (50–200 mg/kg soil) were used. The organism was capable of degrading >60% for a concentration below 20 mg/kg soil and >40% for concentrations up to 200 mg/kg within 8 days. Further the influence of five different surfactants namely Span 80, Tween 20, Triton X‐100, cetyl trimethyl ammonium bromide, and sodium dodecyl sulfate were tested at their critical micelle concentration (CMC) levels for phenanthrene degradation in the soil. The addition of surfactant enhanced the biodegradation and a maximum of 84.49% was obtained for Triton X‐100. Complete phenanthrene degradation by Mycoplana sp. MVMB2 was observed at 3 CMC concentration of Triton X‐100. The optimized parameters obtained were used for the degradation of phenanthrene present in the contaminated soil and 98.6% biodegradation was obtained. Thus, the results obtained in the study suggested that biodegradation of phenanthrene by Mycoplana sp. MVMB2 appeared to be feasible to remediate phenanthrene rich contaminated sites.     

Aquifer vulnerability to pesticide migration through till aquitards

This study investigates the influence of key factors-mainly recharge rate and degradation half-life--on downward migration of the widely used pesticide mecoprop (MCPP) through a typical clayey till aquitard. The study uses the numerical model FRAC3Dvs, which is a three-dimensional discrete fracture/matrix diffusion (DFMD) numerical transport model. The model was calibrated with laboratory and field data from a site near Havdrup, Denmark, but the overall findings are expected to be relevant to many other sites in similar settings. Fracture flow and MCPP transport parameters for the model were obtained through calibration using well-characterized laboratory experiments with large (0.5 m diameter by 0.5 m high) undisturbed columns of the fractured till and a field experiment. A second level of upscaling and sensitivity analysis was then carried out using data on hydraulic head, fracture spacing, and water budget from the field site. The simulations of downward migration of MCPP show that MCPP concentration and mass flux into the underlying aquifer, and hence the aquifer vulnerability to this pesticide compound, is mainly dependent on the degradation rate of the pesticide, the overall aquitard water budget, and the ground water recharge rate into the aquifer. The influence of flow rate, matrix diffusion, and degradation rate are intertwined. This results in one to four orders of magnitude higher MCPP flux into the aquifer from aquifer recharge rates of 20 and 120 mm/yr, respectively, for no degradation and MCPP half-life of 0.5 yr. From a sensitivity analysis it was found that the range of MCPP flux into the aquifer varied less than one order of magnitude due to (1) changing fracture spacing from 1 to 10 m, or (2) preferential flow along inclined thin sand layers, which represent common conditions for the current and other settings of clayey till in Denmark and other glaciated areas in Europe and North America. The results indicate that for aquifers overlain by fractured clayey tills, the vulnerability to contamination with pesticides (pesticide flux into the aquifer) and other widespread agricultural contaminants is going to vary strongly in the watershed as a function of the distribution of aquitard water budget (flow rate) and aquitard redox environment (controlling contaminant degradation rates), even if the thickness of the till is relatively constant. DFMD modeling of cause-effect relationships within such systems has great potential to support decisions in planning, regulation, and contaminant remediation.     

Microbial Mineralization of Dichloroethene and Vinyl Chloride under Hypoxic Conditions

Mineralization of ¹⁴C‐radiolabled vinyl chloride ([1,2‐¹⁴C] VC) and cis‐dichloroethene ([1,2‐¹⁴C] cis‐DCE) under hypoxic (initial dissolved oxygen (DO) concentrations about 0.1 mg/L) and nominally anoxic (DO minimum detection limit = 0.01 mg/L) was examined in chloroethene‐exposed sediments from two groundwater and two surface water sites. The results show significant VC and dichloroethene (DCE) mineralization under hypoxic conditions. All the sample treatments exhibited pseudo‐first‐order kinetics for DCE and VC mineralization over an extended range of substrate concentrations. First‐order rates for VC mineralization were approximately 1 to 2 orders of magnitude higher in hypoxic groundwater sediment treatments and at least three times higher in hypoxic surface water sediment treatments than in the respective anoxic treatments. For VC, oxygen‐linked processes accounted for 65 to 85% of mineralization at DO concentrations below 0.1 mg/L, and ¹⁴CO₂ was the only degradation product observed in VC treatments under hypoxic conditions. Because the lower detection limit for DO concentrations measured in the field is typically 0.1 to 0.5 mg/L, these results indicate that oxygen‐linked VC and DCE biodegradation can be significant under field conditions that appear anoxic. Furthermore, because rates of VC mineralization exceeded rates of DCE mineralization under hypoxic conditions, DCE accumulation without concomitant accumulation of VC may not be evidence of a DCE degradative “stall” in chloroethene plumes. Significantly, mineralization of VC above the level that could reasonably be attributed to residual DO contamination was also observed in several nominally anoxic (DO minimum detection limit = 0.01 mg/L) microcosm treatments.     

