Evaluation of Vapor Intrusion Risk from Ethylene Dibromide Using the Vertical Screening Distance Approach

Vapor intrusion (VI) occurs when volatile contaminants in the subsurface migrate through the vadose zone into overlying buildings. The 2015 U.S. EPA petroleum VI guidance recommends that additional investigation of the VI risk from gasoline hydrocarbons at the underground storage tank (UST) sites is not necessary where the vertical distance between a building and a vapor source exceeds a recommended vertical screening distance. However, due to the lack of soil-gas data on the attenuation of ethylene dibromide (EDB), additional VI investigations to evaluate VI risk from EDB are recommended at UST sites with leaded gasoline releases containing EDB. We analyzed soil-gas and groundwater concentrations of EDB from eight petroleum UST sites using a new analytical method with soil-gas detection limit <0.16 μg/m³ EDB (VI screening level at the 10⁻⁶ risk level). The analysis included (1) assessing the frequency of EDB detections ≤0.16 μg/m³ at various vertical separation distances and (2) predicting vertical screening distances for EDB using the U.S. EPA PVIScreen model for different soil types in the vadose zone above dissolved-phase and LNAPL sources. Ranges of estimated aerobic biodegradation rate constants for EDB, air exchange rates for residential buildings, and source vapor concentrations for other constituents were combined with conservative estimates of EDB source concentrations as model inputs. Concentrations of EDB in soil-gas indicated that the U.S. EPA recommended vertical screening distances are protective of VI risk from EDB. Conversely, vertical screening distances predicted by modeling were >6 ft (1.8 m) for sites with sand and loam soil above dissolved phase sources and >15 ft (4.6 m) for sites with sand soil above LNAPL sources. This predicted dependence on the vapor source type and soil type in the vadose zone highlights the importance of soil characterization for VI screening at sites with EDB sources.     

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.     

Field Study of Vertical Screening Distance Criteria for Vapor Intrusion of Ethylene Dibromide

Several regulatory agencies recommend screening petroleum vapor intrusion (PVI) sites based on vertical screening distance between a petroleum hydrocarbon source in soil or groundwater and a building foundation. U.S. Environmental Protection Agency (U.S. EPA) indicate the risk of PVI is minimal at buildings that are separated by more than 6 feet (1.8 m) from a dissolved-phase source and 15 feet (4.6 m) from a light nonaqueous phase liquid (LNAPL) source. This vertical screening distance method is not, however, recommended at sites with leaded gasoline sources containing ethylene dibromide (EDB) because of a lack of field data to document EDB attenuation in the vadose zone. To help address this gap, depth-discrete soil-gas samples were collected at a leaded gasoline release site in Sobieski, Minnesota (USA). The maximum concentration of EDB in groundwater (175 μg/L) at the site was high relative to those observed at other leaded gasoline release sites. Soil gas was analyzed for EDB using a modification of U.S. EPA Method TO-14A that achieved analytical detection limits below the U.S. EPA Vapor Intrusion Screening Level (VISL) for EDB based on a 10⁻⁶ cancer risk (<0.16 μg/m³). Concentrations of EDB in soil gas above LNAPL reached as high as 960 μg/m³ and decreased below the VISL within a source-separation distance of 7 feet. This result coupled with BioVapor model predictions of EDB concentrations indicate that vertical screening distances recommended by regulatory agencies at PVI sites are generally applicable for EDB over the range of anticipated source concentrations and soil types at most sites.     

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.     

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.     

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).     

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.     

A Comparative Plume Study of DRO,GRO, Benzene,and MTBE: Implications for Risk Management

Groundwater remediation and no-further action decision making at petroleum underground storage tank (UST) sites has largely been based on an understanding of plume length, plume stability, and attenuation rates for key hydrocarbon constituents. Regulatory guidance to support and guide such decisions is based in part on plume studies involving individual hydrocarbon constituents, namely benzene and methyl tert-butyl ether (MTBE). Questions remain regarding whether current guidance is applicable to chemical mixtures such as gasoline range organics (GRO), diesel range organics (DRO), and oxygen containing organic compounds (OCOCs) resulting from hydrocarbon biodegradation. To help address this concern, data from California's GeoTracker database were used to estimate maximum plume lengths, plume stability, and attenuation rates of DRO (which can be used as an analytical surrogate for OCOCs) and GRO relative to benzene and MTBE. The distributions of maximum plume lengths were similar for the four constituents with medians ranging from 27 to 32 m. The fraction of monitoring wells with a decreasing concentration trend ranged from 19% for DRO to 40% for MTBE, while fewer than 7% of the wells had an increasing concentration trend for any of the constituents. Median attenuation rates ranged from 0.10% day⁻¹ for DRO to 0.17% day⁻¹ for MTBE. The results suggest attenuation based risk management is appropriate for DRO and GRO plumes at most petroleum UST sites.     

