The Role of Bioattenuation in the Management of Aromatic Hydrocarbon Plumes in Aquifers

Ground water scientists have made significant advances in understanding the soil interactions, hydrogeology, fate and transport, and subsurface microbiology of aromatic hydrocarbons (BTEX) in aquifer systems. It is now generally recognized that a major factor responsible for the attenuation and mass reduction of BTEX in plumes is the widespread occurrence of hydrocarbon biodegradation by indigenous soil microorganisms in aquifer material. Most well-studied BTEX plumes that develop from the accidental release of gasoline fuels contain low levels of soluble hydrocarbons (< 1 to 5000 ppb) and have been shown to be spatially confined because of natural biotransformation mechanisms. These in situ processes are controlled by source and aquifer characteristics, permeability, sorption, and geochemical properties of the aquifer. Many laboratory subsoil-ground water microcosms and field studies (10 to 20 C) have demonstrated the rapid biodecay (1 to SO percent/day for microcosms and 0.5 to 1.5 percent/day for plumes) of these aromatic compounds under primarily aerobic conditions (i.e., those with sufficient dissolved oxygen). The ability to implement ground water bioremediation will depend upon our understanding of source control and aquifer recharge effects on the spatial distribution of plumes. In addition, estimating the biodegradation of sorbed BTEX, determining limits and potential for in situ biostimulation of soluble plumes, and establishing data requirements for predictive modeling of natural attenuation will be useful for this remediation technology. The use of these tools to manage ground water quality appears to represent the most practical alternative, particularly for low-risk ground water supplies.     

Remediation of Dissolved BTEX Through Surface Application: A Prototype Field Investigation

The feasibility of surface application for remediating monoaromatic hydrocarbons (benzene, toluene, ethylbenzene, and xylenes — termed BTEX as a croup) dissolved in ground water under field conditions was investigated at a site within Canadian Forces Base. Borden. Ontario. The surface area was 25 m² and underlain by 3 to 3.5 m of unsaturated sands soil. For periods of at least 216 hours, between 43 and 72 cm/d of water containing BTEX at concentrations that averaged between 8 and 11 mg/L were continuously applied by drip irrigation. Nitrogen was added to the soil as a nutrient for the final third of the investigation.
Before the applied water reached the water table. BTEX mass losses ranged from of to essentially KM) percent. Less than 6 percent of the BTEX mass losses could be attributed to volatilization from the unsaturated soil. The remaining BTEX mass losses were attributed to biodegradation, mostly in the top 50 cm of the soil, which contained more inorganic nitrogen and organic carbon than the deeper soil. Biodegradation rates increased with applied concentration, nitrogen addition, and exposure to BTEX. Benzene concentrations in ground water attained compliance with Canadian and American drinking water standards only after nitrogen application.     

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.     

Demonstration of a Microbiologically Enhanced Vertical Ground Water Circulation Well Technology at a Superfund Site

A full-scale ground water circulation well (GCW) system was installed and operated to demonstrate in situ remediation of soil and ground water impacted with a mixture of chlorinated and nonchlorinated organic compounds at a Superfund site in upstate New York. System performance and applicability under site-specific conditions were evaluated based on the system's ability to meet the New York State Department of Environmental Conservation (NYSDEC) cleanup goals for target compounds in ground water and soil. Contaminants from the unsaturated zone were mobilized (volatilized) by one-way vacuum extraction, and treated via enhanced biodegradation (bioventing). In the saturated zone, contaminants were mobilized by soil flushing (solubilized) and treated by a combination of air stripping and biodegradation. An in situ aqueous phase bioreactor, and an ex situ gas phase bioreactor, were integrated into the system to enhance treatment via bioremediation. After 15 months of operation, the mass of target contaminants in soil and ground water combined had been reduced by 75%. Removal by biological mechanisms ranged from 35% to 56% of the total observed mass reduction. The in situ and the ex situ bioreactors mineralized 79% and 76%, respectively, of their target biodegradable contaminant loads. Results indicate that some mass reduction in target contaminants may have been from aerobic and aerobic processes within the circulation cell. Nonchlorinated compounds were relatively easy to mobilize (volatilize, solubilize, and/or transport) and treat when compared to chlorinated compounds. The data collected during the 15-month study indicate that remediation could be accomplished at the Sweden-3 Chapman site using the technology tested.     

