Geology ReportsSearch

Geology topics

Arthur L. Baehr

Publications and source records attributed to Arthur L. Baehr.

At least 19 recordsLinked to original sources

An updated model of induced airflow in the unsaturated zone

Simulation of induced movement of air in the unsaturated zone provides a method to determine permeability and to design vapor extraction remediation systems. A previously published solution to the airflow equation for the case in which the unsaturated zone is separated from the atmosphere by a layer of lower permeability (such as a clay layer) has been superseded. The new solution simulates airflow through the layer of lower permeability more rigorously by defining the leakage in terms of the upper boundary condition rather than by adding a leakage term to the governing airflow equation. This note presents the derivation of the new solution. Formulas for steady state pressure, specific discharge, and mass flow in the domain are obtained for the new model and for the case in which the unsaturated zone is in direct contact with the atmosphere.

Water Resources Research

Use of a reactive gas transport model to determine rates of hydrocarbon biodegradation in unsaturated porous media

A mathematical model is presented that simulates the transport and reaction of any number of gaseous phase constituents (e.g. CO 2 , O 2 , N 2 , and hydrocarbons) in unsaturated porous media. The model was developed as part of a method to determine rates of hydrocarbon biodegradation associated with natural cleansing at petroleum product spill sites. The one-dimensional model can be applied to analyze data from column experiments or from field sites where gas transport in the unsaturated zone is approximately vertical. A coupled, non-Fickian constitutive relation between fluxes and concentration gradients, together with the capability of incorporating heterogeneity with respect to model parameters, results in model applicability over a wide range of experimental and field conditions. When applied in a calibration mode, the model allows for the determination of constituent production/consumption rates as a function of the spatial coordinate. Alternatively, the model can be applied in a predictive mode to obtain the distribution of constituent concentrations and fluxes on the basis of assumed values of model parameters and a biodegradation hypothesis. Data requirements for the model are illustrated by analyzing data from a column experiment designed to determine the aerobic degradation rate of toluene in sediments collected from a gasoline spill site in Galloway Township, New Jersey.

Water Resources Research

A compositional multiphase model for groundwater contamination by petroleum products: 1. Theoretical considerations

A mathematical model is developed to describe the fate of hydrocarbon constituents of petroleum products introduced to soils as an immiscible liquid from sources such as leaking underground storage tanks and ruptured pipelines. The problem is one of multiphase transport (oil (immiscible), air, and water phases) of a reactive contaminant with constituents such as benzene, toluene, and xylene found in refined petroleum products like gasoline. In the unsaturated zone, transport of each constituent can occur as a solute in the water phase, vapor in the air phase, and as an unaltered constituent in the oil phase. Additionally, the model allows for adsorption. Molecular transformations, microbially mediated or abiotic, are incorporated as sink terms in the conservation of mass equations. An equilibrium approximation, applicable to any immiscible organic contaminant is applied to partition constituent mass between the air, oil, water, and adsorbed phases for points in the region where the oil phase exists. Outside the oil plume the equilibrium approximation takes on a simpler form to partition constituent mass between the air, water, and adsorbed phases only. Microbial degradation of petroleum products is first discussed in a general model, then the conservation of mass equation for oxygen is incorporated into the analysis which takes advantage of the key role played by oxygen in the metabolism of hydrocarbon utilizing microbes in soil environments. Approximations to two subproblems, oil plume establishment in the unsaturated zone, and solute and vapor transport subsequent to immiscible plume establishment are then developed from the general model.

Water Resources Research

A compositional multiphase model for groundwater contamination by petroleum products: 2. Numerical solution