Influence of Shallow Geology on Volatile Organic Chemical Attenuation from Groundwater to Deep Soil Gas

Vapor intrusion pathway evaluations commonly begin with a comparison of volatile organic chemical (VOC) concentrations in groundwater to generic, or Tier 1, screening levels. These screening levels are typically quite low reflecting both a desired level of conservatism in a generic risk screening process as well as limitations in understanding of physical and chemical processes that impact vapor migration in the subsurface. To study the latter issue, we have collected detailed soil gas and groundwater vertical concentration profiles and evaluated soil characteristics at seven different sites overlying chlorinated solvent contaminant plumes. The goal of the study was to evaluate soil characteristics and their impacts on VOC attenuation from groundwater to deep soil gas (i.e., soil gas in the unsaturated zone within 2 feet of the water table). The study results suggest that generic screening levels can be adjusted by a factor of 100× at sites with fine‐grained soils above the water table, as identified by visual observations or soil air permeability measurements. For these fine‐grained soil sites, the upward‐adjusted screening levels maintain a level of conservatism while potentially eliminating the need for vapor intrusion investigations at sites that may not meet generic screening criteria.     

Development and Testing of a Field Screening Method Based on Bubbling Extraction and Photoionization Detection for Measurement of Benzene and Total VOCs

A field screening method was developed for rapid measurement of benzene and gasoline range total petroleum hydrocarbons (TPHg) concentrations in groundwater. The method is based on collecting photoionization detector (PID) measurements from vapor samples. The vapor samples are collected by bubbling air through groundwater samples (air sparging) with a constant volume, temperature and sparging rate. The level of accuracy, sensitivity, precision, and statistical significance of the estimated concentrations, derived from the screening method, are comparable to conventional laboratory analytical results at concentrations equal to or greater than 150 µg/L for benzene and greater than 50 µg/L for TPHg. The method's concentration estimations can assist in making real‐time decisions regarding location of dissolved plumes and light nonaqueous phase liquid (LNAPL) source zones at many fuel release sites. The screening method was tested in the laboratory and in the field with 208 and 107 samples, respectively. The study concludes that the screening method can be used as a tool to aid in completing a site conceptual model as well as analyzing groundwater from monitoring wells.     

Sewer Gas: An Indoor Air Source of PCE to Consider During Vapor Intrusion Investigations

The United States Environmental Protection Agency (USEPA) is finalizing its vapor intrusion guidelines. One of the important issues related to vapor intrusion is background concentrations of volatile organic compounds (VOCs) in indoor air, typically attributed to consumer products and building materials. Background concentrations can exist even in the absence of vapor intrusion and are an important consideration when conducting site assessments. In addition, the development of accurate conceptual models that depict pathways for vapor entry into buildings is important during vapor intrusion site assessments. Sewer gas, either as a contributor to background concentrations or as part of the site conceptual model, is not routinely evaluated during vapor intrusion site assessments. The research described herein identifies an instance where vapors emanating directly from a sanitary sewer pipe within a residence were determined to be a source of tetrachloroethylene (PCE) detected in indoor air. Concentrations of PCE in the bathroom range from 2.1 to 190 µg/m³ and exceed typical indoor air concentrations by orders of magnitude resulting in human health risk classified as an “Imminent Hazard” condition. The results suggest that infiltration of sewer gas resulted in PCE concentrations in indoor air that were nearly two orders of magnitude higher as compared to when infiltration of sewer gas was not known to be occurring. This previously understudied pathway whereby sewers serve as sources of PCE (and potentially other VOC) vapors is highlighted. Implications for vapor intrusion investigations are also discussed.     

