Evaluation of Seasonal Factors on Petroleum Hydrocarbon Vapor Biodegradation and Intrusion Potential in a Cold Climate

A detailed seasonal study of soil vapor intrusion at a cold climate site with average yearly temperature of 1.9 °C was conducted at a house with a crawlspace that overlay a shallow dissolved‐phase petroleum hydrocarbon (gasoline) plume in North Battleford, Saskatchewan, Canada. This research was conducted primarily to assess if winter conditions, including snow/frost cover, and cold soil temperatures, influence aerobic biodegradation of petroleum vapors in soil and the potential for vapor intrusion. Continuous time‐series data for oxygen, pressure differentials, soil temperature, soil moisture, and weather conditions were collected from a high‐resolution monitoring network. Seasonal monitoring of groundwater, soil vapor, crawlspace air, and indoor air was also undertaken. Petroleum hydrocarbon vapor attenuation and biodegradation rates were not significantly reduced during low temperature winter months and there was no evidence for a significant capping effect of snow or frost cover that would limit oxygen ingress from the atmosphere. In the residual light nonaqueous phase liquid (LNAPL) source area adjacent to the house, evidence for biodegradation included rapid attenuation of hydrocarbon vapor concentrations over a vertical interval of approximately 0.9 m, and a corresponding decrease in oxygen to less than 1.5% v/v. In comparison, hydrocarbon vapor concentrations above the dissolved plume and below the house were much lower and decreased sharply within a few tens of centimeters above the groundwater source. Corresponding oxygen concentrations in soil gas were at least 10% v/v. A reactive transport model (MIN3P‐DUSTY) was initially calibrated to data from vertical profiles at the site to obtain biodegradation rates, and then used to simulate the observed soil vapor distribution. The calibrated model indicated that soil vapor transport was dominated by diffusion and aerobic biodegradation, and that crawlspace pressures and soil gas advection had little influence on soil vapor concentrations.     

Field Trapping of Subsurface Vapor Phase Petroleum Hydrocarbons

Soil gas samples from intact soil cores were collected on adsorbents at a field site, then thermally desorbed and analyzed by laboratory gas chromatography (GC). Vertical concentration profiles of predominant vapor phase petroleum hydrocarbons under ambient conditions were obtained for the zone directly above the capillary fringe. Water and residual phase weathered aviation gasoline were present in this region of the profile.
The sampling, trapping, and GC methodology was effective in most respects. Reproducibility, trapping, and desorption efficiency were generally satisfactory, and different sorbent tubes gave similar results. A minor shortcoming of the method occurred with the most volatile compound, 2,3-dimcthylbutane, which was poorly retained during several weeks of storage lime and was also poorly desorbed.
Vapor phase concentrations of predominant hydrocarbon compounds all increased with depth at one sampling location. At a more highly contaminated location, concentrations of highly volatile compounds increased with depth while concentrations of less volatile compounds remained constant or decreased, possibly indicating distillation effects. Scatier in the data was attributed to heterogeneities in water and residual phase distribution.     

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.     

Evidence for Instantaneous Oxygen-Limited Biodegradation of Petroleum Hydrocarbon Vapors in the Subsurface

Petroleum hydrocarbon vapors biodegrade aerobically in the subsurface. Depth profiles of petroleum hydrocarbon vapor and oxygen concentrations from seven locations in sandy and clay soils across four states of Australia are summarized. The data are evaluated to support a simple model of biodegradation that can be used to assess hydrocarbon vapors migrating toward built environments. Multilevel samplers and probes that allow near‐continuous monitoring of oxygen and total volatile organic compounds (VOCs) were used to determine concentration depth profiles and changes over time. Collation of all data across all sites showed distinct separation of oxygen from hydrocarbon vapors, and that most oxygen and hydrocarbon concentration profiles were linear or near linear with depth. The low detection limit on the oxygen probe data and because it is an in situ measurement strengthened the case that little or no overlapping of oxygen and hydrocarbon vapor concentration profiles occurred, and that indeed oxygen and hydrocarbon vapors were largely only coincident near the location where they both decreased to zero. First‐order biodegradation rates determined from all depth profiles were generally lower than other published rates. With lower biodegradation rates, the overlapping of depth profiles might be expected, and yet such overlapping was not observed. A model of rapid (instantaneous) reaction of oxygen and hydrocarbon vapors compared to diffusive transport processes is shown to explain the important aspects of the 13 depth profiles. The model is simply based on the ratio of diffusion coefficients of oxygen and hydrocarbon vapors, the ratio of the maximum concentrations of oxygen and hydrocarbon vapors, the depth to the maximum hydrocarbon source concentration, and the stoichiometry coefficient. Whilst simple, the model offers the potential to incorporate aerobic biodegradation into an oxygen‐limited flux‐reduction approach for vapor intrusion assessments of petroleum hydrocarbon compounds.     

