In situ MTBE biodegradation supported by diffusive oxygen release

Microcosm studies with sediments from Vandenberg Air Force Base, CA, suggest that native aerobic methyl tert-butyl ether (MTBE)-degrading microorganisms can be stimulated to degrade MTBE. In a series of field experiments, dissolved oxygen has been released into the anaerobic MTBE plume by diffusion through the walls of oxygen-pressurized polymeric tubing placed in contact with the flowing groundwater. MTBE concentrations were decreased from several hundred to less than 10 microg/L during passage through the induced aerobic zone, due apparently to in situ biodegradation: abiotic MTBE loss mechanisms were insignificant. Lag time for initiation of degradation was less than 2 months, and the apparent pseudo-first-order degradation rate was 5.3 day(-1). Additional MTBE was added in steps to raise the influent concentration to a maximum of 2.1 mg/L. With each step, MTBE was degraded within the preestablished aerobic treatment zone at rates ranging from 4.4 to 8.6 day(-1). Excess dissolved oxygen suggested that even higher MTBE concentrations could have been treated. Continued flow through the treatment zone was repeatedly confirmed through tracer and other tests. These and others' results suggest that it is possible to create permeable in situ treatment zones solely by releasing oxygen to support native microbial degradation of MTBE.     

Use of potassium formate in road winter deicing can reduce groundwater deterioration

We present here an aquifer scale study on the fate of potassium formate, an alternative, weakly corrosive deicing agent in soil and subsurfaces. Potassium formate was used to deice a stretch of a highway in Finland. The fate of the formate was examined by monitoring the groundwater chemistry in the underlying aquifer of which a conceptual model was constructed. In addition, we determined aerobic and anaerobic biodegradation rates of formate at low temperatures (-2 to +6 degrees C) in soil microcosms. Our results show that the formate did not enter the saturated zone through the thin vadose zone; thus, no undesirable changes in the groundwater chemistry were observed. Furthermore, the conceptual model explained the distribution of chloride in the aquifer used in deicing for the past 30 years. We recorded mineralization potential up to 97% and up to 17% within 24 h under aerobic and anaerobic conditions, respectively, in the soil and subsurface samples obtained from the site. This demonstrates that biodegradation in the topsoil layers was responsible for the removal of the formate. We conclude that the use of potassium formate can potentially help diminish the negative impacts of road winter deicing on groundwater without jeopardizing traffic safety.     

Biogeochemical processes and microbial characteristics across groundwater-surface water boundaries of the Hanford Reach of the Columbia River

Biogeochemical processes within riverbed hyporheic zones (HZ) can potentially impact the fate and transport of contaminants. We evaluated a modified freeze core technique for the collection of intact cobble-bed samples from the Columbia River HZ along a stretch of the Hanford Reach in Washington State and investigated microbiological and geochemical parameters of corresponding frozen and unfrozen samples. During three sampling periods (March, May, and November 2000), relatively high numbers of viable aerobic heterotrophic bacteria were recovered from both unfrozen (10(6)-10(7) cfu/g) and frozen samples (10(5)-10(6) cfu/g). Relatively large populations of sulfate-, nitrate-, and iron-reducing bacteria were present, and significant concentrations of acid-volatile sulfide were measured in some samples, indicating that anoxic regions exist within this zone. Cr(VI), a priority groundwater pollutant on adjacent U.S. Department of Energy lands, was probably removed from solution in HZ samples by a combination of microbial activity and chemical reduction, presumably via products of anaerobic microbial metabolism. These results suggest that biogeochemical processes in the Columbia River HZ may contribute to the natural attenuation of Cr(VI). Although freezing modestly diminished recovery of viable bacteria, freeze core techniques proved reliable for the collection of intact hyporheic sediments.     

Effect of exposure history on microbial herbicide degradation in an aerobic aquifer affected by a point source

