Contaminant sorption on soil and indoor materials and its possible impact on transients in vapor intrusion- An example based upon trichloroethylene (TCE).

Although building materials are well recognized as potential sources and sinks of indoor volatile organic compounds (VOCs), knowledge about how they affect indoor air concentrations and measurements in vapor intrusion scenarios is limited. This study investigates the potential influence of sorption processes on indoor air contamination in vapor intrusion, relying upon laboratory measurements at relevant concentration levels, and applying these in a numerical transient vapor intrusion model. It was found that the sink effect of adsorption on building materials can lower indoor air concentrations or delay their achieving a steady state, thus cautioning that these processes can affect observed indoor air concentration variability. Building materials can also serve as secondary sources of pollutants in vapor intrusion mitigation scenarios, which might affect the evaluation of the efficiency of mitigation efforts. For example, it was predicted that in a cinderblock structure it could take up to 305 hours to reduce indoor trichloroethylene (TCE) concentrations by 50% due to the re-emission of TCE from the cinderblock, whereas it would take only 1.4 hours without the re-emission process.

Estimation of vapor pressures of perfluoroalkyl substances (PFAS) using COSMOtherm.

The widespread presence of per- and polyfluoroalkyl substances (PFAS) in the environment and a recognition of their possible health effects has, over the past decade, raised public concerns and led to much new research on these materials. In this field, with so many compounds of potential interest or concern, measuring the physical properties of even a small fraction of these compounds is a formidable task. The research community has turned to use of computational methods to begin to predict many useful properties, based just upon the structure of the compound. In this work, a quantum chemistry computational method (COSMO-RS) has been applied for exploring the possibility and accuracy of PFAS compound property estimation. The vapor pressures and boiling points of eleven PFAS are calculated with COSMOtherm and compared with available experimental data and literature calculation data using other packages. In the meantime, these measured results have permitted evaluation of this popular property estimation technique, which has not yet been fully validated for this class of compounds.

Vapor pressure of nine perfluoroalkyl substances (PFASs) determined using the Knudsen Effusion Method.

Sublimation vapor pressures of nine pure perfluoroalkyl substances, including Ammonium perfluoro(2-methyl-3-oxahexanoate) (GenX), 1H,1H,2H,2H-Perfluoro-1-decanol (8:2 FTOH), 1H,1H,2H,2H-Perfluoro-1-dodecanol (10:2 FTOH) and C6 to C11 perfluorocarboxylic acids (PFCAs), were measured using the Knudsen technique at near ambient temperatures. Melting temperatures and fusion enthalpies of these compounds were also measured using differential scanning calorimetry. The vapor pressure of GenX ammonium salt is comparable to that of the much higher molecular weight perfluoroundecanoic acid. GenX ammonium salt also did not show actual melting behavior but instead decomposed at around 470 K. The measured near ambient temperature sublimation vapor pressures of the PFCAs and FTOHs were compared with some earlier reported liquid phase vapor pressures obtained at higher temperatures, and reasonable agreement exists between the data obtained in the different studies. The sublimation enthalpies of the PFCAs indicate that the contribution to the sublimation enthalpy of the CF2 group in the alkyl chain is comparable to that of the CH2 group in the corresponding non-fluorinated analogues, even though the PFCAs show consistently higher vapor pressures than do the corresponding carbon number alkanoic acids.

Very Low Concentration Adsorption Isotherms of Trichloroethylene on Common Building Materials.

Building materials that are found in the indoor environment can play an important role in determining indoor air quality. Previous studies have recognized that building materials are potential sinks/sources of indoor volatile organic compounds (VOCs), but their uptake under extremely low concentrations has not been extensively studied. This study has characterized the capacities of various building materials for adsorption of trichloroethylene (TCE), which is a contaminant of significant concern in vapor intrusion scenarios. The capacities of more than 20 building materials were established at a TCE concentration of 1.12 ppbv (and for selected materials at concentrations up to 12.5 ppbv). This was achieved using a thermal desorption method. Room temperature isotherms for glass wool, polyethylene, nylon carpet, drywall, printer paper, leather, and cinderblock were measured. The results showed that the sorptive capacities of the building materials were at nanograms per gram levels; cinderblock had the largest sorption capacity among all the building materials tested and this is believed to indicate that solid carbon content of materials plays a significant role during the sorption process. TCE desorption from selected building materials was also investigated at room temperature and 100°C.

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 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, 10-4 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.

Evaluation and Management Strategies for Per- and Polyfluoroalkyl Substances (PFASs) in Drinking Water Aquifers: Perspectives from Impacted U.S. Northeast Communities.