Temperature as a Tool to Evaluate Aerobic Biodegradation in Hydrocarbon Contaminated Soil

This study evaluates the theory, and some practical aspects of using temperature measurements to assess aerobic biodegradation in hydrocarbon contaminated soil. The method provides an easily applicable alternative for quantifying the rate of biodegradation and/or evaluating the performance of in situ remediation systems. The method involves two nonintrusive procedures for measuring vertical temperature profiles down existing monitoring wells; one using a thermistor on a cable for one‐time measurements and the other using compact temperature data loggers deployed for 3‐month to 1‐year period. These vertical temperature profile measurements are used to identify the depth and lateral extent of biodegradation as well as to monitor seasonal temperature changes throughout the year. The basic theory for using temperature measurements to estimate the minimum rate of biodegradation will be developed, and used to evaluate field measurements from sites in California where biodegradation of spilled petroleum hydrocarbons is due to natural processes. Following, temperature data will be used to evaluate the relative rates of biodegradation due to natural processes and soil vapor extraction (SVE) at a former refinery site in the North‐Central United States. The results from this study show that the temperature method can be a simple, cost effective tool for assessing biodegradation in the soil, and optimizing remediation systems at a wide variety of hydrocarbon spill sites.     

Small Purge Method to Sample Vapor from Groundwater Monitoring Wells Screened Across the Water Table

Groundwater monitoring wells are present at most hydrocarbon release sites that are being assessed for cleanup. If screened across the vadose zone, these wells provide an opportunity to collect vapor samples that can be used in the evaluation of vapor movement and biodegradation processes occurring at such sites. This paper presents a low purge volume method (modified after that developed by the U.S. EPA) for sampling vapor from monitoring wells that is easy to implement and can provide an assessment of the soil gas total petroleum hydrocarbon (TPH) and O₂ concentrations at the base of the vadose zone. As a result, the small purge method allows for sampling of vapor from monitoring wells to support petroleum vapor intrusion (PVI) risk assessment. The small purge volume method was field tested at the Hal's service station site in Green River, Utah. This site is well‐known for numerous soil gas measurements containing high O₂ and high TPH vapor concentrations in the same samples which is inconsistent with well‐accepted biodegradation models for the vapor pathway. Using the low purge volume method, monitoring wells were sampled over, upgradient, and downgradient of the light nonaqueous phase liquid (LNAPL) footprint. Results from our testing at Hal's show that vapor from monitoring wells over LNAPL contained very low O₂ and high TPH concentrations. In contrast, vapor from monitoring wells not over LNAPL contained high O₂ and low TPH concentrations. The results of this study show that a low purge volume method is consistent with biodegradation models especially for sampling at sites where low permeability soils exist in and around a LNAPL source zone.     