Tracing coalbed natural gas-coproduced water using stable isotopes of carbon

Recovery of hydrocarbons commonly is associated with coproduction of water. This water may be put to beneficial use or may be reinjected into subsurface aquifers. In either case, it would be helpful to establish a fingerprint for that coproduced water so that it may be tracked following discharge on the surface or reintroduction to geologic reservoirs. This study explores the potential of using δ¹³C of dissolved inorganic carbon (DIC) of coalbed natural gas (CBNG)–coproduced water as a fingerprint of its origin and to trace its fate once it is disposed on the surface. Our initial results for water samples coproduced with CBNG from the Powder River Basin show that this water has strongly positive δ¹³C_DIC (12‰ to 22‰) that is readily distinguished from the negative δ¹³C of most surface and ground water (−8‰ to −11‰). Furthermore, the DIC concentrations in coproduced water samples are also high (more than 100 mg C/L) compared to the 20 to 50 mg C/L in ambient surface and ground water of the region. The distinctively high δ¹³C and DIC concentrations allow us to identify surface and ground water that have incorporated CBNG-coproduced water. Accordingly, we suggest that the δ¹³C_DIC and DIC concentrations of water can be used for long-term monitoring of infiltration of CBNG-coproduced water into ground water and streams. Our results also show that the δ¹³C_DIC of CBNG-coproduced water from two different coal zones are distinct leading to the possibility of using δ¹³C_DIC to distinguish water produced from different coal zones.     

Evaluation of BTEX Remediation by Natural Attenuation at a Coastal Facility

Natural attenuation has emerged as a potential alternative for remediating sites contaminated with fuel hydrocarbons. This paper examines the viability of using attenuation through natural processes to remediate ground water at an industrial facility. The research combined field assessments with data analysis and modeling to evaluate plume stability and predict remediation times. Field data on natural attenuation indicate that BTEX contamination at the site is being attenuated at rates that vary within the range of 0.0001 to 0.0073/day. Stability analyses confirm that the BTEX plume has reached steady state. An analysis on mass flux showed that between 1979 and 1996, 95,000 pounds of BTEX were lost via biodegradation, while 8000 pounds were lost through other mechanisms. A first-order biodegradation rate of 0.0002/day for BTEX was obtained from the change in the total mass of dissolved BTEX with time. Cleanup times in excess of 200 years for the site were estimated using analytical modeling of natural attenuation, which agreed well with the remediation times estimated using the attenuation rates calculated for the site.     

Engineering and hydrogeological problems associated with in situ treatment

Abstract

Most organic materials that contaminate soil and the subsurface environment are readily degraded by natural biological processes. To this degree, in situ bioremediation can be thought of as a highly successful purification process. However, some organic molecules are naturally refractory to biodegradation, or other environmental factors induce molecular recalcitrance such as the absence of a proper microbial population or the presence of unsuitable environmental conditions. Examples of recalcitrant groundwater contaminants are soluble components of petroleum hydrocarbons (BTEX) and chlorinated aliphatic hydrocarbons (CAHs). Organic recalcitrance may be changed through introduction of degrading populations of microorganisms or by changing the environmental conditions through introduction of nutrients or other chemicals. The most significant engineering deficiency in in situ bioremediation is the absence of proven methods to introduce such materials into the subsurface environment for efficient mixing with microorganisms and the contaminants of concern.     

Flowpath Independent Monitoring of Reductive Dechlorination Potential in a Fractured Rock Aquifer

The flowpath dependent approaches that are typically employed to assess biodegradation of chloroethene contaminants in unconsolidated aquifers are problematic in fractured rock settings, due to difficulties defining discrete groundwater flowpaths in such systems. In this study, the variation in the potential for chloroethene biodegradation with depth was evaluated in a fractured rock aquifer using two flowpath independent lines of field evidence: (1) the presence of the three biochemical prerequisites [electron donor(s), chloroethene electron acceptor(s), and chlororespiring microorganism(s)] for efficient chloroethene chlororespiration and (2) the in situ accumulation of chloroethene reductive dechlorination daughter products. The validity of this approach was assessed by comparing field results with the results of [1, 2-¹⁴C] cis -DCE microcosm experiments. Microcosms were prepared with depth-specific core material, which was crushed and emplaced in discrete packer intervals for 1 year to allow colonization by the indigenous microbial community. Packer intervals characterized by significant electron donor concentrations, elevated numbers of chlororespiring microorganisms, and high reductive dechlorination product to parent contaminant ratios correlated well with the production of ¹⁴C-labeled reductive dechlorination products in the microcosm experiments. These results indicate that, in the absence of information on discrete groundwater flowpaths, a modified approach emphasizing flowpath independent lines of evidence can provide insight into the temporal and spatial variability of contaminant biodegradation in fractured rock systems.     

