A simple method for calculating growth rates of petroleum hydrocarbon plumes

Consumption of aquifer Fe(III) during biodegradation of ground water contaminants may result in expansion of a contaminant plume, changing the outlook for monitored natural attenuation. Data from two research sites contaminated with petroleum hydrocarbons show that toluene and xylenes degrade under methanogenic conditions, but the benzene and ethylbenzene plumes grow as aquifer Fe(III) supplies are depleted. By considering a one-dimensional reaction front in a constant unidirectional flow field, it is possible to derive a simple expression for the growth rate of a benzene plume. The method balances the mass flux of benzene with the Fe(III) content of the aquifer, assuming that the biodegradation reaction is instantaneous. The resulting expression shows that the benzene front migration is retarded relative to the ground water velocity by a factor that depends on the concentrations of hydrocarbon and bioavailable Fe(III). The method provides good agreement with benzene plumes at a crude oil study site in Minnesota and a gasoline site in South Carolina. Compared to the South Carolina site, the Minnesota site has 25% higher benzene flux but eight times the Fe(III), leading to about one-sixth the expansion rate. Although it was developed for benzene, toluene, ethylbenzene, and xylenes, the growth-rate estimation method may have applications to contaminant plumes from other persistent contaminant sources.     

Laboratory Column Experiments Using Polymer Mats to Remove Selected VOCs, PAHs, and Pesticides from Ground Water

Large-scale column experiments were undertaken to evaluate the potential of polymer mats to remove selected volatile organic compounds, polycyclic aromatic hydrocarbons, and pesticides (atrazine and fenamiphos) from ground water and potentially to act as permeable reactive barriers in contaminated ground water environments. The polymer mats, composed of interwoven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2 m long flow-through columns. The polymer mats proved efficient in physically removing (stripping) benzene and naphthalene from contaminated water. Removal efficiencies for both these compounds from an aqueous phase flowing past a polymer mat were 75% or greater. However, for atrazine and fenamiphos, removal efficiencies were 5% or less, probably as a result of their lower Henry's law constants and possibly lower polymer diffusion coefficients.
These experiments indicate that, at least for relatively volatile compounds, polymer mats can provide a remediation technique for the removal of organic compounds from contaminated water. Application of this technique may be well suited as a longer-term, semipassive strategy to remediate contaminated ground water, using natural ground water flow to deliver contaminated ground water to polymer mats engineered as sorption-stripping barriers.
Additional benefits of this technique may include targeted delivery of gaseous chemical amendments, such as oxygen, to enhance aerobic biodegradation and to further reduce any residual concentrations of contaminants.     

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.     

Rapid evolution of redox processes in a petroleum hydrocarbon-contaminated aquifer

Ground water chemistry data collected over a six-year period show that the distribution of contaminants and redox processes in a shallow petroleum hydrocarbon-contaminated aquifer has changed rapidly over time. Shortly after a gasoline release occurred in 1990, high concentrations of benzene were present near the contaminant source area. In this contaminated zone, dissolved oxygen in ground water was depleted, and by 1994 Fe(III) reduction and sulfate reduction were the predominant terminal electron accepting processes. Significantly, dissolved methane was below measurable levels in 1994, indicating the absence of significant methanogenesis. By 1996, however, depletion of solid-phase Fe(III)-oxyhydrox ides in aquifer sediments and depletion of dissolved sulfate in ground water resulted in the onset of methanogenesis. Between 1996 and 2000, water-chemistry data indicated that methanogenic metabolism became increasingly prevalent. Molecular analysis of 16S-rDNA extracted from sediments shows the presence of a more diverse methanogenic community inside as opposed to outside the plume core, and is consistent with water-chemistry data indicating a shift toward methanogenesis over time. This rapid evolution of redox processes reflects several factors including the large amounts of contaminants, relatively rapid ground water flow (approximately 0.3 m/day [approximately foot/day]), and low concentrations of microbially reducible Fe(III) oxyhydroxides ( approximately 1 micromol/g) initially present in aquifer sediments. These results illustrate that, under certain hydrologic conditions, redox conditions in petroleum hydrocarbon-contaminated aquifers can change rapidly in time and space, and that the availability of solid-phase Fe(III)-oxyhydroxides affects this rate of change.     

