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.     

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.     

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.     

Evidence for Increasing Indoor Sources of 1,2-Dichloroethane Since 2004 at Two Colorado Residential Vapor Intrusion Sites

Groundwater contamination associated with two former industrial facilities in Denver, Colorado, has led to concerns about vapor intrusion into residences adjacent to the facilities. 1,1,1-Trichloroethane (1,1,1-TCA), 1,1-dichloroethene (1,1-DCE), and trichloroethene (TCE) are the main contaminants of concern in groundwater, with trace levels of 1,2-dichloroethane (1,2-DCA) present at one of the sites. Indoor air monitoring programs have been ongoing at these two sites since 1998 and recent results have suggested that background, indoor source, 1,2-DCA has been increasing in the frequency of detection, and median and maximum concentration over the past several years. A lines of evidence evaluation was undertaken for both sites in order to document the predominance of indoor sources of 1,2-DCA. Evidence utilized included spatial evaluation of 1,2-DCA in indoor air; comparison of 1,2-DCA concentrations in mitigated and unmitigated homes; a phone survey to evaluate the potential for smoking to contribute to indoor air 1,2-DCA levels; evaluation of mitigation system effluent data; and an evaluation of volatile organic compound (VOC) ratios in groundwater and indoor air. The results of this evaluation indicated that smoking had no demonstrable influence on measured indoor air concentrations. In addition, it appears that consumer products have had a markedly increased influence on indoor air concentrations since 2005. Data from one of the industrial facilities at one of the sites also indicated that polyvinyl chloride (PVC) and vinyl composite floor adhesive used in a building remodel in 2005 apparently generated elevated levels of indoor 1,2-DCA and vinyl chloride, which have been sustained up to the present time.     

Emissions of 1,2-Dichloroethane from Holiday Decorations as a Source of Indoor Air Contamination

Groundwater contamination associated with an industrial facility in Utah has led to concerns about potential vapor intrusion into residences outside the facility boundary. Trichloroethylene (TCE) is the main contaminant of concern with 1,2-dichloroethane (1,2-DCA) present in some areas. An air-monitoring program implemented to detect vapor intrusion of these compounds found 1,2-DCA in homes outside areas of groundwater contamination, suggesting indoor sources in these cases. Investigative indoor air and product sampling were conducted to isolate consumer products emitting 1,2-DCA and to quantify the emission rates of identified products. The combination of room-by-room air sampling and emission measurements was successfully used to identify molded plastic holiday ornaments, having measured emission rates as high as 0.3 µg 1,2-DCA/min. Subsequent testing of seven comparable retail items found similar 1,2-DCA emissions. Screening-level calculations show that the measured emission rates of 1,2-DCA from these items can lead to indoor concentrations high enough to be of regulatory concern (0.094 to 9.4 µg/m³ based on 10^–6 to 10^–4 cancer risk levels).     

Examining the Use of USEPA's Generic Attenuation Factor in Determining Groundwater Screening Levels for Vapor Intrusion

A value of 0.001 is recommended by the United States Environmental Protection Agency (USEPA) for its groundwater‐to‐indoor air Generic Attenuation Factor (GAFG), used in assessing potential vapor intrusion (VI) impacts to indoor air, given measured groundwater concentrations of volatile chemicals of concern (e.g., chlorinated solvents). The GAFG can, in turn, be used for developing groundwater screening levels for VI given target indoor air quality screening levels. In this study, we examine the validity and applicability of the GAFG both for predicting indoor air impacts and for determining groundwater screening levels. This is done using both analysis of published data and screening model calculations. Among the 774 total paired groundwater‐indoor air measurements in the USEPA's VI database (which were used by that agency to generate the GAFG) we found that there are 427 pairs for which a single groundwater measurement or interpolated value was applied to multiple buildings. In one case, up to 73 buildings were associated with a single interpolated groundwater value and in another case up to 15 buildings were associated with a single groundwater measurement (i.e., that the indoor air contaminant concentrations in all of the associated buildings were influenced by the concentration determined at a single point). In more than 70% of the cases (390 of 536 paired measurements in which horizontal building‐monitoring well distance was recorded) the monitoring wells were located more than 30 m (and one up to over 200 m) from the associated buildings. In a few cases, the measurements in the database even improbably implied that soil gas contaminant concentrations increased, rather than decreased, in an upward direction from a contaminant source to a foundation slab. Such observations indicate problematic source characterization within the data set used to generate the GAFG, and some indicate the possibility of a significant influence of a preferential contaminant pathway. While the inherent value of the USEPA database itself is not being questioned here, the above facts raise the very real possibility that the recommended groundwater attenuation factors are being influenced by variables or conditions that have not thus far been fully accounted for. In addition, the predicted groundwater attenuation factors often fall far beyond the upper limits of predictions from mathematical models of VI, ranging from screening models to detailed computational fluid dynamic models. All these models are based on the same fundamental conceptual site model, involving a vadose zone vapor transport pathway starting at an underlying uniform groundwater source and leading to the foundation of a building of concern. According to the analysis presented here, we believe that for scenarios for which such a “traditional” VI pathway is appropriate, 10^?4 is a more appropriately conservative generic groundwater to indoor air attenuation factor than is the EPA‐recommended 10^?3. This is based both on the statistical analysis of USEPA's VI database, as well as the traditional mathematical models of VI. This result has been validated by comparison with results from some well‐documented field studies.     