In Situ Biotreatment of TBA with Recirculation/Oxygenation

The potential for in situ biodegradation of tert‐butyl alcohol (TBA) by creation of aerobic conditions in the subsurface with recirculating well pairs was investigated in two field studies conducted at Vandenberg Air Force Base. In the first experiment, a single recirculating well pair with bromide tracer and oxygen amendment successfully delivered oxygen to the subsurface for 42 d. TBA concentrations were reduced from approximately 500 μg/L to below the detection limit within the treatment zone and the treated water was detected in a monitoring transect several meters downgradient. In the second experiment, a site‐calibrated model was used to design a double recirculating well pair with oxygen amendment, which successfully delivered oxygen to the subsurface for 291 d and also decreased TBA concentrations to below the detection limit. Methylibium petroleiphilum strain PM1, a known TBA‐degrading bacterium, was detectable at the study site but addition of oxygen had little impact on the already low baseline population densities, suggesting that there was not enough carbon within the groundwater plume to support significant new growth in the PM1 population. Given favorable hydrogeologic and geochemical conditions, the use of recirculating well pairs to introduce dissolved oxygen into the subsurface is a viable method to stimulate in situ biodegradation of TBA or other aerobically degradable aquifer contaminants.     

Degradation of Six Selected Ultraviolet Filters in Aquifer Materials Under Various Redox Conditions

Laboratory biodegradation batch studies were performed to investigate the degradation behavior of six selected UV filters, namely benzophenone‐3 (BP‐3), 3‐(4‐methylbenzylidene) camphor (4‐MBC), Octyl 4‐methoxycinnamate (OMC), Octocrylene (OC), 2‐(3‐t‐butyl‐2‐hydroxy‐5‐methylphenyl)‐5‐chloro benzotriazole (UV‐326), and 2‐(2’‐hydroxy‐5’‐octylphenyl)‐benzotriazole (UV‐329) in an aquifer microcosm (groundwater and aquifer sediment mixture) under aerobic and anaerobic (nitrate, sulfate, and Fe(III) reducing) conditions within 77 d. The results from the biodegradation experiments showed that the six UV filters were degraded well in the aquifer materials under different redox conditions. Rapid biodegradation was observed for BP‐3 and OMC in the aquifer materials, with their half‐lives of 1.5‐8.8 d and 1.3‐5.2 d, respectively. In most cases, aerobic conditions were more favorable for the degradation of the UV filters in aquifer materials. Relatively slow degradation of 4‐MBC, UV‐326, and UV‐329 under anaerobic conditions was noted with their half‐lives ranging between 47 d and 126 d, indicating potential persistence in anaerobic aquifers. The results showed that redox conditions could have significant effects on biodegradation of the UV filters in aquifers.     

Biodegradation and transport of benzene,toluene, and xylenes in a simulated aquifer: comparison of modelled and experimental results

Both laboratory experiments and numerical modelling were conducted to study the biodegradation and transport of benzene–toluene–xylenes (BTX) in a simulated semi‐confined aquifer. The factors incorporated into the numerical model include advection, hydrodynamic dispersion, adsorption, and biodegradation. The various physico‐chemical parameters required by the numerical model were measured experimentally. In the experimental portion of the study, BTX compounds were introduced into the aquifer sand. After the contaminants had been transported through the system, BTX concentrations were measured at 12 equally spaced wells. Subsequently, microorganisms obtained from the activated sludge of a sewage treatment plant and cultured in BTX mixtures were introduced into the aquifer through the 12 sampling wells. The distribution data for BTX adsorption by the aquifer sand form a nonlinear isotherm. The degree of adsorption by the sand varies, depending on the composition of the solute. The degradation time, measured from the time since the bacteria were added to the aquifer until a specific contaminant was no longer detectable, was 35–42 h for BTX. The dissolved oxygen, after degradation by BTX compounds and bacteria, was consumed by about 40–60% in the entire simulated aquifer; thus the aerobic conditions were maintained. This study provides insights for the biodegradation and transport of BTX in aquifers by numerical modelling and laboratory experiments. Experimental and numerical comparisons indicate that the results by Monod degradation kinetics are more accurate than those by the first‐order degradation kinetics. Copyright © 2002 John Wiley & Sons, Ltd.     