A Gas Chromatographic/Chemical Indicator Approach to Assessing Ground Water Contamination by Petroleum Products

The water-soluble fractions of unleaded gasoline, kerosene and diesel fuel were evaluated by U.S. EPA Methods 602, 610, and 625.
Several chemical indicator compounds useful in assessing petroleum contamination of ground water, including benzene, substituted benzenes, n-alkanes, and polynuclear aromatic hydrocarbons, were identified. These were applied to the interpretation of data collected from monitoring wells at gasoline service stations that were undergoing ground water remediation. The chemical indicators are used to identify the likely type(s) of petroleum contamination. Certain hydrocarbons may be unique to specific fuel types.
Gas chromatograms of field sample extracts were compared with chromatograms of laboratory water-soluble fractions (WSFs) and neat fuels (unleaded gasoline, kerosene, and diesel). In some situations, field samples represented water-soluble fractions of the contaminating fuel. In others, a fuel-water agglomeration was indicated, with the chromatograms showing peaks that represented components of both the WSFs and the neat fuels.
The use of both gas chromatography pattern identification and chemical indicators appears to be a viable approach to assessing ground water contamination caused by petroleum products.     

Vertical Delineation of Contamination in Fractured Bedrock Aquifer

The New Jersey Department of Environmental Protection's Technical Regulations require the horizontal and vertical delineation of contamination. Monitor wells screened at increasingly deeper intervals are used to delineate vertical contamination. In New Jersey, the open interval in a bedrock well cannot exceed 7.6 m. Since contamination has been found at depths as great as 91.4 m in a production well in the study area, it would be prohibitively expensive to install monitor wells with 7.6 m open holes at ever-increasing depths until no contamination was found. Isolation of discrete zones in boreholes using pneumatic packers was implemented at a site in north central New Jersey. Ground water samples were collected from selected 6.1 m sections of boreholes drilled into fractured bedrock at three locations on the property and one offsite location. The ground water samples were analyzed in a field laboratory. The analytical results were used to determine the vertical extent of gasoline-related compounds dissolved in the ground water on the property and offsite. These compounds include benzene, ethylbenzene, methyl tertiary butyl ether, toluene, and xylenes. The four boreholes were converted into bedrock monitor wells. The intake interval for each of the wells was selected through evaluation of the vertical distribution of contaminants as determined from analytical results obtained from a field laboratory located onsite. Three wells are used for the recovery of contaminated ground water. The recovered water will be treated at the onsite air-stripping unit. The fourth well is used to chemically and hydraulically monitor the progress of the ground water recovery program.     

MNA as a Remedy for Arsenic Mobilized by Anthropogenic Inputs of Organic Carbon

The potential application of monitored natural attenuation (MNA) as a remedy for ground water contaminated with arsenic (As) is examined for a subset of contaminated sites, specifically those where naturally occurring As has been mobilized due to localized anthropogenic organic carbon (OC) releases. This includes sites subject to petroleum releases, exposure to landfill leachates, and OC additions for biostimulation of reductive dechlorination of chlorinated solvents. The key characteristic of these sites is that, under conditions prevailing before the anthropogenic OC introduction, the naturally occurring As in the subsurface was not mobile and did not adversely affect ground water quality. This suggests that, in the far-field (where background conditions are (re) established), As may be sequestered upon contact of the contaminated ground water with either or both the (uncontaminated) ambient ground water and the background aquifer minerals. The observed extents of elevated concentrations (or "footprints") of As and other chemical species, such as dissolved OC and iron (Fe), and related parameters, such as redox potential ( E _h) and dissolved oxygen, and their evolution over time can be used to assess the mobilization and sequestration of As and the potential feasibility of MNA as a remedial option. Ultimately, the capacity for As sequestration must be assessed in the context of the OC loading to the site, which may require "active" measures for source control. Monitoring is needed to confirm the continuing effectiveness of the MNA remedy or to indicate if contingency measures must be implemented.     

Modelling of benzene distribution in the subsurface of an abandoned gas plant site after a long term of groundwater table fluctuation

The non‐aqueous phase liquid simulator was used to model and interpret the occurrence of a thin benzene‐contaminated soil layer 9.0 m below the groundwater table in an abandoned gas plant site. The simulator was first evaluated in column tests under similar conditions to the contaminated site. Saturation–capillary pressure (S–P) relationships were extended from the laboratory scale of the column tests to the field scale of the subsurface at the abandoned site. Dynamic boundary conditions were established in order to prevent the model from generating excessive vertical velocities. The modelled benzene layer formation process agreed well with the in situ observations. With falling and then rising of the water table, benzene release from the surface migrated downward and then upward and distributed itself below and above the water table. Biochemical degradation of benzene made the distribution discontinuous in the subsurface. These two factors resulted in the thin benzene‐contaminated layer below the groundwater table. Copyright © 2012 John Wiley & Sons, Ltd.     