In this paper we develop a numerical solution to equations developed in part 1 (M. Y. Corapcioglu and A. L. Baehr, this issue) to predict the fate of an immiscible organic contaminant such as gasoline in the unsaturated zone subsequent to plume establishment. This solution, obtained by using a finite difference scheme and a method of forward projection to evaluate nonlinear coefficients, provides estimates of the flux of solubilized hydrocarbon constituents to groundwater from the portion of a spill which remains trapped in a soil after routine remedial efforts to recover the product have ceased. The procedure was used to solve the one-dimensional (vertical) form of the system of nonlinear partial differential equations defining the transport for each constituent of the product. Additionally, a homogeneous, isothermal soil with constant water content was assumed. An equilibrium assumption partitions the constituents between air, water, adsorbed, and immiscible phases. Free oxygen transport in the soil was also simulated to provide an upper bound estimate of aerobic biodgradation rates. Results are presented for a hypothetical gasoline consisting of eight groups of hydrocarbon constituents. Rates at which hydrocarbon mass is removed from the soil, entering either the atmosphere or groundwater, or is biodegraded are presented. A significant sensitivity to model parameters, particularly the parameters characterizing diffusive vapor transport, was discovered. We conclude that hydrocarbon solute composition in groundwater beneath a gasoline contaminated soil would be heavily weighted toward aromatic constituents like benzene, toluene, and xylene.

Water Resources Research

Selective transport of hydrocarbons in the unsaturated zone due to aqueous and vapor phase partitioning

Long-term groundwater contamination can result from vapors and solutes emanating from organic liquids spilled in the unsaturated zone. The mathematical modeling analysis presented in this paper demonstrates for gasoline-range hydrocarbons, and other volatile organics commonly spilled, that diffusive transport in the unsaturated zone is a significant transport mechanism which can cause aqueous and vapor plumes to spread away from the immiscible liquid source, resulting in increasing groundwater contaminating potential. An analytical solution to a one-dimensional version of the transport model allows for the definition of a retardation coefficient which is dependent on phase-partitioning coefficients and moisture content. Significant differences in migration rates should be anticipated between hydrocarbons. A numerical solution was developed for a radially symmetric version of the model defining transport for a multiconstituent contaminant like gasoline. Differences in anticipated migration rates between aromatic and nonaromatic hydrocarbons was clearly demonstrated. A simulation based on the composition of an actual gasoline revealed that aromatic constituents, although constituting a fraction of the initial gasoline composition, completely defined the groundwater contaminating potential. This potential changes in time as constituents are selectively removed from the unsaturated zone. Further, the groundwater contaminating potential is quite sensitive to the ground surface boundary characterization.

Water Resources Research

Application of the Stefan-Maxwell Equations to determine limitations of Fick's law when modeling organic vapor transport in sand columns

The organic component of the vapor phase of a porous medium contaminated by an immiscible organic liquid can be significant enough to violate the condition of a dilute species diffusing in a bulk phase assumed by Fick's law. The Stefan-Maxwell equations provide a more comprehensive model for quantifying steady state transport for a vapor phase composed of arbitrary proportions of its constituents. The application of both types of models to the analysis of column experiments demonstrates that use of a Fickian-based transport model can lead to significant overestimates of soil tortuosity constants. Further, the physical displacement of naturally occurring gases (e.g., O 2 ), predicted by the Stefan-Maxwell model but not by application of Fick's Law, can be attributed improperly to a sink term such as microbial degradation in a Fickian-based transport model.

Water Resources Research

Evaluation of unsaturated zone air permeability through pneumatic tests

Predicting the steady state distribution of air pressure in the unsaturated zone resulting from a pneumatic test provides a method for determining air-phase permeability. This technique is analogous to the inverse problem of well hydraulics; however, air flow is more complicated than ground water flow because of air compressibility, the Klinkenberg effect, variations in air density and viscosity that result from temperature fluctuations in the unsaturated zone and the possibility of inducing water movement during the pneumatic test. An analysis of these complicating factors reveals that, when induced water movement can be neglected, a linear version of the airflow equation can provide an appropriate approximation for the purpose of determining air-phase permeability. Two analytical solutions for steady state, two-dimensional, axisymmetric airflow to a single well partially screened in the unsaturated zone are developed. One solution applies where there is a stratum of relatively low air permeability, separating the stratum in which the well is completed, from the atmosphere. The other solution applies where there is no separating stratum between the domain and atmosphere. In both situations the water table forms the lower horizontal boundary. Applications of both solutions to determine air permeability from data collected during pneumatic tests are presented.

