Understanding vapor intrusion (VI) temporal variability is key for the design of sampling strategies intended to assess reasonable maximum exposure of indoor air concentrations of volatile organic compounds (VOCs) as well as risk evaluation and mitigation planning. VI temporal variability has previously been shown to be dependent on the complex interactions of multiple independent variables-meteorological, hydrogeological, and human behavioral. Several meteorological variables, including barometric pressure, wind speed, and rainfall, are linked during tropical and extratropical storm events. High-frequency meteorological and indoor VOC data from a series of seven tropical storms and four extratropical storms were collected at a single industrial building with multiple heating, ventilation, and air conditioning (HVAC) zones. The storms and sampling zones showed a variety of effects on trichloroethylene (TCE) concentrations in indoor air. In one zone (supply room), increases in TCE concentrations often, but not always, closely coincided with decreasing barometric pressure, sustained wind speeds over 32 km/h (20 mph), and differential pressures indicating subslab to indoor flow. A second zone, in a restroom, did not show a consistent pattern of temporal correlation between meteorological factors and indoor air concentrations. While peak indoor air concentrations may be associated with the passage of cyclonic storms at some sampling locations, this does not appear to be generalizable to all sampling locations. The observed increase in indoor air concentration potentially attributable to these storms is typically less than an order of magnitude and the duration ranges from a day to a week.

Soil vapor extraction (SVE) can be applied for remediation, and also as an alternative to sub-slab depressurization (SSD) for vapor intrusion (VI) mitigation. This study compares capital, operation, and treatment costs of SVE and SSD systems using data collected during a multi-year demonstration project conducted at eight buildings in an urban setting. The capital cost of the SVE system is substantially less than the estimated total capital cost of individual SSD systems. The SVE operating costs are higher, especially in the early operating years when it is being operated for mass removal and treatment. As a result, the cumulative SVE system cost rises above that of the SSD systems in the sixth year of operation. A significant portion of the operations and maintenance cost advantage of the SSD systems comes from the assumption that off-gas treatment is not required. Alternative cases show SVE costs are likely to be lower in scenarios where numerous small buildings requiring independent SSD systems overlie the SVE zone of influence. Conversely, SSD systems are less costly for cases with few small buildings overlying the SVE zone of influence. An additional benefit of SVE is continued mass removal. In a situation where an existing SVE can be repurposed for VI protection from residual volatile organic carbon (VOC) mass, the SVE cumulative costs over 30years can remain lower than the cost of installing and operating SSD systems in multiple buildings.

Published literature for reported sorption coefficients (K) of eight anionic per- and polyfluoroalkyl substances (PFAS) in soil was reviewed. K values spanned three to five log units indicating that no single value would be appropriate for use in estimating PFAS impacts to groundwater using existing soil-water partition equations. Regression analysis was used to determine if the soil or solution parameters might be used to predict K values. None of the 15 experimental parameters collected could individually explain variability in reported K values. Significant associations between K and soil calcium and sodium content were found for many of the selected PFAS, suggesting that soil cation content may be critical to PFAS sorption, as previously noted in sources like Higgins and Luthy (2006), while organic carbon content was significant only at elevated levels (>5%). Unexplained discrepancies between the results from studies where PFAS were introduced to soil and desorbed in the laboratory and those that used material from PFAS-impacted sites suggest that laboratory experiments may be overlooking some aspects critical to PFAS sorption. Future studies would benefit from the development and use of standardized analytical methods to improve data quality and the establishment of soil parameters appropriate for collection to produce more complete data sets for predictive analysis.

Temporal and spatial variability of indoor air volatile organic compound (VOC) concentrations can complicate vapor intrusion (VI) assessment and decision-making. Indicators and tracers (I&T) of VI, such as differential temperature, differential pressure, and indoor radon concentration, are low-cost lines of evidence to support sampling scheduling and interpretation of indoor air VOC sampling results. This study compares peak indoor air chlorinated VOC concentrations and I&T conditions before and during those peak events at five VI sites. The sites differ geographically and in their VI conceptual site models (CSM). Relative to site-specific baseline values, the results show that cold or falling outdoor temperatures, rising cross slab differential pressures, and increasing indoor radon concentrations can predict peak VOC concentrations. However, cold outdoor air temperature was not useful at one site where elevated shallow soil temperature was a better predictor. Correlations of peak VOC concentrations to elevated or rising barometric pressure and low wind speed were also observed with some exceptions. This study shows how the independent variables that control or predict peak indoor air VOC concentrations are specific to building types, climates, and VI CSMs. More I&T measurements at VI sites are needed to identify scenario-specific baseline and peak related I&T conditions to improve decision-making.