Characterization and identification of na-cl sources in ground water

Elevated concentrations of sodium (Na+) and chloride (Cl-) in surface and ground water are common in the United States and other countries, and can serve as indicators of, or may constitute, a water quality problem. We have characterized the most prevalent natural and anthropogenic sources of Na+ and Cl- in ground water, primarily in Illinois, and explored techniques that could be used to identify their source. We considered seven potential sources that included agricultural chemicals, septic effluent, animal waste, municipal landfill leachate, sea water, basin brines, and road deicers. The halides Cl-, bromide (Br), and iodide (I) were useful indicators of the sources of Na+-Cl- contamination. Iodide enrichment (relative to Cl-) was greatest in precipitation, followed by uncontaminated soil water and ground water, and landfill leachate. The mass ratios of the halides among themselves, with total nitrogen (N), and with Na+ provided diagnostic methods for graphically distinguishing among sources of Na+ and Cl- in contaminated water. Cl/Br ratios relative to Cl- revealed a clear, although overlapping, separation of sample groups. Samples of landfill leachate and ground water known to be contaminated by leachate were enriched in I and Br; this provided an excellent fingerprint for identifying leachate contamination. In addition, total N, when plotted against Cl/Br ratios, successfully separated water contaminated by road salt from water contaminated by other sources.     

Natural Attenuation of Aromatic Hydrocarbons in a Shallow Sand Aquifer

Inadvertent release of petroleum products such as gasoline into the subsurface can initiate ground water contamination, particularly by the toxic, water-soluble and mobile gasoline components: benzene, toluene and xylenes (BTX). This study was undertaken to examine the processes controlling the rate of movement and the persistence of dissolved BTX in ground water in a shallow, unconfined sand aquifer.
Water containing about 7.6 mg/ L total BTX was introduced below the water table and the migration of contaminants through a sandy aquifer was monitored using a dense sampling network. BTX components migrated slightly slower than the ground water due to sorptive retardation. Essentially all the injected mass of BTX was lost within 434 days due to biodegradation. Rates of mass loss were similar for all monoaromatics; benzene was the only component to persist beyond 270 days. Laboratory biodegradation experiments produced similar rates, even when the initial BTX concentration varied.
A dominant control over BTX biodegradation was the availability of dissolved oxygen. BTX persisted at the field site in layers low in dissolved oxygen. Decreasing mass loss rates over time observed in the field experiment are not likely due to first-order deeradation rates, but rather to the persistence of small fractions of BTX mass in anoxic layers.     

Pesticides in Nebraska's Ground Water

More than 2263 well water samples were collected throughout Nebraska and analyzed for pesticides. Thirteen and one-half percent contained detectable levels of atrazine, but only 22 wells exceeded the health advisory of 3.0 ppb. Although the samples came from almost every county in the state, this sampling is not based solely on a randomly selected group of wells. The highest frequency of detections occurred in irrigated corn-growing areas with less than 50 feet to ground water. These areas were sampled at a greater frequency than the less vulnerable areas. Cyanazine, together with the additional triazines — simazine, propazine, prometone, and ametryne, also were detected in some well waters; however, their frequency of detection was well below that of atrazine. The triazine metribuzin was not detected.
Alachlor, propachlor, and metolachlor also were detected in trace levels in several wells. Five of 2072 samples analyzed for alachlor exceeded the health advisory of 0.4 ppb. Almost all of the contaminated wells were in vulnerable areas. The relatively high frequency of propachlor detections occurred in predominately irrigated corn-growing areas, rather than in areas where propachlor is traditionally applied.
The factors that appear most directly involved in the observed distribution of pesticides in ground water are the intensity of areal usage, pesticide persistence and mobility, irrigation, soil drainage capacity, and depth to ground water.
Fifteen pesticide residues were detected during this study. If ethylene dibromide and carbon tetrachloride, which were detected in ground water adjacent to grain elevators are included, a total of 17 pesticide residues have been detected in Nebraska's ground water.     

In Situ Bioreclamation: A Cost-Effective Technology to Remediate Subsurface Organic Contamination

In situ bioreclamation is a proven technology that cost-effectively treats organic contamination in subsurface environments. As a remediation strategy, it reduces both the contamination dissolved in ground water, as well as residual soil-bound contamination.
To maximize biodegradation, the technology is applied after conducting laboratory studies. Application of the technology involves infiltrating necessary nutrients to the contaminated subsurface.
Results of a specific case study indicate excellent performance with rapid cleanup of petroleum hydrocarbon contamination from soils and ground water.
Costs associated with in situ bioreclamation technology showed a savings of approximately 50 percent over simple pump-and-treat technology. Time frame for cleanup was shown to be approximately 30 percent of the projected time frame of simple pump-and-treat technology.     