Water Resources Research

Occurrence of diatoms in lakeside wells in northern New Jersey as an indicator of the effect of surface water on ground-water quality

In a novel approach for detecting ground-water/surface-water interaction, diatoms were used as an indicator that surface water affects ground-water quality in lakeside communities in northern New Jersey. The presence of diatoms, which are abundant in lakes, in adjacent domestic wells demonstrated that ground water in these lakeside communities was under the direct influence of surface water. Entire diatom frustules were present in 17 of 18 water samples collected in August 1999 from domestic wells in communities surrounding Cranberry Lake and Lake Lackawanna. Diatoms in water from the wells were of the same genus as those found in the lakes. The presence of diatoms in the wells, together with the fact that most static and stressed water levels in wells were below the elevation of the lake surfaces, indicates that ground-water/surface-water interaction is likely. Ground-water/surface-water interaction also probably accounts for the previously documented near-ubiquitous presence of methyl tertiary-butyl ether in the ground-water samples. Recreational use of lakes for motor boating and swimming, the application of herbicides for aquatic weed control, runoff from septic systems and roadways, and the presence of waterfowl all introduce contaminants to the lake. Samples from 4 of the 18 wells contained Navicula spp., a documented significant predictor of Giardia and Cryptosporidium. Because private well owners in New Jersey generally are not required to regularly monitor their wells, and tests conducted by public-water suppliers may not be sensitive to indicators of ground-water/surface-water interaction, these contaminants may remain undetected. The presence of diatoms in wells in similar settings can warn of lake/well interactions in the absence of other indicators.

New Jersey

Methodology to evaluate the effect of sorption in the unsaturated zone on the storage of nitrate and other ions and their transport across the water table, southern New Jersey

A new field-based approach for determining sorption in the unsaturated zone and its effect on the storage of ions and their transport in recharge to ground water has been demonstrated for a small agricultural watershed in the Coastal Plain of southern New Jersey. Moisture-content and chemical-concentration data obtained from unsaturated-zone-core and shallow-ground-water samples were used to estimate the mass flux of chemical constituents across the water table, as well as sorption coefficients (Kd). The selectivity order of the Kd values for cations is consistent with the expected selectivity order: for example, Na+ > Mg++ > Ca++ for sands. Although calculated sorption coefficients, as expected, were greater for cations than for anions, sorption had a substantial effect on the transport of anions through the unsaturated zone; in particular, average Kd values for NO3- were 0.22 liters per milligram for sands and 0.62 liters per milligram for finer grained sediments. The unsaturated zone in the study area is a large reservoir for nitrogen. Models that do not account for sorption are likely to result in unrealistic predictions of contaminant transport rate and provide overly optimistic expectations for natural cleansing in this watershed and those in other similar hydrogeologic settings.

New Jersey

Evaluation of volatilization as a natural attenuation pathway for MTBE

Volatilization and diffusion through the unsaturated zone can be an important pathway for natural attenuation remediation of methyl tert-butyl ether (MTBE) at gasoline spill sites. The significance of this pathway depends primarily on the distribution of immiscible product within the unsaturated zone and the relative magnitude of aqueous-phase advection (ground water recharge) to gaseous-phase diffusion. At a gasoline spill site in Laurel Bay, South Carolina, rates of MTBE volatilization from ground water downgradient from the source are estimated by analyzing the distribution of MTBE in the unsaturated zone above a solute plume. Volatilization rates of MTBE from ground water determined by transport modeling ranged from 0.0020 to 0.0042 g m- 2 /year, depending on the assumed rate of ground water recharge. Although diffusive conditions at the Laurel Bay site are favorable for volatilization, mass loss of MTBE is insignificant over the length (230 m) of the solute plume. Based on this analysis, significant volatilization of MTBE from ground water downgradient from source areas at other sites is not likely. In contrast, model results indicate that volatilization coupled with diffusion to the atmosphere could be a significant mass loss pathway for MTBE in source areas where residual product resides above the capillary zone. Although not documented, mass loss of MTBE at the Laurel Bay site due to volatilization and diffusion to the atmosphere are predicted to be two to three times greater than mass loading of MTBE to ground water due to dissolution and recharge. This result would imply that volatilization in the source zone may be the critical natural attenuation pathway for MTBE at gasoline spill sites, especially when considering capillary zone limitations on volatilization of MTBE from ground water and the relative recalcitrance of MTBE to biodegradation.