Predicting Vertical LNAPL Distribution in the Subsurface under the Fluctuating Water Table Effect

The present study proposes a methodology for predicting the vertical light nonaqueous-phase liquids (LNAPLs) distribution within an aquifer by considering the influence of water table fluctuations. The LNAPL distribution is predicted by combining (1) information on air/LNAPL and LNAPL/water interface elevations with (2) the initial elevation of the water table without LNAPL effect. Data used in the present study were collected during groundwater monitoring undertaken over a period of 4 months at a LNAPL-impacted observation well. In this study, the water table fluctuations raised the free LNAPL in the subsurface to an elevation of 206.63 m, while the lowest elevation was 205.70 m, forming a thickness of 0.93 m of LNAPL-impacted soil. Results show that the apparent LNAPL thickness in the observation well is found to be three times greater than the actual free LNAPL thickness in soil; a finding that agrees with previous studies reporting that apparent LNAPL thickness in observation wells typically exceeds the free LNAPL thickness within soil by a factor estimated to range between 2 and 10. The present study provides insights concerning the transient variation of LNAPL distribution within the subsurface and highlights the capability of the proposed methodology to mathematically predict the actual LNAPL thickness in the subsurface, without the need to conduct laborious field tests. Practitioners can use the proposed methodology to determine by how much the water table should be lowered, through pumping, to isolate the LNAPL-impacted soil within the unsaturated zone, which can then be subjected to in situ vadose zone remedial treatment.     

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.     

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).     

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.     

Prediction of Indoor Air Quality from Soil-Gas Data at Industrial Buildings

Subslab or shallow soil-gas data are often compared with indoor air concentration data in vapor intrusion (VI) evaluations. If no indoor air data are available or confounding sources are present, or if future scenarios are considered, the soil-gas data may be used to estimate the indoor air concentrations due to VI. The typical approach in risk assessments is to use the 95th percentile values from a set of concentration data. For VI studies, however, this rarely is an option because the data sets tend to be quite small. Therefore, various guidance documents urge the use of maximum soil-gas values. This may be reasonable for small residential buildings, but can lead to very conservatively biased estimates if applied to large industrial buildings with localized areas of contamination, especially given that the sampling locations may not be randomly selected and instead are biased toward worst-case locations. By this approach, VI guidance implicitly tolerates a large percentage of false positive decision errors to minimize the number of false negative decision errors. In this paper, implications of using maximum values are discussed and illustrated with data sets from a number of large industrial buildings at various sites. An alternative approach to using maximum soil-gas values is proposed that serves to reduce the number of false positive results while controlling the number of false negatives to an acceptable level.     

探地雷达在LNAPL污染土壤探测中的应用进展研究

轻非水相液体(LNAPL)的不当使用、渗漏及不当处置等会造成严重的土壤和地下水污染,威胁环境和公共卫生安全.探地雷达(GPR)作为一项重要的浅表地球物理观测技术已在LNAPL污染土壤探测中发挥重要作用.本文对近年来国内外学者利用GPR探测LNAPL污染土壤方面的理论和应用研究进行梳理,结合实例主要从以下几个方面开展评述.这些方面包括LNAPL污染土壤电性特征、基于GPR探测的LNAPL污染土壤建模、GPR信号响应、GPR的测量方式等.这些理论与应用研究为如何从场地的地质和水文背景中提取与污染有关的GPR信号做出了指导与成功的示范.现场和实验室的大量的研究工作表明,所有成功的案例都不可能倚赖单一的手段或方法.直接(例如,钻孔)和间接(例如,GPR)调查结合,多手段、多方法的有效配合,才有可能最大程度的减小探测结果的非唯一性,达到全面准确了解污染场地的目的.     