Intrinsic bioremediation of a petroleum-impacted wetland

Following the 1994 San Jacinto River flood and oil spill in southeast Texas, a petroleum-contaminated wetland was reserved for a long-term research program to evaluate bioremediation as a viable spill response tool. The first phase of this program, presented in this paper, evaluated the intrinsic biodegradation of petroleum in the contaminated wetland. Sediment samples from six test plots were collected 11 times over an 11-month period to assess the temporal and spatial petroleum concentrations. Petroleum concentrations were evaluated using gas chromatography-mass spectrometer analyses of specific target compounds normalized to the conservative biological marker, C(30)17alpha,21beta(H)-hopane. The analyses of specific target compounds were able to characterize that significant petroleum biodegradation had occurred at the site over the one-year period. Total resolved saturate and total resolved aromatic hydrocarbon data indicated the petroleum was degraded more than 95%. In addition, first-order biodegradation rate constants were calculated for the hopane-normalized target compounds and supported expected biodegradation patterns. The rapid degradation rates of the petroleum hydrocarbons are attributed to conditions favorable to biodegradation. Elevated nutrient levels from the flood deposition and the unconsolidated nature of the freshly deposited sediment possibly provided a nutrient rich, oxic environment. Additionally, it is suggested that an active and capable microbial community was present due to prior exposure to petroleum. These factors provided an environment conducive for the rapid bioremediation of the petroleum in the contaminated wetland.     

Synergistic Application of Four Remedial Techniques at an Industrial Site

The soil and ground water at a General Motors plant site were contaminated with petroleum products from leaking underground storage tanks. Based on the initial assessment, the site was complex from the standpoint of geology (clay layers), hydrology (a recharge zone with a perched water table), and contaminant (approximately 4800 gallons of mixed gasoline and oil). After a thorough study of remedial alternatives, a synergistic remedial approach was adopted including pump and treat, product removal, vapor extraction, and bioventing. The system was designed and implemented at the site through 22 dual-extraction wells. Over a 21-month period, 4400 gallons of gasoline and oil were removed from the system, including 59 percent by vapor extraction, 28 percent by bioventing, and 13 percent by pump and treat. Synergism between the various remedial methods was demonstrated clearly. Ground water pump and treat lowered the water table, allowing air to flow for vapor extraction. The vacuum applied for vapor extraction increased the ground water removal rate and the efficiency of pump and treat. The vapor extraction system also added oxygen to the soil to stimulate aerobic biodegradation.     

Multimedia Risk-Based Soil Cleanup at a Gasoline-Contaminated Site Using Vapor Extraction

At a utility service center, gasoline from an underground storage tank had leaked into subsurface vadose zone soils for several years. To remediate the site, a soil vapor extraction (SVE) system was installed and operated. At the completion of the SVE operation, gasoline-containing residues in several confirmation soil borings exceeded agency-mandated cleanup levels. Rather than continue with SVE, a risk-based approach was developed to evaluate what levels of gasoline-containing residues could be left in the soil and still protect human health. The risk-based approach consisted of simulating the fate of chemical residues through the vadose zone and then into both the ground water and atmosphere. Receptor point concentrations were predicted, and health risks were assessed. The risk assessment concluded that ingestion of contaminated ground water and inhalation of air while showering were the largest potential contributors to risk, and that risks associated with inhalation of vapor-containing ambient air are small. However, all predicted risks are below the acceptable risk levels of 10⁻⁶ individual cancer risk probability and 1.0 hazard index. Therefore, the lead agency accepted the recommendation that the site requires no further remediation. The service center continues normal operations today.     

Influence of aquifer properties on phytoremediation effectiveness

Recent research has shown that planting deep-rooted trees, such as poplar, can take up and degrade important ground water pollutants such as trichloroethylene (TCE) as they transpire water from the capillary fringe of shallow contaminated aquifers. The effect of hydrogeologic factors on the minimum plantation area needed to prevent downgradient migration of contaminated ground water is not well known. Accordingly, the objective of this research was to identify the hydrogeologic parameters that control phytoremediation effectiveness. We used a numerical ground water flow model to evaluate the effect that natural variations in hydrogeologic parameters and growing season duration have on the minimum plantation area required for capture. We found that the plantation area that was needed to completely capture a ground water contamination plume was directly proportional to aquifer horizontal hydraulic conductivity, saturated thickness, and ground water gradient. The plantation area needed for capture increased nonlinearly with increasing plume width, aquifer anisotropy, and decreasing growing season duration. The plantation area needed for capture was generally insensitive to aquifer-specific yield and storativity. Steady-state simulations can be used to predict the plantation area needed for capture in many applications. A particularly important finding of this work is that evapotranspiration fluxes through plantations appropriately sized to contain the plume substantially exceeded the ground water flux through the plume itself.     