A Study of Long-Term MTBE Attenuation in the Borden Aquifer, Ontario, Canada

In 1988 and 1989, a natural gradient tracer test was performed in the shallow, aerobic and aquifer at Canadian Forces Base (CFB) Borden. A mixture of ground water containing dissolved oxygenated gasoline was injected below the water table along with chloride (Cl-) as a conservative tracer. The migration of BTEX, MTBE, and Cl was monitored in detail for 16 moths. The mass of BTEX compounds in the plume diminished significantly with time due to intrinsic aerobic biodegradation, while MTBE showed only a small decrease in mass over the 16-month period. In 1995/96, a comprehensive ground water sampling program was undertaken to define the mass of MTBE still present in the aquifer. Since the plume had migrated into an unmonitored section of the Borden Aquifer, numerical modeling and geostatistical methods were applied to define an optimal sampling grid and to improve the level of confidence in the results. A drive point profiling system was used to obtain ground water samples. Numerical modeling with no consideration of degradation pedicted maximum concentrations in excess of 3000 μg/L; field sampling found maximum concentrations of less than 200 μg/L. A mass balance for the remaining MTBE mass in the aquifer eight years after injection showed that only 3% of the original mass remained. Sorption, volatilization, a biotic degradation, and plant uptake are not considered significant attenuation processes for the field conditions. Therefore, we suggest that biodegradation may have played a major role in the attenuation of MTBE within the Borden Aquifer.     

In Situ Measurement and Numerical Simulation of Oxygen Limited Biotransformation

Enhanced subsurface biorestoration is rapidly becoming recognized as a valuable tool for the restoration of hydrocarbon-contaminated aquifers and sediments. Previous field and laboratory studies at a former wood creosoting facility near Conroe, Texas, have indicated that insufficient oxygen is the primary factor limiting the biotransformation of polynuclear aromatics (PNAs) in sediments and ground water at this site. A series of laboratory experiments and field push-pull injection tests were performed as part of this project to: (1) study the effect of low oxygen concentrations on the biotransformation of PNAs; (2) identify the minimum concentration of PNAs that could be achieved through the addition of oxygen alone; (3) confirm that enhanced subsurface biorestoration is feasible at this site; and (4) test an existing numerical model of the biotransformation process (BIOPLUME). The laboratory studies demonstrated that biotransformation of the PNAs was not inhibited at dissolved oxygen concentrations as low as 0.7 mg/L although this work did suggest that there may be a minimum PNA concentration of 30 to 70 μg/L total PNAs below which biotransformation was inhibited. The field push-pull tests confirmed that addition of oxygen was effective in enhancing the subsurface biodegradation of the PNAs. The minimum concentration achieved using oxygen alone was approximately 60 μg/L total PNAs. Minimal biotransformation of these compounds was observed without oxygen addition. The numerical model BIOPLUME was tested against monitoring data from the field experiments and appears to provide a good approximation of the biodegradation process.     

Estimating Aquifer Sensitivity to Nitrate Contamination Using Geochemical Information