An Excel®‐Based Visualization Tool of Two‐Dimensional Soil Gas Concentration Profiles in Petroleum Vapor Intrusion

In this study, we present a petroleum vapor intrusion (PVI) tool implemented in Microsoft^® Excel^® using Visual Basic for Applications and integrated within a graphical interface. The latter helps users easily visualize two‐dimensional soil gas concentration profiles and indoor concentrations as a function of site‐specific conditions such as source strength and depth, biodegradation reaction rate constant, soil characteristics and building features. This tool is based on a two‐dimensional explicit analytical model that combines steady‐state diffusion‐dominated vapor transport in a homogeneous soil with a piecewise first‐order aerobic biodegradation model, in which rate is limited by oxygen availability. As recommended in the recently released United States Environmental Protection Agency's final PVI guidance, a sensitivity analysis and a simplified Monte Carlo uncertainty analysis are also included in the spreadsheet.     

Transport and Biological Fate of Toluene in Low-Permeability Soils

The effect of simultaneous sorption, diffusion, and biodegradation on the fate and transport of toluene in low-permeability soil formations was examined. A transport model accounting for vapor and liquid sorption, vapor diffusions, and first-order biodegradation was developed to describe the movement of volatile solute in unsaturated soils. Modeling studies were followed with laboratory batch and column studies on fine-grained soil samples obtained from a gasoline-contaminated site. Batch experiments yielded the sorption and diffusion coefficients for generating theoretical solute transport profiles. Column studies were conducted to examine toluene sorption, diffusion, and biodegradation under aerobic and denitrifying conditions. Results from the column studies indicated that vapor sorption onto the soil was minimal due to the high moisture content of the soil. Comparison of model predictions with experimental results indicated that the SASK model, which is based on the resistivity theory, provided a more accurate prediction of the vapor phase tortuosity than the frequently used Millington-Quirk equation. Laboratory results of toluene concentration profiles matched well with the model predictions and yielded degradation rates comparable to those obtained in the field. Column studies, examining toluene biodegradation under aerobic and denitrifying conditions in low-permeability soils, indicated that the presence of excess nitrate in aerobic environments yielded higher solute degradation rates than those observed under exclusively aerobic systems.     

Vapor Intrusion Screening at Petroleum UST Sites

Detailed site investigations to assess potential inhalation exposure and risk to human health associated with the migration of petroleum hydrocarbon vapors from the subsurface to indoor air are frequently undertaken at leaking underground storage tank (UST) sites, yet documented occurrences of petroleum vapor intrusion are extremely rare. Additional assessments are largely driven by low screening‐level concentrations derived from vapor transport modeling that does not consider biodegradation. To address this issue, screening criteria were developed from soil‐gas measurements at hundreds of petroleum UST sites spanning a range of environmental conditions, geographic regions, and a 16‐year time period (1995 to 2011). The data were evaluated to define vertical separation (screening) distances from the source, beyond which, the potential for vapor intrusion can be considered negligible. The screening distances were derived explicitly from benzene data using specified soil‐gas screening levels of 30, 50, and 100 µg/m³ and nonparametric Kaplan‐Meier statistics. Results indicate that more than 95% of benzene concentrations in soil gas are ≤30 µg/m³ at any distance above a dissolved‐phase hydrocarbon source. Dissolved‐phase petroleum hydrocarbon sources are therefore unlikely to pose a risk for vapor intrusion unless groundwater (including capillary fringe) comes in contact with a building foundation. For light nonaqueous‐phase liquid (LNAPL) hydrocarbon sources, more than 95% of benzene concentrations in soil gas are ≤30 µg/m³ for vertical screening distances of 13 ft (4 m) or greater. The screening distances derived from this analysis are markedly different from 30 to 100 ft (10 to 30 m) vertical distances commonly found cited in regulatory guidance, even with specific allowances to account for uncertainty in the hydrocarbon source depth or location. Consideration of these screening distances in vapor intrusion guidance would help eliminate unnecessary site characterization at petroleum UST sites and allow more effective and sustainable use of limited resources.     