Biodegradation of Petroleum Hydrocarbons in Fractured, Unsaturated Dolomite at a Field Site

Gasoline constituents were detected in unsaturated soil and rock during abandonment of a leaky underground storage tank (UST). The unsaturated sequence beneath the former UST consists of 90 feet of silty till, fractured dolomite, and friable sand-stone. Pore gas probes were installed in each of the unsaturated units, both in the source area and in a background on-site location. Pore gas samples were collected to evaluate the nature, extent, and fate of residual hydrocarbons in the vadose zone. Pore gas from the till and dolomite in the source area was enriched in petroleum hydrocarbons and carbon dioxide, and was depleted in oxygen, relative to pore gas from the background area. During two years of ground water monitoring at the site, methyl tertiary butyl ether was periodically detected in the ground water beneath the source area as pulses of recharge passed through the unsaturated zone, but no other gasoline constituents were detected. Apparently, the most degradable fraction of the gasoline (aromatic hydrocarbons) is being attenuated in the vadose zone before the water table is reached.     

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.     

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.     

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.     

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.     

LNAPL Volume Calculation: Parameter Estimation by Nonlinear Regression of Saturation Profiles

An estimation of the volume of light nonaqueous phase liquids (LNAPL) is often required during site assessment, remedial design, or litigation. LNAPL volume can be estimated by a strictly empirical approach whereby core samples, distributed throughout the vertical and lateral extent of LNAPL, are analyzed for LNAPL content, and these data are then integrated to compute a volume. Alternatively, if the LNAPL has obtained vertical equilibrium, the thickness of LNAPL in monitoring wells can be used to calculate of LNAPL in monitoring wells can be used to calculate LNAPL volume at the well locations if appropriate soil and LNAPL properties can be estimated.
A method is described for estimating key soil and LNAPL properties by nonlinear regression of vertical profiles of LNAPL saturation. The methods is relatively fast, cost effective, and amenable to quantitative analysis of uncertainty. Optionally, the method allows statistical determination of best-fit values for the Van Genuchten capillary parameters (n, α_oil-water and α_oil-air), residual water saturation and ANAPL density. The sensitivity of the method was investigated by fitting field LNAPL saturation profiles and then determining the variation in misfit (mean square residual) as a function of parameter value for each parameter. Using field data from a sandy aquifer, the fitting statistics were found to be highly sensitive to LNAPL density, α_oil-water and α_oil-air moderately sensitive to the Van Genuchten n value, and weakly sensitive to residual water saturation. The regression analysis also provides information that can be used to estimate uncertainty in the estimated parameters, which can then be used to estimate uncertainty in calculated values of specific volume.     

Monitoring In Situ Biodegradation of MTBE Using Multiple Rounds of Compound‐Specific Stable Carbon Isotope Analysis

At a large industrial facility, methyl tert‐butyl ether (MTBE) was released to the subsurface and dispersed into the light, non‐aqueous phase liquids (LNAPL), in the first aquifer, with the LNAPL serving as a continuous source of MTBE in groundwater. Compound‐specific isotope analysis was conducted on both MTBE and tert‐butyl alcohol (TBA) in groundwater samples collected in 2008, 2011, and 2013 from wells located along and off the center line of the MTBE plume. The study demonstrated the onset and progress of biodegradation of MTBE between 2008 and 2013. The TBA observed in 2008 appears to be derived only in part from MTBE transformation while a significant portion of TBA might be contributed directly from LNAPL sources. In 2011 to 2013, the dominant source of TBA in the mid‐gradient plume was MTBE transformation. A contribution of an offsite LNAPL source, in particular to the down‐gradient area of the plume, is possible but could not be unequivocally confirmed. The time series provided direct evidence for MTBE biodegradation, but also a valuable insight on the sources of TBA.