Estimation of Generic Subslab Attenuation Factors for Vapor Intrusion Investigations

Generic indoor air:subslab soil gas attenuation factors (SSAFs) are important for rapid screening of potential vapor intrusion risks in buildings that overlie soil and groundwater contaminated with volatile chemicals. Insufficiently conservative SSAFs can allow high‐risk sites to be prematurely excluded from further investigation. Excessively conservative SSAFs can lead to costly, time‐consuming, and often inconclusive actions at an inordinate number of low‐risk sites. This paper reviews two of the most commonly used approaches to develop SSAFs: (1) comparison of paired, indoor air and subslab soil gas data in empirical databases and (2) comparison of estimated subslab vapor entry rates and indoor air exchange rates (IAERs). Potential error associated with databases includes interference from indoor and outdoor sources, reliance on data from basements, and seasonal variability. Heterogeneity in subsurface vapor plumes combined with uncertainty regarding vapor entry points calls into question the representativeness of limited subslab data and diminishes the technical defensibility of SSAFs extracted from databases. The use of reasonably conservative vapor entry rates and IAERs offers a more technically defensible approach for the development of generic SSAF values for screening. Consideration of seasonal variability in building leakage rates, air exchange rates, and interpolated vapor entry rates allows for the development of generic SSAFs at both local and regional scales. Limitations include applicability of the default IAERs and vapor entry rates to site‐specific vapor intrusion investigations and uncertainty regarding applicability of generic SSAFs to assess potential short‐term (e.g., intraday) variability of impacts to indoor air.     

Portable GC/MS Methods to Evaluate Sources of cVOC Contamination in Indoor Air

A portable gas chromatograph‐mass spectrometer (GC/MS) was used to investigate sources of chlorinated volatile organic compound (cVOC) contamination in indoor air at 46 residences around Hill AFB, Utah, that were potentially affected by vapor intrusion. Analytical methods were developed to allow sample turnaround times of less than 10 min and method detection limits (MDLs) generally less than 1 μg/m³ for a selected list of cVOCs. Area‐by‐area sampling was used to identify the likely vapor source locations. In many cases, individual container/enclosure sampling and subsequent field emission rate measurements from isolated consumer products were used to determine if identified products were likely to be the primary source of vapors in the residence. The portable GC/MS was also used to characterize vapor intrusion in two residences. In one of these two residences, building pressure control was used to enhance vapor entry in order to facilitate the investigation resulting in confirmation of vapor intrusion and identification of a primary route of vapor entry. cVOCs were identified in 42 of the 46 homes investigated, subsurface vapor intrusion was identified in two homes, and two homes had inconclusive results.     

Petroleum Hydrocarbon Bioventing Kinetics Determined in Soil Core, Microcosm, and Tubing Cluster Studies

Aerobic biodegradation of vapor-phase petroleum hydrocarbons was evaluated in an intact soil core from the site of an aviation gasoline release. An unsaturated zone soil core was subjected to a flow of nitrogen gas, oxygen, water vapor, and vapor-phase hydrocarbons in a configuration analogous to a biofilter or an in situ bioventing or sparging situation. The vertical profiles of vapor-phase hydrocarbon concentration in the soil core were determined by gas chromatography of vapor samples. Biodegradation reduced low influent hydrocarbon concentrations by 45 to 92 percent over a 0.6-m interval of an intact soil core. The estimated total hydrocarbon concentration was reduced by 75 percent from 26 to 7 parts per million. Steady-state concentrations were input to a simple analytical model balancing advection and first-order biodegradation of hydrocarbons. First-order rate constants for the major hydrocarbon compounds were used to calibrate the model to the concentration profiles. Rate constants for the seven individual hydrocarbon compounds varied by a factor of 4. Compounds with lower molecular weights, fewer methyl groups, and no quaternary carbons tended to have higher rate constants. The first-order rate constants were consistent with kinetic parameters determined from both microcosm and tubing cluster studies at the field site.     

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.     

High Purge Volume Sampling—A New Paradigm for Subslab Soil Gas Monitoring

Subslab soil gas sampling and analysis is a common line of evidence for assessing human health risks associated with subsurface vapor intrusion to indoor air for volatile organic compounds; however, conventional subslab sampling methods have generated data that show substantial spatial and temporal variability, which often makes the interpretation difficult. A new method of monitoring has been developed and tested that is based on a concept of integrating samples over a large volume of soil gas extracted from beneath the floor slab of a building to provide a spatially averaged subslab concentration. Regular field screening is also conducted to assess the trend of concentration as a function of the volume removed to provide insight into the spatial distribution of vapors at progressive distances away from the point of extraction. This approach minimizes the risk of failing to identify the areas of elevated soil vapor concentrations that may exist between discrete sample locations, and can provide information covering large buildings with fewer holes drilled through the floor. The new method also involves monitoring the extraction flow rate and transient vacuum response for mathematical analysis to help interpret the vapor concentration data and to support an optimal design for any subslab venting system that may be needed.     