In Situ Remediation of Jet A in Soil and Ground Water by High Vacuum, Dual Phase Extraction

This report summarizes the initial results of subsurface remediation at Terminal 1, Kenneth International Airport, to remediate soil and ground water contaminated with Jet A fuel. The project was driven and constrained In the const ruction schedule of a major new terminal at the facility. The remediation system used a combination of ground water pumping, air injection, and soil vapor extraction. In the first five months of operation, the combined processes of dewatering, volatilization, and biodegradation removed a total of 36,689 pounds of total volatile and semivolatile organic jet fuel hydrocarbons from subsurface soil and ground water. The. results of this case study have shown that 62 percent of the removal resulted from biodegradation, 21 percent occurred as a result of liquid removal, and 11 percent resulted from the extraction of volatile organic compounds (VOC's).     

Spatial Variability of Soil-Gas Concentrations near and beneath a Building Overlying Shallow Petroleum Hydrocarbon–Impacted Soils

Data requirements for assessing the significance of the soil vapor intrusion pathway are evolving, and the collection and interpretation of subslab and near-slab soil-gas samples are under discussion. The potential for different assessment paradigms for aerobically biodegradable and recalcitrant chemicals is also frequently debated. In this work, the soil-gas distribution beneath and around a slab-on-grade building overlying shallow (0.5 to >1.5 m below ground surface) petroleum hydrocarbon–impacted coarse alluvial soils was studied. The study spanned about 12 months, including the sampling of soil-gas hydrocarbon and oxygen concentrations, subslab soil vs. building pressure differentials and included weather conditions. Three-dimensional soil-gas concentration "snapshots" using samples from 79 soil-gas sampling points are presented here. Significant spatial variability was observed with hydrocarbon and oxygen concentrations ranging from about <0.01 to 200 mg/L and 0 to 21% v/v, respectively. The presence of oxygen and the depth to petroleum-impacted soils appeared to be the dominant factors in controlling the soil-gas distribution; the depletion of hydrocarbons over short lateral and vertical distances (<2 m) was observed in the well-oxygenated regions. Composition data suggest preferential biodegradation of lighter compounds at some points, as reflected in the ratio of the masses of chemicals eluting on the gas chromatography between methane and pentane (C1 and C5) and all others after pentane (>C5).     

Hydrocarbon Vapor Diffusion in Intact Core Sleeves

The diffusion of 2,2,4-trimethylpentane (TMP) and 2,2,5-trimethylhexane (TMH) vapors put of residually contaminated sandy soil from the U.S. Environmental Protection Agency (EPA) field research site at Traverse City, Michigan, was measured and modeled. The headspace of an intact core sleeve sample was swept with nitrogen gas to simulate the diffusive release of hydrocarbon vapors from residual aviation gasoline in and immediately above the capillary fringe to a soil-venting air flow in the unsaturated zone. The resulting steady-state profile was modeled using existing diffusivity and air porosity estimates in a balance of diffusive flux and a first order source term. The source strength, which was calibrated with the observed flux of 2,2,4-TMP leaving the sleeve, varied with the residual gasoline remaining in the core, but was independent of the headspace sweep flow rate. This finding suggested that lower soil-venting air flow rates were in principle as effective as higher air flow rates in venting LNAPL vapors from contaminated soils. The saturated vapor concentration ratio of 2,2,4-TMP to 2,2,5-TMH decreased from 6.6 to 3.5 over the duration of the experiments in an expression of distillation effects. The vertical profile model was tested against sample port data in four separate experiments for both species, yielding mean errors ranging from 0 to—24 percent in magnitude.     

Simulated Soil Vapor Intrusion Attenuation Factors Including Biodegradation for Petroleum Hydrocarbons

Aerobic biodegradation can contribute significantly to the attenuation of petroleum hydrocarbons vapors in the unsaturated zone; however, most regulatory guidance for assessing potential human health risks via vapor intrusion to indoor air either neglect biodegradation in developing generic screening levels or allow for only one order of magnitude additional attenuation for aerobically degradable compounds, which may be overly conservative in some cases. This paper describes results from three-dimensional numerical model simulations of vapor intrusion for petroleum hydrocarbons to assess the influence of aerobic biodegradation on the attenuation factor for a variety of source concentrations and depths for residential buildings with basements and slab-on-grade construction. The simulations conducted in this study provide a framework for understanding the degree to which bioattenuation will occur under a variety of scenarios and provide insight into site conditions that will result in significant biodegradation. This improved understanding may be used to improve the conceptual model of contaminant transport, guide field data collection and interpretation, and estimate semi-site-specific attenuation factors for combinations of source concentrations, source depth, oxygen distribution, and building characteristics where site conditions reasonably match the scenarios simulated herein.     