Soil vapor extraction (SVE) is effective for removing volatile organic compound (VOC) mass from the vadose zone and reducing the potential for vapor intrusion (VI) into overlying and surrounding buildings. However, the relationship between residual mass in the subsurface and VI is complex. Through a series of alternating extraction (SVE on) and rebound (SVE off) periods, this field study explored the relationship and aspects of SVE applicable to VI mitigation in a commercial/light-industrial setting. The primary objective was to determine if SVE could provide VI mitigation over a wide area encompassing multiple buildings, city streets, and subsurface utilities and eliminate the need for individual subslab depressurization systems. We determined that SVE effectively mitigates offsite VI by intercepting or diluting contaminant vapors that would otherwise enter buildings through foundation slabs. Data indicate a measurable (5 Pa) influence of SVE on subslab/indoor pressure differential may occur but is not essential for effective VI mitigation. Indoor air quality improvements were evident in buildings 100 to 200 feet away from SVE including those without a measurable reversal of differential pressure across the slab or substantial reductions in subslab VOC concentration. These cases also demonstrated mitigation effects across a four-lane avenue with subsurface utilities. These findings suggest that SVE affects distant VI entry points with little observable impact on differential pressures and without relying on subslab VOC concentration reductions.

Building pressure cycling (BPC) is becoming an increasingly important tool for studying vapor intrusion. BPC has been used to distinguish subslab and indoor sources of vapor intrusion as well as to define reasonable worst case volatile organic compound mass discharge into a structure. Analyses have been performed both semi-quantitatively with concentration trends and quantitatively with more rigorous flux calculation and source attribution methods. This paper reviews and compares the protocols and outcomes from multiple published applications of this technology to define the key variables that control performance. Common lessons learned are identified, including those that help define the range of building size and type to which BPC is applicable. Differences in test protocols are discussed, recognizing that the complexity of the test protocol required depends on the particular objectives of each project. Research gaps are identified and tabulated for future validation studies and applications.

This paper presents model simulation results of vapor intrusion into structures built atop sites contaminated with volatile or semi-volatile chemicals of concern. A three-dimensional finite element model was used to investigate the importance of factors that could influence vapor intrusion when the site is characterized by non-homogeneous soils. Model simulations were performed to examine how soil layers of differing properties alter soil gas concentration profiles and vapor intrusion rates into structures. The results illustrate difference in soil gas concentration profiles and vapor intrusion rates between homogeneous and layered soils. The findings support the need for site conceptual models to adequately represent the site's geology when conducting site characterizations, interpreting field data and assessing the risk of vapor intrusion at a given site. For instance, in layered geologies, a lower permeability and diffusivity soil layer between the source and building often limits vapor intrusion rates, even if a higher permeability layer near the foundation permits increased soil gas flow rates into the building. In addition, the presence of water-saturated clay layers can considerably influence soil gas concentration profiles. Therefore, interpreting field data without accounting for clay layers in the site conceptual model could result in inaccurate risk calculations. Important considerations for developing more accurate conceptual site models are discussed in light of the findings.

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 meters (and some up to over 200 meters) 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 dataset 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 is a more appropriately conservative generic groundwater to indoor air attenuation factor than is the EPA-recommended 10. 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.

Many hydrological and geochemical studies rely on data resulting from injection of tracers and chemicals into groundwater wells. The even distribution of liquids to multiple injection points can be challenging or expensive, especially when using multiple pumps. An injection system was designed using one chemical metering pump to evenly distribute the desired influent simultaneously to 15 individual injection points through an injection manifold. The system was constructed with only one metal part contacting the fluid due to the low pH of the injection solutions. The injection manifold system was used during a three-month pilot scale injection experiment at the Vineland Chemical Company Superfund site. During the two injection phases of the experiment (Phase I = 0.27 L/min total flow, Phase II = 0.56 L/min total flow), flow measurements were made 20 times over three months; an even distribution of flow to each injection well was maintained (RSD <4%). This durable system is expandable to at least 16 injection points and should be adaptable to other injection experiments that require distribution of air-stable liquids to multiple injection points with a single pump.

Methods are developed to use data collected during cyclic operation of soil vapor extraction (SVE) systems to help characterize the magnitudes and timescales of mass flux associated with vadose zone contaminant sources. Operational data collected at the Department of Energy's Hanford site are used to illustrate the use of such data. An analysis was conducted of carbon tetrachloride vapor concentrations collected during and between SVE operations. The objective of the analysis was to evaluate changes in concentrations measured during periods of operation and non-operation of SVE, with a focus on quantifying temporal dynamics of the vadose zone contaminant mass flux, and associated source strength. Three mass-flux terms, representing mass flux during the initial period of a SVE cycle, during the asymptotic period of a cycle, and during the rebound period, were calculated and compared. It was shown that it is possible to use the data to estimate time frames for effective operation of an SVE system if a sufficient set of historical cyclic operational data exists. This information could then be used to help evaluate changes in SVE operations, including system closure. The mass-flux data would also be useful for risk assessments of the impact of vadose-zone sources on groundwater contamination or vapor intrusion.