Groundwater

Effects of stormwater infiltration on quality of groundwater beneath retention and detention basins

Infiltration of storm water through detention and retention basins may increase the risk of groundwater contamination, especially in areas where the soil is sandy and the water table shallow, and contaminants may not have a chance to degrade or sorb onto soil particles before reaching the saturated zone. Groundwater from 16 monitoring wells installed in basins in southern New Jersey was compared to the quality of shallow groundwater from 30 wells in areas of new-urban land use. Basin groundwater contained much lower levels of dissolved oxygen, which affected concentrations of major ions. Patterns of volatile organic compound and pesticide occurrence in basin groundwater reflected the land use in the drainage areas served by the basins, and differed from patterns in background samples, exhibiting a greater occurrence of petroleum hydrocarbons and certain pesticides. Dilution effects and volatilization likely decrease the concentration and detection frequency of certain compounds commonly found in background groundwater. High recharge rates in storm water basins may cause loading factors to be substantial even when constituent concentrations in infiltrating storm water are relatively low.

New Jersey

Estimating spatial variability of recharge in southern New Jersey from unsaturated-zone measurements

Spatial variability of recharge in southern New Jersey was studied by sampling the unsat-urated zone at 48 sites distributed over approximately 930 square kilometers. Samples of unsaturated-zone sediment were collected during the summer and fall of 1996. Unsaturated flow was calculated using moisture-content data and estimates of conductivity and matric potential derived from sediment-size data. Matric forces were found to be important at about 70 percent of the sites despite the expectation that unsaturated flow in a humid climate is gravity driven. Upward water movement occurred at about 17 percent of the sites. The lower sediment layer at these sites consisted of sandy loam, indicating that upward movement can occur at depth only where the sediments are relatively fine-grained. At the other extreme, calculated flow at about 17 percent of the sites exceeded 250 centimeters per year. Because of the uncertainty inherent in unsaturated-flow calculations, the method provides only a scaling of recharge variability; however, the median calculated flow of 29.1 centimeters per year compares favorably with recharge estimates from previous water-budget studies. A map developed by spatial analysis of the recharge estimates identified an agricultural part of the study area where recharge was known to be low relative to recharge in other basins.

New Jersey

Frequently co‐occurring pesticides and volatile organic compounds in public supply and monitoring wells, southern New Jersey, USA

One or more pesticides were detected with one or more volatile organic compounds (VOCs) in more than 95% of samples collected from 30 public supply and 95 monitoring wells screened in the unconsolidated surficial aquifer system of southern New Jersey, USA. Overall, more than 140,000 and more than 3,000 unique combinations of pesticides with VOCs were detected in two or more samples from the supply and monitoring wells, respectively. More than 400 of these combinations were detected in 20% or more of the samples from the supply wells, whereas only 17 were detected in 20% or more of the samples from the monitoring wells. Although many constituent combinations detected in water from the supply and monitoring wells are similar, differences in constituent combinations also were found and can be attributed, in part, to differences in the characteristics of these two well types. The monitoring wells sampled during this study yield water that typically was recharged beneath a single land‐use setting during a recent, discrete time interval and that flowed along relatively short paths to the wells. Public supply wells, in contrast, yield large volumes of water and typically have contributing areas that are orders of magnitude larger than those of the monitoring wells. These large contributing areas generally encompass multiple land uses; moreover, because flow paths that originate in these areas vary in length, these wells typically yield water that was recharged over a large temporal interval. Water withdrawn from public supply wells, therefore, contains a mixture of waters of different ages that were recharged beneath various land‐use settings. Because public supply wells intercept water flowing along longer paths with longer residence times and integrate waters from a larger source area than those associated with monitoring wells, they are more likely to yield water that contains constituents that were used in greater quantities in the past, that were introduced from point sources, and/or that are derived from the degradation of parent compounds along extended flow paths.