Subsurface Venting of Vapors Emanating from Hydrocarbon Product on Ground Water

The results of an API-sponsored pilot-scale subsurface venting system study are presented. The purpose of this study was to evaluate the effectiveness of forced venting techniques in controlling and removing hydrocarbon vapors from a subsurface formation. Both qualitative and quantitative sampling and analytical procedures were developed to measure hydrocarbon vapors extracted from the soil. Vapor recovery and equivalent liquid product recovery rates were measured at each test cell evacuation rate.
Two identical test cells were installed. Each cell contained 16 vapor monitoring probes spaced at distances from 4 to 44 feet from a vapor extraction (vacuum) well. Each cell was also configured with two air inlet wells to allow atmospheric air to enter the subsurface formation. The vapor monitoring probes were installed at three discrete elevations above the capillary zone. In situ vapor samples were obtained periodically from these probes to measure changes in vapor concentration and composition while extracting vapors from the vacuum well at three different flow rates (18.5 scfm, 22.5 scfm and 39.8 scfm). In situ vapor samples were analyzed using a portable gas chromatograph to quantify and speciate the vapors. Vacuum levels were also measured at each vapor sampling probe and at the vacuum well.
The soil venting techniques evaluated during this study offer an alternative approach for controlling and eliminating spilled or leaked hydrocarbons from sand or gravel formations of high porosity and moderate permeability. These techniques may also be used to augment conventional liquid recovery methods. The data collected during this study will be useful in optimizing subsurface venting systems for removing and controlling hydrocarbon vapors in soil. Study results indicate pulsed venting techniques may offer a cost-effective means of controlling or eliminating hydrocarbon vapors in soil.     

Vertical Screening Distance Criteria to Evaluate Vapor Intrusion Risk from 1,2-Dichloroethane (1,2-DCA)

Vapor intrusion (VI) involves migration of volatile contaminants from subsurface through unsaturated soil into overlying buildings. In 2015, the US EPA recommended an approach for screening VI risks associated with gasoline releases from underground storage tank (UST) sites. Additional assessment of the VI risk from petroleum hydrocarbons was deemed unnecessary for buildings separated from vapor sources by more than recommended vertical screening distances. However, these vertical screening distances did not apply to potential VI risks associated with releases of former leaded gasoline containing 1,2-dichloroethane (1,2-DCA), because of a lack of empirical data on the attenuation of 1,2-DCA in soil gas. This study empirically evaluated 144 paired measurements of 1,2-DCA concentrations in soil gas and groundwater collected at 47 petroleum UST sites combined with BioVapor modeling. This included (1) assessing the frequency of 1,2-DCA detections in soil gas below 10⁻⁶ risk-based screening levels at different vertical separation distances and (2) comparing the US EPA recommended vertical screening distances with those predicted by BioVapor modeling. Vertical screening distances were predicted for different soil types using aerobic biodegradation rate constants estimated from the measured soil-gas data combined with conservative estimates of source concentrations. The modeling indicates that the vertical screening distance of 6 feet (1.8 m) recommended for dissolved-phase sources is applicable for 1,2-DCA below certain threshold concentrations in groundwater, while 15 feet (4.6 m) recommended for light nonaqueous phase liquid (LNAPL) sources is applicable for sites with clay and loam soils in the vadose zone, but not sand, if 1,2-DCA concentrations in groundwater exceed 150 μg/L. This dependence of the predicted vertical screening distances on soil type places added emphasis on proper soil characterization for VI screening at sites with 1,2-DCA sources. The soil-gas data suggests that a vertical screening distance of 15 feet (4.6 m) is necessary for both dissolved-phase and LNAPL sources.     