Land Application of Sulfate Salts for Enhanced Natural Attenuation of Benzene in Groundwater: A Case Study

Sulfate reducing conditions are widely observed in groundwater plumes associated with petroleum hydrocarbon releases. This leads to sulfate depletion in groundwater which can limit biodegradation of hydrocarbons (usually benzene, toluene, ethylbenzene, xylenes [BTEX] compounds) and can therefore result in extended timeframes to achieve groundwater cleanup objectives by monitored natural attenuation. Under these conditions, sulfate addition to the subsurface can potentially enhance BTEX biodegradation and facilitate enhanced natural attenuation. However, a delivery approach that enables effective contact with the hydrocarbons and is able to sustain elevated and uniform sulfate concentrations in groundwater remains a key challenge. In this case study, sulfate addition to a groundwater plume containing predominantly benzene by land application of agricultural gypsum and Epsom salt is described. Over 4 years of groundwater monitoring data from key wells subjected to pilot‐scale and site‐wide land application events are presented. These are compared to data from pilot testing employing liquid Epsom salt injections as an alternate sulfate delivery approach. Sulfate land application, sulfate retention within the vadose zone, and periodic infiltration following ongoing precipitation events resulted in elevated sulfate concentrations (>150 mg/L) in groundwater that were sustained over 12 months between application events and stimulated benzene biodegradation as indicated by declines in dissolved benzene concentration, and compound‐specific isotope analysis data for carbon in benzene. Long‐term groundwater benzene concentration reductions were achieved in spite of periodic rebounds resulting from water table fluctuations across the smear zone. Land application of gypsum is a potentially cost‐effective sulfate delivery approach at sites with open, unpaved surfaces, relatively permeable geology, and shallow hydrocarbon impacts. However, more research is needed to understand the fate and persistence of sulfate and to improve the likelihood of success and effectiveness of this delivery approach.     

Investigation of Ground Water Contamination by Fenamiphos and Atrazine in a Residential Area: Source and Distribution of Contamination

Ground water in a residential area of Perth. Western Australia, was contaminated with fenamiphos and atrazine. probably as a result of the storage and handling of these chemicals at a residential properly. Sampling of existing wells indicated that atrazine and fenamiphos concentrations in ground water beneath a neighboring property were 2000 μg/L and 1000 μg/L, respectively. Fenamiphos concentrations were sufficiently high to be toxic on prolonged skin contact, and contamination posed a public health threat to nearby residents with private wells. Management of the contamination problem included restricting ground water use in the area and using a recovery well to pump contaminated ground water.     

Analysis of recharge-induced geochemical change in a contaminated aquifer

Recharge events that deliver electron acceptors such as O2, NO3, SO4, and Fe3+ to anaerobic, contaminated aquifers are likely important for natural attenuation processes. However, the specific influence of recharge on (bio)geochemical processes in ground water systems is not well understood. The impact of a moderate-sized recharge event on ground water chemistry was evaluated at a shallow, sandy aquifer contaminated with waste fuels and chlorinated solvents. Multivariate statistical analyses coupled with three-dimensional visualization were used to analyze ground water chemistry data (including redox indicators, major ions, and physical parameters) to reveal associations between chemical parameters and to infer processes within the ground water plume. Factor analysis indicated that dominant chemical associations and their interpreted processes (anaerobic and aerobic microbial processes, mineral precipitation/dissolution, and temperature effects) did not change significantly after the spring recharge event of 2000. However, the relative importance of each of these processes within the plume changed. After the recharge event, the overall importance of aerobic processes increased from the fourth to the second most important factor, representing the variability within the data set. The anaerobic signatures became more complex, suggesting that zones with multiple terminal electron-accepting processes (TEAPs) likely occur in the same water mass. Three-dimensional visualization of well clusters showed that water samples with similar chemical associations occurred in distinct water masses within the aquifer. Water mass distinctions were not based on dominant TEAPs, suggesting that the recharge effects on TEAPs occurred primarily at the interface between infiltrating recharge water and the aquifer.