Impact of Temperature on Groundwater Source Attenuation Rates at Hydrocarbon Sites

The temperature sensitivity of microbial populations is reflected in measured source attenuation rates at hydrocarbon‐impacted sites. The objective of this study was to evaluate the correlation between temperature and source attenuation rates (concentration vs. time attenuation rate over many years) of benzene and toluene by analyzing groundwater monitoring data from >2000 hydrocarbon sites. Historical monitoring records were obtained from three databases, processed to yield long‐term multiyear source attenuation rates, and then compared with representative temperatures at each site. Statistically significant and positive relationships between temperature and source attenuation rates were established for benzene and toluene, indicating that temperature does impact hydrocarbon degradation, but is one of many factors that contribute to source attenuation. There was an observed 1.1 to 1.6 times increase in attenuation rates per 10 °C increase in temperature, which is less than the rate increases predicted by the Arrhenius equation. The temperature dependence on attenuation rate is consistent with several lines of evidence that methanogenesis plays a key role in the rate of hydrocarbon source zone attenuation rather than being controlled strictly by the availability of electron acceptors. First, methanogenesis is known to be strongly influenced by temperature, with significantly higher rates up to about 35 °C. Second, the temperature‐degradation rate relationship was stronger at sites with deeper water tables (>30 ft) that are less susceptible to oxygen influx than sites with shallow water tables (<15 ft). Third, dissolved methane concentrations were higher at sites with warmer temperatures. Overall, these results provide indirect support for a conceptual model where methanogenesis is a key degradation process at hydrocarbon sites, and that attenuation of these source zones is temperature‐sensitive.     

Review of Quantitative Surveys of the Length and Stability of MTBE,TBA, and Benzene Plumes in Groundwater at UST Sites

Quantitative information regarding the length and stability condition of groundwater plumes of benzene, methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) has been compiled from thousands of underground storage tank (UST) sites in the United States where gasoline fuel releases have occurred. This paper presents a review and summary of 13 published scientific surveys, of which 10 address benzene and/or MTBE plumes only, and 3 address benzene, MTBE, and TBA plumes. These data show the observed lengths of benzene and MTBE plumes to be relatively consistent among various regions and hydrogeologic settings, with median lengths at a delineation limit of 10 µg/L falling into relatively narrow ranges from 101 to 185 feet for benzene and 110 to 178 feet for MTBE. The observed statistical distributions of MTBE and benzene plumes show the two plume types to be of comparable lengths, with 90th percentile MTBE plume lengths moderately exceeding benzene plume lengths by 16% at a 10‐µg/L delineation limit (400 feet vs. 345 feet) and 25% at a 5‐µg/L delineation limit (530 feet vs. 425 feet). Stability analyses for benzene and MTBE plumes found 94 and 93% of these plumes, respectively, to be in a nonexpanding condition, and over 91% of individual monitoring wells to exhibit nonincreasing concentration trends. Three published studies addressing TBA found TBA plumes to be of comparable length to MTBE and benzene plumes, with 86% of wells in one study showing nonincreasing concentration trends.     

Evaluation of the Johnson and Ettinger Model for Prediction of Indoor Air Quality

Screening level models are now commonly used to estimate vapor intrusion for subsurface volatile organic compounds (VOCs). Significant uncertainty is associated with processes and models and, to date, there has been only limited field-based evaluation of models for this pathway. To address these limitations, a comprehensive evaluation of the Johnson and Ettinger (J&E) model is provided through sensitivity analysis, comparisons of model-predicted to measured vapor intrusion for 11 petroleum hydrocarbon and chlorinated solvent sites, and review of radon and flux chamber studies. Significant intrusion was measured at five of 12 sites with measured vapor attenuation ratios (α_m's) (indoor air/source vapor) ranging from ∼1 × 10⁻⁶ to 1 × 10⁻⁴. Higher attenuation ratios were measured for studies using radon, inert tracers, and flux chambers; however, these ratios are conservative owing to boundary conditions and tracer properties that are different than those at most VOC-contaminated sites. Reasonable predictions were obtained using the J&E model with comparisons indicating that model-predicted vapor attenuation ratios (α_p's) were on the same order, or less than the α_m's. For several sites, the (m were approximately two orders of magnitude less than the a 's indicating that the J&E model is conservative in these cases. The model comparisons highlight the importance in using appropriate input parameters for the J&E model. The regulatory implications associated with use of the J&E model to derive screening criteria are also discussed.