The effects of in situ exposure to low concentrations (micrograms per liter) of herbicides on aerobic degradation of herbicides in aquifers were studied by laboratory batch experiments. Aquifer material and groundwater were collected from a point source with known exposure histories to the herbicides mecoprop (MCPP), dichlorprop, BAM, bentazone, isoproturon, and DNOC. Degradation of the phenoxy acids, mecoprop and dichlorprop, was observed in five of six sampling points from within the plume. Mecoprop was mineralized, and up to 70% was recovered as 14CO2. DNOC was degraded in only two of six sampling points from within the plume, and neither BAM, bentazone, nor isoproturon was degraded in any sampling point. A linear correlation (R2 > or = 0.83) between pre-exposure and amount of herbicide degraded within 50 days was observed for the phenoxy acids, mecoprop and dichlorprop. An improved model fit was obtained from using Monod degradation kinetics compared to zero- and first-order degradation kinetics. An exponential correlation (R2 > or = 0.85) was also found between numbers of specific phenoxy acid degrading bacteria and pre-exposure. Combination of these results strongly indicates that the low concentration exposure to phenoxy acids in the aquifer resulted in the presence of acclimated microbial communities, illustrated bythe elevated numbers of specific degraders as well as the enhanced degradation capability. The findings support application of natural attenuation to remediate aerobic aquifers contaminated by phenoxy acids from point sources.     

Groundwater discharge: potential association with fecal indicator bacteria in the surf zone

Short-lived radium isotopes (223Ra and 224Ra) are used to investigate the potential association between groundwater discharge and microbial pollution at Huntington Beach, CA. We establish the tidally driven exchange of groundwater from the surficial beach aquifer across the beach face. Groundwater is found to be a source of nutrients (silica, inorganic nitrogen, and orthophosphate) to the surf zone, and these nutrients could possibly provide an environment for enhanced growth or increased persistence of fecal indicator bacteria (FIB). Ammonium and ortho-phosphate explain up to 12-20% of the variance in FIB levels in the surf zone. Elevated levels of FIB were only found in 1 of the 26 groundwater samples. However, FIB in the surf zone covary with radium at fortnightly, diurnal, and semi-diurnal tidal periods. In addition, radium accounts for up to 38% of the variance in log-FIB levels in the surf zone. A column experiment illustrates that Enterococcus suspended in Huntington Beach saline groundwater is not significantly filtered by sand collected from the field. This work establishes a mechanism for the subterranean delivery of FIB pollution to the surf zone from the surficial aquifer and presents evidence that supports an association between groundwater discharge and FIB.     

Redox processes and release of organic matter after thermal treatment of a TCE-contaminated aquifer

Redox conditions in heated and unheated microcosm experiments were studied to evaluate the effect of thermal remediation treatment on biogeochemical processes in subsurface environments. The results were compared to field-scale observations from thermal treatments of contaminated sites. Trichloroethene-contaminated aquifer material and groundwater from Ft. Lewis, WA were incubated for 200 days at ambient temperature (i.e., 10 degrees C) or heated to 100 degrees C for 10 days and cooled slowly over a period of 150 days to mimic a thermal treatment. Increases of up to 14 mM dissolved organic carbon were observed in the aqueous phase after heating. Redox conditions did generally not change during heating in the laboratory experiment, and only minor changes occurred as an effect of heat treatment in the field. The conditions were slightly manganese/iron-reducing in two sediments and possibly sulfate-reducing in the third sediment based on production of up to 0.20 mM dissolved iron and 0.15 mM dissolved manganese and consumption of 0.08 mM sulfate. The calculated energy gain of less than -20 kJ/mol H2 for iron and sulfate reduction as well as methane production indicated that these processes were thermodynamically favorable. Sulfate reduction and methane production occurred in the unheated microcosms upon lactate amendment. Little or no reduction of the redox level was identified in heated lactate-amended microcosms, possibly because of limited microbial activity. Because the redox conditions, pH, and alkalinity remained within normal aquifer levels upon heating, bioaugmentation may be feasible for stimulating anaerobic dechlorination in heated samples or in future field applications.     

Chlorinated solvents in groundwater of the United States

Four chlorinated solvents-methylene chloride, perchloroethene (PCE), 1,1,1-trichloroethane, and trichloroethene (TCE)-were analyzed in samples of groundwater taken throughout the conterminous United States by the U.S. Geological Survey. The samples were collected between 1985 and 2002 from more than 5,000 wells. Of 55 volatile organic compounds (VOCs) analyzed in groundwater samples, solvents were among the most frequently detected. Mixtures of solvents in groundwater were common and may be the result of common usage of solvents or degradation of one solvent to another. Relative to other VOCs with Maximum Contaminant Levels (MCLs), PCE and TCE ranked high in terms of the frequencies of concentrations greater than or near MCLs. The probability of occurrence of solvents in groundwater was associated with dissolved oxygen content of groundwater, sources such as urban land use and population density, and hydraulic properties of the aquifer. The results reinforce the importance of understanding the redox conditions of aquifers and the hydraulic properties of the saturated and vadose zones in determining the intrinsic susceptibility of groundwater to contamination by solvents. The results also reinforce the importance of controlling sources of solvents to groundwater.     