New Jersey

Effects of land use and travel time on the distribution of nitrate in the Kirkwood-Cohansey aquifer system in southern New Jersey

Residents of the southern New Jersey Coastal Plain are increasingly reliant on the unconfined Kirkwood-Cohansey aquifer system for public water supply as a result of increasing population and restrictions on withdrawals from the deeper, confined aquifers. Elevated nitrate concentrations above background levels have been found in wells in the surficial aquifer system in agricultural and urban parts of this area. A three-dimensional steady-state ground-water-flow model of a 400-square-mile study area near Glassboro, New Jersey, was used in conjunction with particle tracking to examine the effects of land use and travel time on the distribution of nitrate in ground and surface water in southern New Jersey. Contributing areas and ground-water ages, or travel times, of water at ground-water discharge points (streams and wells) in the study area were simulated. Concentrations of nitrate were computed by linking land use and age-dependent nitrate concentrations in recharge to the discharge points. Median concentrations of nitrate in water samples collected during 1996 from shallow monitoring wells in different land-use areas were used to represent the concentration of nitrate in aquifer recharge since 1990. On the basis of upward trends in the use of nitrogen fertilizer, the concentrations of nitrate in aquifer recharge in agricultural and urban areas were assumed to have increased linearly from the background value in 1940 (0.07 mg/L as N) to the 1990 (2.5-14 mg/L as N) concentrations. Model performance was evaluated by comparing the simulation results to measured nitrate concentrations and apparent ground-water ages. Apparent ground-water ages at 32 monitoring wells in the study area determined from tritium/helium-3 ratios and sulfur hexafluoride concentrations favorably matched simulated travel times to these wells. Simulated nitrate concentrations were comparable to concentrations measured in 27 water-supply wells in the study area. A time series (1987-98) of nitrate concentrations at base-flow conditions in three streams that drain basins of various sizes and with various land uses was compared to simulated concentrations in these streams. In all three of the streams, a reasonable fit to the measured concentrations was achieved by multiplying the simulated concentration by 0.6. Because nitrate appeared to move conservatively (not degraded or adsorbed) in ground water to wells, the apparent non-conservative behavior in streams indicates that about 40 percent of the nitrate in aquifer recharge is removed by denitrification in the aquifer near the streams and (or) by in-stream processes. The model was used to evaluate the effects of various nitrate management options on the concentration of nitrate in streams and water-supply wells. Nitrate concentrations were simulated under the following management alternatives: an immediate ban on nitrate input, reduction of input at a constant rate, and fixed input at the current (2000) level. The time required for water to move through the aquifer results in a time lag between the reduction of nitrate input in recharge and the reduction of nitrate concentration in streams and wells. In the gradual-reduction alternative, nitrate concentrations in streams and wells continued to increase for several years after the reduction was enacted. In both the immediate-ban and gradual-reduction alternatives, nitrate concentrations remained elevated above background concentrations long after nitrate input ceased. In the fixed-use alternative, concentrations in streams and wells continued to increase for 30 to 40 years before reaching a constant level. The spatial distributions of simulated nitrate concentrations in streams in 2000 and 2050 were examined with the assumption of no change in land use, nitrate concentration in recharge, or ground-water withdrawals. As expected, nitrate concentrations were highest in agricultural areas and lowest in largely undeveloped areas.

New Jersey

Water quality and occurrence of methyl-tert butyl ether (MTBE) and other fuel related compounds in lakes and ground water at lakeside communities in Sussex and Morris Counties, New Jersey, 1998-1999