Enhanced Degradation of Dissolved Benzene and Toluene Using a Solid Oxygen-Releasing Compound

A field lest to evaluate the applicability of an oxygon-releasing compound (ORC) to the rernediation of ground water contaminated with benzone and toluene was conducted in the Borden Aquifer in Ontario. Canada. Benzene and toluene were injected as organic substrates to represent BTEX compounds, bromide was used as a tracer, and nitrate was added to avoid nitrate-limited conditions.
The fate of the solutes was monitored along four lines of monitoring points and wells. Two lines studied the behavior of the solutes upgradient and downgradient of two large-diameter well screens filled with briquets containing ORC and briquets without ORC. One line was used to study the solute behavior upgradient and downgradient of columns of ORC powder placed directly in the saturated zone. The remaining line was a control.
The results indicate that ORC in both briquet and powder form can release significant amounts of oxygen to conlaminated ground water passing by it. In the formulation used in this work, oxygen release persisted for at least 10 weeks. Furthemiore, the study indicates that the enhancement of the available dissolved oxygen content of at least 4 mg/L each of the ground water by ORC can support biodegradation of benzene and toluene dissolved in ground water. Such concentrations are typical of those encountered at sites contaminated with petroleum hydrocarbons; therefore, these results suggest that there is promise for ORC to enhance in situ biodegradation of BTKX contaminants at such sites using passive (nonpumping) systems to contact the contaminated ground water with the oxygen source.     

Fate of MTBE Relative to Benzene in a Gasoline-Contaminated Aquifer (1993–98)

Methyl tert -butyl ether (MTBE) and benzene have been measured since 1993 in a shallow, sandy aquifer contaminated by a mid-1980s release of gasoline containing fuel oxygenates. In wells downgradient of the release area, MTBK was detected before benzene, reflecting a chromatographic-like separation of these compounds in the direction of ground water flow. Higher concentrations of MTBE and benzene were measured in the deeper sampling ports of multilevel sampling wells located near the release area, and also up to 10 feet (3 m) below the water table surface in nested wells located farther from the release area. This distribution of higher concentrations at depth is caused by recharge events that deflect originally horizontal ground water flowlines. In the laboratory, microcosms containing aquifer material incubated with uniformly labeled ¹⁴C-MTBE under aerobic and anaerobic. Fe(III)-reducing conditions indicated a low but measurable biodegradation potential (<3%¹⁴C-MTBW as ¹⁴CO₂) after a seven-month incubation period, Tert -butyl alcohol (TBA), a proposed microbial-MTBE transformation intermediate, was detected in MTBE-contaminated wells, but TBA was also measured in unsaturated release area sediments. This suggests that TBA may have been present in the original fuel spilled and does not necessarily reflect microbial degradation of MTBE. Combined, these data suggest that milligram per liter to microgram per liter decreases in MTBE concentrations relative to benzene are caused by the natural attenuation processes of dilution and dispersion with less-contaminated ground water in the direction of flow rather than biodegradation at this point source gasoline release site.     

Geochemical Indicators of Intrinsic Bioremediation

A detailed field investigation has been completed at a gasoline-contaminated aquifer near Rocky Point, NC, to examine possible indicators of intrinsic bioremediation and identify factors that may significantly influence the rate and extent of bioremediation. The dissolved plume of benzene, toluene, ethylbenzene, and xylene (BTEX) in ground water is naturally degrading. Toluene and o-xylene are most rapidly degraded followed by m-, p-xylene, and benzene. Ethylbenzene appears to degrade very slowly under anaerobic conditions present in the center of the plume. The rate and extent of biodegradation appears to be strongly influenced by the type and quantity of electron acceptors present in the aquifer. At the upgradient edge of the plume, nitrate, ferric iron, and oxygen are used as terminal electron acceptors during hydrocarbon biodegradation. The equivalent of 40 to 50 mg/I of hydrocarbon is degraded based on the increase in dissolved CO₂ relative to background ground water. Immediately downgradient of the source area, sulfate and iron are the dominant electron acceptors. Toluene and o-xylene are rapidly removed in this region. Once the available oxygen, nitrate, and sulfate are consumed, biodegradation is limited and appears to be controlled by mixing and aerobic biodegradation at the plume fringes.     