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 chemicals (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 ug/m 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.

The potential for in situ biodegradation of tert-butyl alcohol (TBA) by creation of aerobic conditions in the subsurface with recirculating well pairs was investigated in two field studies conducted at Vandenberg Air Force Base (VAFB). In the first experiment, a single recirculating well pair with bromide tracer and oxygen amendment successfully delivered oxygen to the subsurface for 42 days. TBA concentrations were reduced from approximately 500 μg/L to below the detection limit within the treatment zone and the treated water was detected in a monitoring transect several meters downgradient. In the second experiment, a site-calibrated model was used to design a double recirculating well pair with oxygen amendment, which successfully delivered oxygen to the subsurface for 291 days and also decreased TBA concentrations to below the detection limit. Methylibium petroleiphilum strain PM1, a known TBA-degrading bacterium, was detectable at the study site but addition of oxygen had little impact on the already low baseline population densities, suggesting that there was not enough carbon within the groundwater plume to support significant new growth in the PM1 population. Given favorable hydrogeologic and geochemical conditions, the use of recirculating well pairs to introduce dissolved oxygen into the subsurface is a viable method to stimulate in situ biodegradation of TBA or other aerobically-degradable aquifer contaminants.

The objective of this study was to characterize the behavior of a groundwater contaminant (trichloroethene) plume after implementation of a source-containment operation at a site in Arizona. The plume resides in a quasi three-layer system comprising a sand/gravel unit bounded on the top and bottom by relatively thick silty clayey layers. The system was monitored for 60 months beginning at start-up in 2007 to measure the change in contaminant concentrations within the plume, the change in plume area, the mass of contaminant removed, and the integrated contaminant mass discharge. Concentrations of trichloroethene in groundwater pumped from the plume extraction wells have declined significantly over the course of operation, as have concentrations for groundwater sampled from 40 monitoring wells located within the plume. The total contaminant mass discharge associated with operation of the plume extraction wells peaked at 0.23 kg/d, decreased significantly within one year, and thereafter began an asymptotic decline to a current value of approximately 0.03 kg/d. Despite an 87% reduction in contaminant mass and a comparable 87% reduction in contaminant mass discharge for the plume, the spatial area encompassed by the plume has decreased by only approximately 50%. This is much less than would be anticipated based on ideal flushing and mass-removal behavior. Simulations produced with a simplified 3-D numerical model matched reasonably well to the measured data. The results of the study suggest that permeability heterogeneity, back diffusion, hydraulic factors associated with the specific well field system, and residual discharge from the source zone are all contributing to the observed persistence of the plume, as well as the asymptotic behavior currently observed for mass removal and for the reduction in contaminant mass discharge.

Although the anaerobic biodegradation of methyl -butyl ether (MTBE) and -butyl alcohol (TBA) has been documented in the laboratory and the field, knowledge of the microorganisms and mechanisms involved is still lacking. In this study, DNA-stable isotope probing (SIP) was used to identify microorganisms involved in anaerobic fuel oxygenate biodegradation in a sulfate-reducing MTBE and TBA plume. Microorganisms were collected in the field using Bio-Sep® beads amended with C-MTBE, C-MTBE (only methoxy carbon labeled), orC-TBA. C-DNA and C-DNA extracted from the Bio-Sep beads were cloned and 16S rRNA gene sequences were used to identify the indigenous microorganisms involved in degrading the methoxy group of MTBE and the -butyl group of MTBE and TBA. Results indicated that microorganisms were actively degrading C-labeled MTBE and TBA in situ and the C was incorporated into their DNA. Several sequences related to known MTBE- and TBA-degraders in the Burkholderiales and the Sphingomonadales orders were detected in all threeC clone libraries and were likely to be primary degraders at the site. Sequences related to sulfate-reducing bacteria and iron-reducers, such as and , were only detected in the clone libraries where MTBE and TBA were fully labeled with C, suggesting that they were involved in processing carbon from the -butyl group. Sequences similar to the genus predominated in the clone library where only the methoxy carbon of MTBE was labeled with C. It is likely that members of this genus were secondary degraders cross-feeding on C-labeled metabolites such as acetate.

In this study we present a petroleum vapor intrusion tool implemented in Microsoft Excel using Visual Basic for Applications (VBA) 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 Petroleum Vapor Intrusion guidance, a sensitivity analysis and a simplified Monte Carlo uncertainty analysis are also included in the spreadsheet.