Densely populated communities surround many of the larger lakes in northwestern New Jersey. These communities derive most of their water supply from wells. The lakes can be navigated by gasoline-powered watercraft, can be in various stages of eutrophication, may contain pathogens associated with bathing and waterfowl, and are periodically subjected to chemical applications to control aquatic plant growth. Another feature that contributes to water-quality concerns in lakeside communities is the widespread use of septic tanks. Concentrations of methyl tert-butyl ether (MTBE), a gasoline oxygenate, in samples from Cranberry Lake and Lake Lackawanna ranged from 20 to 30 ug/L (micrograms per liter) and 5 to 14 ug/L during the summers of 1998 and 1999, respectively. These levels were persistent throughout the depth of the lakes when mixing conditions were present. MTBE concentrations in samples from the top 20 feet of Lake Hopatcong during summer 1999 were about 10 ug/L and about 2 to 3 ug/L in samples below 20 feet. The source of the MTBE in the lakes was determined to be gasoline-powered watercraft. Other constituents of gasoline--tertiary amyl methyl ether (TAME) and benzene, toluene, ethylbenzene, and xylenes (BTEX)--were detected in the lakes but at much lower concentrations than MTBE. Ambient ground-water quality at Cranberry Lake and Lake Lackawanna appears to be affected by the use of gasoline-powered watercraft. MTBE was detected in water samples from 13 of the 14 wells sampled at Cranberry Lake in fall 1998 and summer 1999. The wells were selected to monitor ambient ground-water quality and had no history of contamination. In ground-water samples collected during fall 1998, MTBE concentrations ranged from 0.12 to 19.8 ug/L, and the median concentration was 0.43 ug/L. In samples from summer 1999, MTBE concentrations ranged from 0.14 to 13.2 ug/L, and the median concentration was 0.38 ug/L. MTBE was detected in samples from four of the five wells at Lake Lackawanna in summer 1999;concentrations ranged from 0.05 to 0.19 ug/L. Lake/ground water interaction is a feasible explanation for the nearly ubiquitous presence of MTBE in ground water. The movement of water from lakes to wells is feasible because many static water levels and essentially all pumped water levels in the wells were below lake levels. Furthermore, diatom fragments were present in samples from the wells. Ambient ground water at Cranberry Lake also may be affected by septic-tank effluent, as indicated by the relation among concentrations of nitrate, boron, and chloroform. This result indicates potential vulnerability of the water supply to contamination by other chemicals and pathogens. Radon in ambient ground water is a concern throughout northern New Jersey. In particular, the median radon concentrations in ground-water samples collected from 14 wells at Cranberry Lake in 1998 and 1999 were 1,282 and 1,046 pCi/L, respectively. The median radon concentration in five ground-water samples collected at Lake Lackawanna in 1999 was 340 pCi/L. Although these values exceed regulatory levels, they are not high relative to radon concentrations measured in northwestern New Jersey. Eight wells in a neighborhood of Cranberry Lake with known MTBE contamination were sampled by the U.S. Geological Survey in summer 1998. MTBE was detected at concentrations greater than or equal to 40 ug/L in five of the wells. Concentrations of TAME, another gasoline oxygenate, were highly correlated with concentrations of MTBE; MTBE concentrations were about 10 times the TAME concentrations. In all samples, however, the concentrations of the BTEX compounds were less than 0.05 ug/L, and the sample from the most highly contaminated well, where the MTBE concentration was 900 ug/L, had no detectable BTEX.

New Jersey

Evaluation of the atmosphere as a source of volatile organic compounds in shallow groundwater

The atmosphere as a source of volatile organic compounds (VOCs) in shallow groundwater was evaluated over an area in southern New Jersey. Chloroform, methyl tertbutyl ether (MTBE), 1,1,1‐trichloroethane, tetrachloroethylene (PCE), and carbon disulfide (not a VOC) were detected frequently at low‐level concentrations in a network of 78 shallow wells in the surficial Kirkwood‐Cohansey aquifer system. The atmosphere was sampled for these compounds and only MTBE concentrations were high enough to potentially explain frequent detection in shallow groundwater. A mathematical model of reactive transport through the unsaturated zone is presented to explain how variations in unsaturated properties across the study area could explain differences in MTBE concentrations in shallow groundwater given the atmosphere as the source. Even when concentrations of VOCs in groundwater are low compared to regulatory concentration limits, it is critical to know the source. If the VOCs originate from a point source((), concentrations in groundwater could potentially increase over time to levels of concern as groundwater plumes evolve, whereas if the atmosphere is the source, then groundwater concentrations would be expected to remain at low‐level concentrations not exceeding those in equilibrium with atmospheric concentrations. This is the first analysis of VOC occurrence in shallow groundwater involving colocated atmosphere data.