Methods for predicting aquifer sensitivity to contamination typically ignore geochemical factors that affect the occurrence of contaminants such as nitrate. Use of geochemical information offers a simple and accurate method for estimating aquifer sensitivity to nitrate contamination. We developed a classification method in which nitrate-sensitive aquifers have dissolved oxygen concentrations > 1.0 mg/L, Eh values >250 mV, and either reduced iron concentrations < 0.1 mg/L or total iron concentrations < 0.7 mg/L. We tested the method in four Minnesota aquifer systems having different geochemical and hydrologic conditions. A surficial sand aquifer in central Minnesota exhibited geochemical zonation, with a rapid shift from aerobic to anaerobic conditions 5 m below the water table. A fractured bedrock aquifer in east-central Minnesota remained aerobic to depths of 50 m, except in areas where anaerobic ground water discharged upward from an underlying aquifer. A bedrock aquifer in southeast Minnesota exhibited aerobic conditions when overlain by surficial deposits lacking shale, whereas anaerobic conditions occurred under deposits that contained shale. Surficial sand aquifers in northwest Minnesota contained high concentrations of sulfate and were anaerobic throughout their extent. Nitrate-nitrogen was detected at concentrations exceeding 1 mg/L in 135 of 149 samples classified as sensitive. Nitrate was not detected in any of the 109 samples classified as not sensitive. We observed differences between our estimates of sensitivity and existing sensitivity maps, which are based on methods that do not consider aquifer geochemistry. Because dissolved oxygen, reduced iron, and Eh are readily measured in the field, use of geochemistry provides a quick and accurate way of assessing aquifer sensitivity to nitrate contamination.     

Tidal influence on BTEX biodegradation in sandy coastal aquifers

A numerical study was conducted to investigate the influence of tides on the fate of terrestrially derived BTEX discharging through an unconfined aquifer to coastal waters. Previous studies have revealed that tide-induced seawater circulations create an active salt–freshwater mixing zone in the near-shore aquifer and alter the specific subsurface pathway for contaminants discharging to the coastal environment. Here the coupled density-dependent flow and multi-species reactive transport code PHWAT was used to examine the impact of these tidal effects on the aerobic biodegradation of BTEX released in a coastal aquifer and its subsequent loading to coastal waters. Simulations indicated that tides significantly enhance BTEX attenuation in the near-shore aquifer. They also reduce the rate of chemical transfer from the aquifer to the ocean and exit concentrations at the beach face. For the base case consisting of toluene transport and biodegradation, 79% of toluene initially released in the aquifer was attenuated prior to discharge with tides present, compared to only 1.8% for the non-tidal case. The magnitude of tidal forcing relative to the fresh groundwater flow rate was shown to influence significantly the extent of biodegradation as it controls the intensity of salt–freshwater mixing, period of exposure of the contaminant to the mixing zone and rate of oxygen delivery to the aquifer. The oxygen available for biodegradation also depends on the rate at which oxygen is consumed by natural processes such as organic matter decomposition. While simulations conducted with heterogeneous conductivity fields highlighted the uncertainties associated with predicting contaminant loadings, the study revealed overall that BTEX may undergo significant attenuation in tidally influenced aquifers prior to discharge.     

Enhancement of In Situ Bioremediation of BTEX-Contaminated Ground Water by Oxygen Diffusion from Silicone Tubing

A field study of oxygen-enhanced biodegradation was carried out in a sandy iron-rich ground water system contaminated with gasoline hydrocarbons. Prior to the oxygen study, intrinsic microbial biodegradation in the contaminant plume had depleted dissolved oxygen and created anaerobic conditions. An oxygen diffusion system made of silicone polymer tubing was installed in an injection well within an oxygen delivery zone containing coarse highly permeable sand. During the study, this system delivered high dissolved oxygen (DO) levels (39 mg/L) to the ground water within a part of the plume. The ground water was sampled at a series of monitors in the test zone downgradient of the delivery well to determine the effect of oxygen on dissolved BTEX, ground water geochemistry, and microbially mediated biodegradation processes. The DO levels and Eh increased markedly at distances up to 2.3 m (7.5 feet) downgradient. Potential biofouling and iron precipitation effects did not clog the well screens or porous medium. The increased dissolved oxygen enhanced the population of aerobes while the activity of anaerobic sulfate-reducing bacteria and methanogens decreased. Based on concentration changes, the estimated total rate of BTEX biodegradation rose from 872 mg/day before enhancement to 2530 mg/day after 60 days of oxygen delivery. Increased oxygen flux to the test area could account for aerobic biodegradation of 1835 mg/day of the BTEX. The estimated rates of anaerobic biodegradation processes decreased based on the flux of sulfate, iron (II), and methane. Two contaminants in the plume, benzene and ethylbenzene, are not biodegraded as readily as toluene or xylenes under anaerobic conditions. Following oxygen enhancement, however, the benzene and ethylbenzene concentrations decreased about 98%, as did toluene and total xylenes.