The risk that benzene and toluene from spills of gasoline will impact drinking water wells is largely controlled by the natural anaerobic biodegradation of benzene and toluene. Benzene and toluene, as well as ethanol and other biofuels, are degraded under anaerobic conditions to the same pool of degradation products. Biodegradation of biofuels may produce concentrations of degradation products that make the thermodynamics for degradation of benzene and toluene infeasible under methanogenic conditions and produce larger plumes of benzene and toluene. This study evaluated the concentrations of fuel alcohols that are necessary to inhibit the anaerobic degradation of benzene and toluene under methanogenic conditions. At two ethanol spill sites, concentrations of ethanol greater ≥42 mg/L inhibited the anaerobic degradation of toluene. The pH and concentrations of acetate, dissolved inorganic carbon, and molecular hydrogen were used to calculate the Gibbs free energy for the biodegradation of toluene. In general, the anaerobic biodegradation of toluene was not thermodynamically feasible in water with ≥42 mg/L ethanol. In a microcosm study, when the concentrations of ethanol were ≥14 mg/L or the concentrations of n-butanol were ≥16 mg/L, the biodegradation of the alcohols consistently produced concentrations of hydrogen, dissolved inorganic carbon, and acetate that would preclude natural anaerobic biodegradation of benzene and toluene by syntrophic organisms. In contrast, iso-butanol and n-propanol only occasionally produced conditions that would preclude the biodegradation of benzene and toluene.

Contaminant rebound and low contaminant removal are reported more frequently with in situ chemical oxidation than other in situ technologies. Although there are multiple causes for these results, a critical analysis indicates that low oxidant volume delivery is a key issue. The volume of oxidant injected is critical and porosity of the aquifer matrix can be used to estimate the pore volume. The total porosity ( ) is the volume of voids relative to the total volume of aquifer material. The mobile porosity ( ) is the fraction of voids that readily contributes to fluid displacement, and is less than leading to smaller estimates of oxidant volume. Injecting low-oxidant volume may result in inadequate oxidant distribution and postinjection dispersal within the radius of influence, insufficient oxidant contact and oxidant loading, and incomplete treatment; whereas, greater oxidant volume achieves a greater oxidant footprint and may involve risk that the injected oxidant may migrate into nontarget areas and displacement of contaminated groundwater. Design guidelines and recommendations are provided that could help achieve more effective technology deployment, reduce the role of heterogeneities in the subsurface, and result in greater probability the oxidant is delivered to the targeted treatment zone.

Hazardous waste site investigations have shown that volatile organic compounds (VOCs) can be transported via sewer pipes and migrate into indoor spaces. Despite field data confirming the presence of this exposure pathway, there is lack of context-based numerical models that provide guidance to characterize and predict VOCs concentration in sewer gas at vapor intrusion sites. Particularly, this poses a challenge when assessing and mitigating risks associated with these exposure pathways. Therefore, a numerical model has been developed to simulate the concentration of VOCs in sewer gas in different stages throughout the sewer lines. The developed model considers various input parameters, including temperature, sewer liquid depth, groundwater depth, and sewer construction characteristics to incorporate local and operational conditions. The model's output is verified using field data from a sewer system constructed near a Superfund site. Moreover, a sensitivity analysis was conducted to evaluate the model's response to variation of the external input parameters. To the best of our knowledge, this study is the first attempt to model VOCs concentration in sewer gas, particularly to address vapor intrusion. The developed model can be used as a numerical tool to support the development of sewer assessment guidelines, risk assessment studies, and mitigation strategies.

Back diffusion of contaminants from secondary sources may hamper site remediation if it is not properly addressed in the remedial design. A review of all reported technologies and strategies that have been or could be applied to address plume persistence due to back diffusion as published in the peer-reviewed literature is provided. We classify these into four major categories. The first category consists of those approaches that do not include active measures to specifically address contamination in the low permeable zones (LPZs) and can therefore be considered passive LPZ management approaches. A disadvantage of these approaches is the long duration that may be required to meet acceptable endpoints; however, this allows degradation to potentially play a significant part even at modest rates. The remaining three categories all use approaches to specifically address contaminants in the LPZ. The second category consists of strategies that promote contaminant destruction through the forward diffusion of amendments into the LPZ. A variety of laboratory tests indicate concentration or flux reductions range from no improvement, to reductions as high as four orders-of-magnitude depending on the evaluation metric. The third category consists of strategies that alter physical characteristics of the secondary source, and includes viscosity modification, fracturing, and soil mixing. Each of these offer unique advantages and are often used to deliver one or more amendments for contaminant treatment. The final category consists of thermal and electrokinetic remediation, both less susceptible to permeability contrast limitations. However, they are not routinely used for secondary-source treatment.