Evaluation of a Carbon Adsorption Method for Sampling Gasoline Vapors in the Subsurface

Monitoring of the vapor phase has emerged as a very convenient method for detecting volatile organic contaminants in the subsurface. It can provide a reliable way of placing ground water monitoring and recovery wells. The most common method uses a driveable ground probe (DGP) to extract a vapor-phase sample followed by direct injection of the vapor into a portable gas chromatograph (GC). However, many regional offices of regulatory agencies and consultants do not have ready access to such equipment. This research explores an alternative–the carbon adsorption method—in which the vapor is withdrawn by the DGP but concentrated on a small activated carbon trap (150mg). The carbon traps can be returned to a central laboratory for solvent extraction and GC analysis. This provides the advantages of increased sensitivity, reduction in field equipment and convenience of in-lab analyses (multiple GC injections are possible). A simple DGP and carbon trap system was constructed and tested at a field site. Vapor-phase concentrations of target compounds present in gasoline were mapped quite conveniently, ranging from 10,000μg/liter (vapor phase) to less than 10μg/L. These concentrations were also shown to decrease in the direction of the ground surface, as expected. Measurements of target compounds in soil showed that the vapor phase contributed a large fraction of the total contaminant burden where a non-aqueous-phase layer (NAPL) had been identified; as important, however, is the rather uniform contamination of the soil outside the NAPL region. Finally, the concentrations of target compounds in the vapor phase and ground water could be related in a manner roughly described by a simple equilibrium model, although exceptions were noted.     

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.     

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.     

Modeling Volatile Chemical Transport, Biodecay, and Emission to Indoor Air

A model is presented for estimating vapor concentrations in buildings because of volatilization from soil contaminated by non- aqueous phase liquids (NAPL) or from dissolved contaminants in ground water. The model considers source depletion, diffusive- dispersive transport of the contaminant of concern (COC) and of oxygen and oxygen-limited COC biodecay. Diffusive-advective transport through foundations and vapor losses caused by foundation cross-flow are considered. Competitive oxygen use by various species is assumed to be proportional to the product of the average dissolved-phase species concentration and a biopreference factor. Laboratory and field data indicate the biopreference factor to be proportional to the organic carbon partition coefficient for the fuel hydrocarbons studied. Predicted indoor air concentrations were sensitive to soil type and subbase permeability. Lower concentrations were predicted for buildings with shallow foundations caused by flushing of contaminants by cross-flow. NAPL source depletion had a large impact on average exposure concentration. Barometric pumping had a minor effect on indoor air emissions for the conditions studied. Risk-based soil cleanup levels were much lower when biodecay was considered because of the existence of a threshold source concentration below which no emissions occur. Computed cleanup levels at NAPL-contaminated sites were strongly dependent on total petroleum hydrocarbon (TPH) content and COC soil concentration. The model was applied to two field sites with gasoline-contaminated ground water. Confidence limits of predicted indoor air concentrations spanned approximately two orders of magnitude considering uncertainty in model parameters. Measured contaminant concentrations in indoor air were within model-predicted confidence limits.     

A Surface-Flux Measurement Method for Screening Contamination from Volatile Organic Compounds

Measurement of the vapor flux from volatile organic compounds (VOCs) provides a rapid means for screening large areas of potential contamination. The vapor flux is determined from the rate of VOC concentration buildup inside a 3.1L accumulator device that is sealed to the surface of the contaminated soil. After the VOC concentrations are allowed to increase for a few minutes, they are analyzed with a portable gas chromatograph or a total organic vapor analyzer.
The measurement approach was evaluated at a field site in an area where the ground water and soil had been impacted with Jet Fuel No. 4 (JP-4). An indication of the areal extent of impact was determined by mapping the surface VOC vapor flux. The pattern revealed by the flux measurements was found to coincide, in rough outline, with the known extent of toluene concentrations in the ground water and with conventional soil-gas survey results. In addition, a mathematical model describing VOC diffusion into the accumulator device was verified by performing laboratory measurements of the surface VOC vapor flux on a sandbox designed to simulate a hazardous waste site.