Fringe-controlled natural attenuation of phenoxy acids in a landfill plume: integration of field-scale processes by reactive transport modeling

Data obtained from a field study of an aquifer contaminated by landfill leachate and related laboratory experiments suggest that natural attenuation of phenoxy acid herbicides such as mecoprop (MCPP) occurs in the transition zone between the anaerobic plume core and the overlying aerobic water body. The location of this transition zone is assumed to be primarily controlled by vertical transverse dispersion processes occurring downstream of the pollution source. A reactive transport modeling study was carried out to evaluate this conceptual model. The transport was simulated for a two-dimensional vertical cross section to quantify the combined physical, geochemical, and microbial processes that affect the fate of the phenoxy acid herbicides. The simulations, showing removal of phenoxy acids, an increase of phenoxy acid degraders in the fringe zone, and a dependency of the results on vertical transverse dispersivity, are compatible with the hypothesis of fringe-controlled aerobic biodegradation of the phenoxy acids.     

Pathway-dependent isotope fractionation during aerobic and anaerobic degradation of monochlorobenzene and 1,2,4-trichlorobenzene

Stable carbon isotope fractionation is a valuable tool for monitoring natural attenuation and to establish the fate of groundwater contaminants. In this study, we measured carbon isotope fractionation during aerobic and anaerobic degradation of two chlorinated benzenes: monochlorobenzene (MCB) and 1,2,4-trichlorobenzene (1,2,4-TCB). MCB isotope fractionation was measured in anaerobic methanogenic microcosms, while 1,2,4-TCB isotope experiments were carried out in both aerobic and anaerobic microcosms. Large isotope fractionation was observed in both the anaerobic microcosm experiments. Enrichment factors (ε) for anaerobic reductive dechlorination of MCB and 1,2,4-TCB were -5.0‰ ± 0.2‰ and -3.0‰ ± 0.4‰, respectively. In contrast, no significant isotope fractionation was found during aerobic microbial degradation of 1,2,4-TCB. The cleavage of a C-Cl σ bond occurs during anaerobic reductive dechlorination of MCB and 1,2,4-TCB, while no σ bond cleavage is involved during aerobic degradation via dioxygenase. The difference in isotope fractionation for aerobic versus anaerobic biodegradation of MCB and 1,2,4-TCB can be explained by the difference in the initial step of aerobic versus anaerobic biodegradation pathways.     

Small-volume releases of gasoline in the vadose zone: impact of the additives MTBE and ethanol on groundwater quality

A controlled gasoline spill experiment was performed under outdoor conditions typical for winter in temperate regions to study the fate of methyl tert-butyl ether (MTBE), ethanol, benzene, and selected other petroleum hydrocarbons. Artificial gasoline containing MTBE and ethanol (5% w/w of each) was placed at a defined depth into a 2.3 m thick unsaturated zone of alluvial sand overlying a gravel aquifer in a lysimeter. During an initial period of 41 days without recharge, MTBE and hydrocarbon vapors migrated by vapor-phase diffusion to groundwater, while ethanol vapors were naturally attenuated. In a subsequent period of 30 days with 5-mm daily recharge, all soluble compounds including ethanol were transported to the groundwater. Ethanol disappeared concomitantly with benzene and all other petroleum hydrocarbons except isooctane from the aerobic groundwater due to biodegradation. MTBE persisted for longer than 6 months at concentrations larger than 125000 microg L(-1). No evidence for MTBE biodegradation was found, whereas > 99.6% of ethanol removal from the lysimeter was due to biodegradation. It is concluded that MTBE-free gasoline would be less harmful for groundwater resources and that ethanol is an acceptable substitute.     