Water Resources Research

Quantification of aerobic biodegradation and volatilization rates of gasoline hydrocarbons near the water table under natural attenuation conditions

Aerobic biodegradation and volatilization near the water table constitute a coupled pathway that contributes significantly to the natural attenuation of hydrocarbons at gasoline spill sites. Rates of hydrocarbon biodegradation and volatilization were quantified by analyzing vapor transport in the unsaturated zone at a gasoline spill site in Beaufort, South Carolina. Aerobic biodgradation rates decreased with distance above the water table, ranging from 0.20 to 1.5 g m −3 d −1 for toluene, from 0.24 to 0.38 g m −3 d −1 for xylene, from 0.09 to 0.24 g m −3 d −1 for cyclohexene, from 0.05 to 0.22 g m −3 d −1 for ethylbenzene, and from 0.02 to 0.08 g m −3 d −1 for benzene. Rates were highest in the capillary zone, where 68% of the total hydrocarbon mass that volatilized from the water table was estimated to have been biodegraded. Hydrocarbons were nearly completely degraded within 1m above the water table. This large loss underscores the importance of aerobic biodradation in limiting the transport of hydrocarbon vapors in the unsaturated zone and implies that vapor‐plume migration to basements and other points of contact may only be significant if a source of free product is present. Furthermore, because transport of the hydrocarbon in the unsaturated zone can be limited relative to that of oxygen and carbon dioxide, soil‐gas surveys conducted at hydrocarbon‐spill sites would benefit by the inclusion of oxygen‐ and carbon‐dioxide‐gas concentration measurements. Aerobic degradation kinetics in the unsaturated zone were approximately first‐order. First‐order rate constants near the water table were highest for cyclohexene (0.21–0.65 d −1 ) and nearly equivalent for ethylbenzene (0.11–0.31 d −1 ), xylenes (0.10–0.31 d −1 ), toluene (0.09–0.30 d −1 ), and benzene (0.07–0.31 d −1 ). Hydrocarbon mass loss rates at the water table resulting from the coupled aerobic biodgradation and volatilization process were determined by extrapolating gas transport rates through the capillary zone. Mass loss rates from groundwater were highest for toluene (0.20–0.84 g m −2 d −1 ), followed by xylenes (0.12–0.69 g m −2 d −1 ), cyclohexene (0.05–0.15 g m −2 d −1 ), ethylbenzene (0.02–0.12 g m −2 d −1 ), and benzene (0.01–0.04 g m −2 d −1 ). These rates exceed predicted rates of solubilization to groundwater, demonstrating the effectiveness of aerobic biodgradation and volatilization as a combined natural attenuation pathway.

Water Resources Research

Simulating transport of volatile organic compounds in the unsaturated zone using the computer model R-UNSAT

Subsurface spills of gasoline and other petroleum products are a common environmental problem throughout the industrialized world. The U.S. Environmental Protection Agency has estimated that 40 percent of the more than 200,000 retail service stations in the United States have had accidental releases of petroleum hydrocarbons to the subsurface (U.S. Environmental Protection Agency, 1991). Restoration of a contaminated aquifer to regulatory standards is a technically difficult problem even when best engineering strategies are applied. Natural attenuation, a remediation strategy that relies on intrinsic physical, chemical, and biological processes to decrease contaminant concentrations, is gaining widespread acceptance in aquifer restoration efforts (Tremblay and others, 1995). The potential for successful remediation by natural attenuation depends on the fate of the organic constituents of the spilled product, which may include additives such as methyl tert-butyl ether (MTBE). These compounds can dissolve in ground water, adsorb to subsurface sediments, volatilize and diffuse through the unsaturated zone, or undergo chemical and biological reactions (fig. 1). Volatilization and biodegradation near the water table are two processes that can contribute significantly to the natural attenuation of volatile organic compounds (VOCs) in shallow ground water (McAllister and Chiang, 1994). To date, quantitative information on the rates at which these processes occur has been limited. R-UNSAT, a computer model designed for quantifying rates of volatilization and biodegradation of organic compounds near the water table, was developed and documented by the U.S. Geological Survey (USGS) and is now available to the public. R-UNSAT also can be applied, however, to other unsaturated-zone transport problems that involve gas diffusion, such as radon migration, and the deposition of compounds from the atmosphere to shallow ground water. This fact sheet describes the transport model and demonstrates its capabilities through applications to point- and nonpoint-source contamination.

Fact Sheet