Effects of Process Control Changes on Aquifer Oxygenation Rates During In Situ Air Sparging in Homogeneous Aquifers

In situ air sparging is used to remediate petroleum fuels and chlorinated solvents present as submerged contaminant source /ones and dissolved contaminant plumes, or to provide barriers to dissolved contaminant plume migration. Contaminant removal occurs through a combination of volatilization and aerobic biodegradation: thus, the performance at any given site depends on the contaminant and oxygen mass transfer rates induced by the air injection. It has been hypothesized that these rates are sensitive to changes in process flow conditions and site lithology, but no data is available to identify trends or the magnitude of the changes. In this work, oxygenation rates were measured for a range of air injection rates, ground water flow rates, and pulsing frequencies using a laboratory-scale two-dimensional physical model constructed to simulate a homogeneous hydrogeologic setting. Experiments were conducted with water having low chemical and biochemical oxygen demand. Results suggest the following: that there is an optimum air injection rate: advective How of ground water can be a significant factor when ground water velocities are > 0.3 m/d: and pulsing the air injection had little effect on the oxygenation rate relative lo the continuous air injection case.     

Analysis of Petroleum-Contaminated Water by GC/FID with Direct Aqueous Injection

A direct aqueous injection capillary gas chromatography/flame ionization (GC/FID) procedure for the analysis of petroleum-contaminated water was developed and applied to seven water samples saturated with different petroleum products. Separation of C₁ to C₄ alcohols, C₆ to C₉ monoaromatics, MTBE, phenol, aniline, and other compounds, and the detection of BTEX compounds at concentrations at or below their maximum contaminant levels (MCLs) is reported. Among the test compounds analyzed, the only pair found to coelute were 1-butanol and benzene. A method for confirmation of alcohols and polar compounds in the presence of dissolved petroleum hydrocarbons was also evaluated. In this case, water samples were analyzed before and after purging. Polar compounds were found to be significant components of the water soluble fractions of commercial petroleum products.     

Origins of hydrocarbons in the Sagara oil field, central Japan

Abstract   We collected free-gas and in situ fluid samples up to a depth of 200.6 m from the Sagara oil field, central Japan (34°44'N, 138°15'E), during the Sagara Drilling Program (SDP) and measured the concentrations and stable carbon isotopic compositions of CH₄ and C₂H₆ in the samples. A combination of the CH₄/C₂H₆ ratios with the carbon isotope ratios of methane indicates that the hydrocarbon gases are predominantly of thermogenic origin at all depths. The isotope signature of hydrocarbon gases of δ¹³      < δ¹³     suggests that these gases in the Sagara oil field are not generated by polymerization, but by the decomposition of organic materials.     

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.     

Delayed impact of new volcanic ejecta on ground water quality

We observed long-term changes in the concentrations of dissolved ions in ground water caused by leachate from new volcanic ejecta deposited on the ground surface of the volcanic Miyakejima Island, Japan. Water samples were collected from nine wells and two rain collectors over a period of more than 10 years, and samples of runoff water were collected periodically. The samples were analyzed for temperature, pH, alkalinity, Cl⁻, and SO₄²⁻; some of the samples were also analyzed for δ¹³C. Because the leachate from the volcanic ejecta contained sulfate, we recorded an increase in SO₄²⁻ concentrations in the (unconfined) well water. The increase in SO₄²⁻ was initially detected between less than 1.4 and 5.2 years after the eruption, showing peak concentrations from 2.4 to 6.4 years after the eruption. This delayed response reflects the transit time of downward-moving SO₄²⁻ in the vadose zone, corresponding to an apparent movement rate of 0.4 to 7.2 cm/d. The rate relates to the mean recharge, represented as a fraction of local mean rainfall, and is calculated using the Cl⁻ balance method. The magnitude of the recorded increases reflects the volume of volcanic mudflow on the ground surface within the basin. For the management of ground water after an eruption, it is therefore important to know the chemical properties of the volcanic ejecta and the spatial distribution of mudflow to estimate the magnitude of the effect of ejecta on ground water quality.     

Analytical approximation to characterize the performance of in situ aquifer bioremediation

The performance of in situ bioremediation to remove organic contaminants from contaminated aquifers depends on the physical and biochemical parameters. We characterize the performance by the contaminant removal rate and the region where biodegradation occurs, the biologically active zone (BAZ). The numerical fronts obtained by one-dimensional in situ bioremediation modeling reveal a traveling wave behavior: fronts of microbial mass, organic contaminant and electron acceptor move with a constant velocity and constant front shape through the domain. Hence, only one front shape and a linear relation between the front position and time is found for each of the three compounds. We derive analytical approximations for the traveling wave front shape and front position that agree perfectly with the traveling wave behavior resulting from the bioremediation model. Using these analytical approximations, we determine the contaminant removal rate and the BAZ. Furthermore, we assess the influence of the physical and biochemical parameters on the performance of the in situ bioremediation technique.     