BACKGROUND: Multiple Northeast U.S. communities have discovered per- and polyfluoroalkyl substances (PFASs) in drinking water aquifers in excess of health-based regulatory levels or advisories. Regional stakeholders (consultants, regulators, and others) need technical background and tools to mitigate risks associated with exposure to PFAS-affected groundwater. OBJECTIVES: The aim was to identify challenges faced by stakeholders to extend best practices to other regions experiencing PFAS releases and to establish a framework for research strategies and best management practices. METHODS AND APPROACH: Management challenges were identified during stakeholder engagement events connecting attendees with PFAS experts in focus areas, including fate/transport, toxicology, and regulation. Review of the literature provided perspective on challenges in all focus areas. Publicly available data were used to characterize sources of PFAS impacts in groundwater and conduct a geospatial case study of potential source locations relative to drinking water aquifers in Rhode Island. DISCUSSION: Challenges in managing PFAS impacts in drinking water arise from the large number of relevant PFASs, unconsolidated information regarding sources, and limited studies on some PFASs. In particular, there is still considerable uncertainty regarding human health impacts of PFASs. Frameworks sequentially evaluating exposure, persistence, and treatability can prioritize PFASs for evaluation of potential human health impacts. A regional case study illustrates how risk-based, geospatial methods can help address knowledge gaps regarding potential sources of PFASs in drinking water aquifers and evaluate risk of exposure. CONCLUSION: Lessons learned from stakeholder engagement can assist in developing strategies for management of PFASs in other regions. However, current management practices primarily target a subset of PFASs for which in-depth studies are available. Exposure to less-studied, co-occurring PFASs remains largely unaddressed. Frameworks leveraging the current state of science can be applied toward accelerating this process and reducing exposure to total PFASs in drinking water, even as research regarding health effects continues. https://doi.org/10.1289/EHP2727.

A two-dimensional analytical model of vapor intrusion involving vertical heterogeneity.

In this work, we present an analytical chlorinated vapor intrusion (CVI) model that can estimate source-to-indoor air concentration attenuation by simulating two-dimensional (2-D) vapor concentration profile in vertically heterogeneous soils overlying a homogenous vapor source. The analytical solution describing the 2-D soil gas transport was obtained by applying a modified Schwarz-Christoffel mapping method. A partial field validation showed that the developed model provides results (especially in terms of indoor emission rates) in line with the measured data from a case involving a building overlying a layered soil. In further testing, it was found that the new analytical model can very closely replicate the results of three-dimensional (3-D) numerical models at steady state in scenarios involving layered soils overlying homogenous groundwater sources. By contrast, by adopting a two-layer approach (capillary fringe and vadose zone) as employed in the EPA implementation of the Johnson and Ettinger model, the spatially and temporally averaged indoor concentrations in the case of groundwater sources can be higher than the ones estimated by the numerical model up to two orders of magnitude. In short, the model proposed in this work can represent an easy-to-use tool that can simulate the subsurface soil gas concentration in layered soils overlying a homogenous vapor source while keeping the simplicity of an analytical approach that requires much less computational effort.

Investigating the Role of Soil Texture in Vapor Intrusion from Groundwater Sources.

Soil texture is believed to play a significant role in the migration of subsurface volatile chemicals into buildings at contaminated sites, an exposure process known as vapor intrusion (VI). In this study, we investigated the role of soil texture in determining the attenuation of contaminant soil gas concentration from groundwater source to receptor building. We performed soil column experiments, numerical simulations, and statistical analysis of the USEPA's VI database. The soil column experiments were conducted with commercial sand and soils with sand and sandy loam textures. Measured one-dimensional soil gas concentration profiles were compared with numerical predictions. Good agreement between experiments and model results supports the use of the classical multiphase chemical transport equation for simulating contaminant vapor transport from groundwater through the vadose zone. A full three-dimensional numerical model was then used to simulate typical VI scenarios with groundwater sources. Results indicate that, although soil particle texture can play a role in determining subslab-to-indoor air concentration attenuation, there is no obvious relationship between soil particle size and groundwater source-to-subslab except in the case of a shallow contaminant source. This conclusion is consistent with results reported in USEPA's VI database, in which variation in soil particle size does not affect source-to-subslab attenuation factors but does influence subslab-to-indoor air concentration attenuation factors by an average of about 0.4 order of magnitude. This finding suggests that an appropriate focus of VI site investigation should include the shallow soil beneath the building foundation.

Three-Dimensional Simulation of Land Drains as a Preferential Pathway for Vapor Intrusion into Buildings.