Biological enhancement of tetrachloroethene dissolution and associated microbial community changes

A bench-scale study was performed to evaluate the enhancement of tetrachloroethene (PCE) dissolution from a dense nonaqueous phase liquid (DNAPL) source zone due to reductive dechlorination. The study was conducted in a pair of two-dimensional bench-scale aquifer systems using soil and groundwater from Dover Air Force Base, DE. After establishment of PCE source zones in each aquifer system, one was biostimulated (addition of electron donor) while the other was biostimulated and then bioaugmented with the KB1 dechlorinating culture. Biostimulation resulted in the growth of iron-reducing bacteria (Geobacter) in both systems as a result of the high iron content of the Dover soil. After prolonged electron donor addition methanogenesis dominated, but no dechlorination was observed. Following bioaugmentation of one system, dechlorination to ethene was achieved, coincident with growth of introduced Dehalococcoides and other microbes in the vicinity and downgradient of the PCE DNAPL (detected using DGGE and qPCR). Dechlorination was not detected in the nonbioaugmented system over the course of the study, indicating that the native microbial community, although containing a member of the Dehalococcoides group, was not able to dechlorinate PCE. Over 890 days, 65% of the initial emplaced PCE was removed in the bioaugmented, dechlorinating system, in comparison to 39% removal by dissolution from the nondechlorinating system. The maximum total ethenes concentration (3 mM) in the bioaugmented system occurred approximately 100 days after bioaugmentation, indicating that there was at least a 3-fold enhancement of PCE dissolution atthis time. Removal rates decreased substantially beyond this time, particularly during the last 200 days of the study, when the maximum concentrations of total ethenes were only about 0.5 mM. However, PCE removal rates in the dechlorinating system remained more than twice the removal rates of the nondechlorinating system. The reductions in removal rates over time are attributed to both a shrinking DNAPL source area, and reduced flow through the DNAPL source area due to bioclogging and pore blockage from methane gas generation.     

Simultaneous utilization of acetate and hydrogen by Geobacter sulfurreducens and implications for use of hydrogen as an indicator of redox conditions

Dissolved hydrogen concentrations, in conjunction with other geochemical indicators, are becoming an accepted means to determine terminal electron acceptor processes (TEAPs) in groundwater aquifers. Aqueous hydrogen concentrations have been found to fall within specific ranges under methanogenic, sulfate-reducing, iron-reducing, and denitrification conditions. Although hydrogen is gaining in acceptance for determining subsurface TEAPs, there is a dearth of data with regards to the kinetic coefficients for hydrogen utilization in the presence or absence of an additional electron donor under different TEAPs. This study expands the kinetic data for hydrogen utilization through a series of batch experiments, which were conducted to study the utilization of acetate and hydrogen by Geobacter sulfurreducens under iron-reducing conditions. The results of these experiments indicate that the kinetic coefficients (cell yield and first-order degradation rate) describing the rate of hydrogen utilization by G. sulfurreducens under iron-reducing conditions correlate energetically with the coefficients found in previous experiments under methanogenic and sulfate-reducing conditions. In addition, with acetate and hydrogen as simultaneous electron donors, there is slight inhibition between the two electron donors for G. sulfurreducens, and this can be modeled through competitive inhibition terms in the classic Monod formulation. Finally, a key result of this study is that the TEAP-dependent hydrogen concentration in aquifers is not related solely to the microbial kinetics of the hydrogen-consuming organisms as previously suggested but is affected by the multi-substrate kinetics of hydrogen being consumed simultaneously with other electron donors as well as the availability of the electron acceptor.     

Field evaluation of in situ source reduction of trichloroethylene in groundwater using bioenhanced in-well vapor stripping

Two technologies in combination, cometabolic bioremediation and in-well vapor stripping, were applied to reduce trichloroethylene (TCE) concentrations in groundwater at a contaminant source area without the need to pump contaminated groundwater to the surface for treatment. The vapor-stripping well reduced source TCE concentrations (as high as 6-9 mg/L) by over 95%. Effluent from the well then flowed to two bioremediation wells, where additional reductions of approximately 60% were achieved. TCE removal was extensively monitored (for research and not regulatory purposes) using an automated system that collected samples about every 45 min at 55 locations over an area of approximately 50 x 60 m2. During 4.5 months of system operation, total TCE mass removal was 8.1 kg, 7.1 kg of which resulted from in-well vapor stripping and 1.0 kg from biotreatment. The system reduced the average TCE concentration of about 3000 microg/L in the source-zone groundwater to about 250 microg/L in water leaving the treatment zone, effecting greater than 92% TCE removal. A 6 month rebound study after system operation ceased found TCE concentrations then increased significantly in the treatment zone due to diffusion from the fractured rock below and perhaps other processes, with mass increases of about 1.5 kg in the lower aquifer and 0.3 kg in the upper aquifer.     