MTBE, TBA, and TAME Attenuation in Diverse Hyporheic Zones

Groundwater contamination by fuel-related compounds such as the fuel oxygenates methyl tert -butyl ether (MTBE), tert -butyl alcohol (TBA), and tert -amyl methyl ether (TAME) presents a significant issue to managers and consumers of groundwater and surface water that receives groundwater discharge. Four sites were investigated on Long Island, New York, characterized by groundwater contaminated with gasoline and fuel oxygenates that ultimately discharge to fresh, brackish, or saline surface water. For each site, contaminated groundwater discharge zones were delineated using pore water geochemistry data from 15 feet (4.5 m) beneath the bottom of the surface water body in the hyporheic zone and seepage-meter tests were conducted to measure discharge rates. These data when combined indicate that MTBE, TBA, and TAME concentrations in groundwater discharge in a 5-foot (1.5-m) thick section of the hyporheic zone were attenuated between 34% and 95%, in contrast to immeasurable attenuation in the shallow aquifer during contaminant transport between 0.1 and 1.5 miles (0.1 to 2.4 km). The attenuation observed in the hyporheic zone occurred primarily by physical processes such as mixing of groundwater and surface water. Biodegradation also occurred as confirmed in laboratory microcosms by the mineralization of U- ¹⁴C-MTBE and U-¹⁴C-TBA to ¹⁴CO₂ and the novel biodegradation of U- ¹⁴C-TAME to ¹⁴CO₂ under oxic and anoxic conditions. The implication of fuel oxygenate attenuation observed in diverse hyporheic zones suggests an assessment of the hyporheic zone attenuation potential (HZAP) merits inclusion as part of site assessment strategies associated with monitored or engineered attenuation.     

Pore Water Characteristics Following a Release of Neat Ethanol onto Pre-existing NAPL

Neat ethanol (75.7 L) was released into the upper capillary zone in a continuous-flow, sand-packed aquifer tank (8.2 m³) with an average seepage velocity of 0.75 m/day. This model aquifer system contained a residual nonaqueous phase liquid (NAPL) that extended from the capillary zone to 10 cm below the water table. Maximum aqueous concentrations of ethanol were 20% v/v in the capillary zone and 0.08% in the saturated zone at 25 and 30 cm downgradient from the emplaced NAPL source, respectively. A bench-scale release experiment was also conducted for a similar size spill (scaled to the plan area). The concentrations of ethanol in ground water for both the bench- and pilot-scale experiments were consistent with advective–dispersive limited mass transfer from the capillary to the saturated zone. Concentrations of monoaromatic hydrocarbons and isooctane increased in the pore water of the capillary zone as a result of both redistribution of residual NAPL (confirmed by visualization) and enhanced hydrocarbon dissolution due to the cosolvent effect exerted by ethanol. In the tank experiment, higher hydrocarbon concentrations in ground water were also attributed to decreased hydrocarbon biodegradation activity caused by preferential microbial utilization of ethanol and the resulting depletion of oxygen. These results infer that spills of highly concentrated ethanol will be largely confined to the capillary zone due to its buoyancy, and ethanol concentrations in near-source zone ground water will be controlled by mass transfer limitations and hydrologic conditions. Furthermore, highly concentrated ethanol releases onto pre-existing NAPL will likely exacerbate impacts to ground water, due to NAPL mobilization and dissolution, and decreased bioattenuation of hydrocarbons.     

Nitrate Source Identification Using δ15N in a Ground Water Plume Near an Intensive Swine Operation

Nitrate-contaminated ground water beneath and adjacent to an intensive swine ( Sus scrofa domesticus ) production facility in the Middle Coastal Plain of North Carolina was analyzed for δ¹⁵N of nitrate (δ¹⁵N-NO₃). Results show that the isotopic signal of animal waste nitrogen is readily identifiable and traceable in nitrate in this ground water. The widespread land application of animal wastes from intensive livestock operations constitutes a potential source of nitrogen contamination to natural water throughout large regions of the United States and other countries. The site of the present study has been suspected as a nitrate contamination source to nearby domestic supply wells and has been monitored for several years by government and private water quality investigators through sampling of observation wells, ditches, and streams. δ¹⁵N of nitrate allowed direct identification of animal waste-produced nitrate in 11 of 14 wells sampled in this study, as well as recognition of nitrate contributions from non-animal waste agricultural sources in remaining wells.