Signature metabolites attesting to the in situ attenuation of alkylbenzenes in anaerobic environments

Accurate assessment of the fate of hydrocarbons spilt in aquifers is essential for gauging associated health and ecological risks. Regulatory pressure to actively remediate such contaminated ecosystems can be substantially diminished if solid evidence for in situ microbial destruction of pollutants is obtained. In laboratory incubations, sediment-associated microorganisms from a gas condensate-contaminated aquifer anaerobically biodegraded toluene, ethylbenzene, xylene, and toluic acid isomers with stoichiometric amounts of sulfate consumed or methane produced. The activation of the alkylated aromatic contaminants involved conversion to their corresponding benzylsuccinic acid derivatives, a reaction known to occur for toluene and m-xylene decay, but one previously unrecognized for ethylbenzene, o- and p-xylene, and m-toluate metabolism. Benzylsuccinates were further biodegraded to toluates, phthalates, and benzoate. In laboratory incubations, these metabolites were transiently produced. Several of the metabolites were also detected in groundwater samples from an aquifer where alkylbenzene concentrations decreased over time, suggesting that anaerobic microbial metabolism of these contaminants also occurs in situ. Our studies confirm the utility of the aforementioned compounds as signature metabolites attesting to the natural attenuation of aromatic hydrocarbons in anaerobic environments.     

GeoChip-based analysis of microbial functional gene diversity in a landfill leachate-contaminated aquifer

The functional gene diversity and structure of microbial communities in a shallow landfill leachate-contaminated aquifer were assessed using a comprehensive functional gene array (GeoChip 3.0). Water samples were obtained from eight wells at the same aquifer depth immediately below a municipal landfill or along the predominant downgradient groundwater flowpath. Functional gene richness and diversity immediately below the landfill and the closest well were considerably lower than those in downgradient wells. Mantel tests and canonical correspondence analysis (CCA) suggested that various geochemical parameters had a significant impact on the subsurface microbial community structure. That is, leachate from the unlined landfill impacted the diversity, composition, structure, and functional potential of groundwater microbial communities as a function of groundwater pH, and concentrations of sulfate, ammonia, and dissolved organic carbon (DOC). Historical geochemical records indicate that all sampled wells chronically received leachate, and the increase in microbial diversity as a function of distance from the landfill is consistent with mitigation of the impact of leachate on the groundwater system by natural attenuation mechanisms.     

Leaching and primary biodegradation of sulfonated naphthalenes and their formaldehyde condensates from concrete superplasticizers in groundwater affected by tunnel construction

Sulfonated naphthalenes and their formaldehyde condensates (SNFC) are used as concrete superplasticizers fortunnel construction through aquifers.This paperdiscusses their primary biodegradation in groundwater affected by construction activities. The analyses of groundwater samples collected 5 m away from a construction site clearly indicated that components of the applied SNFC product leached into the groundwater. A maximum total concentration of these compounds of 233 microg/L was found, and it was shown that only the monomeric sulfonated naphthalenes andthe condensates uptothetetramerleached in substantial amounts. The decrease in concentration of several monomeric components could not be explained by mere dispersion but rather indicates a biological transformation in the aquifer. This was confirmed at a second field site and by laboratory degradation experiments with piezometer material as inoculum. Lag phases for the individually degradable sulfonated naphthalenes ranged from 0 to 96 d. Naphthalene-1,5-disulfonate and the oligomeric components were neither degraded in the aquifer nor in the laboratory experiments within an observation time of up to 195 d. This clearly indicates their persistence in subsurface waters.     

Microbial mercury transformation in anoxic freshwater sediments under iron-reducing and other electron-accepting conditions

Potential rates of microbial methylation of inorganic mercury (added as HgCl2) and degradation of methyl mercury (MeHg) (added as CH3HgCl) were investigated in anoxic sediments from the Mobile Alabama River Basin (MARB) dominated by different terminal electron-accepting processes (TEAPs). Potential rates of methylation were comparable under methanogenic and sulfate-reducing conditions but suppressed under iron-reducing conditions, in slurries of freshwater wetland sediment In contrast, MeHg degradation rates were similar under all three TEAPs. Microbial Hg methylation and MeHg degradation were also investigated in surface sediment from three riverine sites, two of which had iron reduction and one sulfate reduction, as the dominant TEAP (as determined by 14C-acetate metabolism and other biogeochemical measurements). Methylation was active in sulfate-reducing sediments of a tributary creek and suppressed in iron-reducing, sandy sediments from the open river, whereas MeHg degradation was active at all three sites. Although iron-reducing conditions often suppressed methylation, some methylation activity was observed in two out of three replicates from iron-reducing sediments collected near a dam. Given that MeHg degradation was consistently observed under all TEAPs, our results suggest that the net flux of MeHg from iron-reducing surface sediments may be suppressed (due to inhibition of gross MeHg production) compared to sediments supporting other TEAPs.     

Dissolution of an emplaced source of DNAPL in a natural aquifer setting

Field-scale dissolution of a multicomponent DNAPL (dense nonaqueous-phase liquid) source intentionally emplaced below the water table is evaluated in a well-characterized natural aquifer setting. The block-shaped source contained 23 kg of a trichloromethane, trichloroethene, and perchloroethene mixture homogeneously distributed at 5% saturation of pore space. Dissolution was monitored for 3 yr via down-gradient samplers (1-m fence) and occasional intra-source sampling. Although intra-source equilibrium dissolution was shown and endorsed by supporting modeling and literature lab data, less than equilibrium concentrations were predominantly monitored in the 1-m fence. This was ascribed to significant by-passing of the source by groundwater flow due to its low permeability relative to the aquifer and associated dilution of concentrations emitted from the source. Heterogeneous source dissolution occurred despite the relative homogeneity of the source and aquifer and was ascribed to dissolution fingering, which has not been previously field-demonstrated. Bulk bypass of groundwater flow around the source zone caused slow dissolution rates, with 77% of the source remaining after 3 yr and a projected longevity of approximately 25 yr. Observed dissolution fingering would have significantly increased longevity as it increasingly caused intra-source bypass of remaining DNAPL. Our dissolution interpretations were endorsed by additional data collected after 6 yr during source remediation via permanganate oxidation.     

Shifts in biodegradation kinetics of the herbicides MCPP and 2,4-D at low concentrations in aerobic aquifer materials

Biodegradation kinetics of two phenoxy acid herbicides, MCPP [(+/-)-2-(4-chloro-2-methylphenoxy)propanoic acid; mecoprop] and 2,4-D [2,4-dichlorophenoxyacetic acid] were studied in laboratory batch microcosms at low concentrations (0.025-100 microg/L) using 14C technique with sediments and groundwater from a shallow aerobic sandy aquifer. Below a certain threshold concentration of approximately 1 microg/L for 2,4-D and 10 microg/L for MCPP, the biodegradation followed first-order nongrowth kinetics, and no adaptation was observed within the experimental period of 341 d. Half-lifes for ultimate degradation were 500 d for 2,4-D and 1100 d for MCPP at 10 degrees C in unpolluted aquifer sediment in this environmentally relevant concentration regime. Above the threshold concentrations, the biodegradation rate accelerated gradually due to selective growth of specific biomass, which was ascertained from 14C most probable number enumerations of specific phenoxy acid degraders. Atthe highest concentration tested (100 microg/ L), specific degraders increased from 10(-1) to 10(5) cells/g during the experiment, and half-lifes after adaptation decreased to approximately 5 d. The enhanced rate of degradation by adapted systems was maintained during degradation of the last residuals measured to less than 0.1 microg/L. In situ long-term preexposure of the aquifer sediment also resulted in significant higher degradation rates of the phenoxy acids.     

In situ stimulation of groundwater denitrification with formate to remediate nitrate contamination

In situ stimulation of denitrification has been proposed as a mechanism to remediate groundwater nitrate contamination. In this study, sodium formate was added to a sand and gravel aquifer on Cape Cod, MA, to test whether formate could serve as a potential electron donor for subsurface denitrification. During 16- and 10-day trials, groundwater from an anoxic nitrate-containing zone (0.5-1.5 mM) was continuously withdrawn, amended with formate and bromide, and pumped back into the aquifer. Concentrations of groundwater constituents were monitored in multilevel samplers after up to 15 m of transport by natural gradient flow. Nitrate and formate concentrations were decreased 80-100% and 60-70%, respectively, with time and subsequent travel distance, while nitrite concentrations inversely increased. The field experiment breakthrough curves were simulated with a two-dimensional site-specific model that included transport, denitrification, and microbial growth. Initial values for model parameters were obtained from laboratory incubations with aquifer core material and then refined to fit field breakthrough curves. The model and the lab results indicated that formate-enhanced nitrite reduction was nearly 4-fold slower than nitrate reduction, but in the lab, nitrite was completely consumed with sufficient exposure time. Results of this study suggest that a long-term injection of formate is necessary to test the remediation potential of this approach for nitrate contamination and that adaptation to nitrite accumulation will be a key determinative factor.