Preferential pathways can be significant vapor intrusion (VI) contributors, causing potentially higher inhalation risk to residents of affected buildings than that arising through traditional intrusion pathways. To assess land drains as a preferential pathway, a three-dimensional model, validated using data from a 4-yr field study, was used to study the roles of subfoundation soil permeability on soil gas flow and indoor depressurization. Results indicated that it is almost impossible for an indirect preferential pathway like a land drain ending in subfoundation soils with a permeability <10 m to affect indoor air quality if the land drain connects to a source with the same vapor concentration as that of the groundwater source beneath the building. An equation was developed to estimate the threshold permeability. We also found that even after the preferential pathway was identified using indoor depressurization (also known as controlled pressure method [CPM]) and then turned off, the influence of the preferential pathway and indoor depressurization on indoor concentration might last for months, although it may not be significant (i.e., may not exceed one order of magnitude, in this study). In the absence of such a preferential VI pathway, CPM may actually reduce indoor air concentrations of contaminants below those present under natural indoor pressure conditions, due to the emission rate limit determined by the upward diffusion rate from the vapor source. Our study highlights the role of measuring subfoundation soil permeability to soil gas flow in site investigations and warns practitioners about the possible mischaracterization of indoor air concentration after applying CPM in the absence of a preferential pathway.

Estimating the oxygenated zone beneath building foundations for petroleum vapor intrusion assessment.

Previous studies show that aerobic biodegradation can effectively reduce hydrocarbon soil gas concentrations by orders of magnitude. Increasingly, oxygen limited biodegradation is being included in petroleum vapor intrusion (PVI) guidance for risk assessment at leaking underground storage tank sites. The application of PVI risk screening tools is aided by the knowledge of subslab oxygen conditions, which, however, are not commonly measured during site investigations. Here we introduce an algebraically explicit analytical method that can estimate oxygen conditions beneath the building slab, for PVI scenarios with impervious or pervious building foundations. Simulation results by this new model are then used to illustrate the role of site-specific conditions in determining the oxygen replenishment below the building for both scenarios. Furthermore, critical slab-width-to-source-depth ratios and critical source depths for the establishment of a subslab "oxygen shadow" (i.e. anoxic zone below the building) are provided as a function of key parameters such as vapor source concentration, effective diffusion coefficients of concrete and building depth. For impervious slab scenarios the obtained results are shown in good agreement with findings by previous studies and further support the recommendation by U.S. EPA about the inapplicability of vertical exclusion distances for scenarios involving large buildings and high source concentrations. For pervious slabs, results by this new model indicate that even relatively low effective diffusion coefficients of concrete can facilitate the oxygen transport into the subsurface below the building and create oxygenated conditions below the whole slab foundation favorable for petroleum vapor biodegradation.

Field data and numerical modeling: A multiple lines of evidence approach for assessing vapor intrusion exposure risks.

USEPA recommends a multiple lines of evidence approach to make informed decisions at vapor intrusion sites because the vapor intrusion pathway is notoriously difficult to characterize. Our study uses this approach by incorporating groundwater, soil gas, indoor air field measurements and numerical models to evaluate vapor intrusion exposure risks in a Metro-Boston neighborhood known to exhibit lower than anticipated indoor air concentrations based on groundwater concentrations. We collected and evaluated five rounds of field sampling data over the period of one year. Field data results show a steep gradient in soil gas concentrations near the groundwater surface; however as the depth decreases, soil gas concentration gradients also decrease. Together, the field data and the numerical model results suggest that a subsurface feature is limiting vapor transport into indoor air spaces at the study site and that groundwater concentrations are not appropriate indicators of vapor intrusion exposure risks in this neighborhood. This research also reveals the importance of including relevant physical models when evaluating vapor intrusion exposure risks using the multiple lines of evidence approach. Overall, the findings provide insight about how the multiple lines of evidence approach can be used to inform decisions by using field data collected using regulatory-relevant sampling techniques, and a well-established 3-D vapor intrusion model.

An Excel®-based visualization tool of 2-D soil gas concentration profiles in petroleum vapor intrusion.

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.

Impacts of Changes of Indoor Air Pressure and Air Exchange Rate in Vapor Intrusion Scenarios.

There has, in recent years, been increasing interest in understanding the transport processes of relevance in vapor intrusion of volatile organic compounds (VOCs) into buildings on contaminated sites. These studies have included fate and transport modeling. Most such models have simplified the prediction of indoor air contaminant vapor concentrations by employing a steady state assumption, which often results in difficulties in reconciling these results with field measurements. This paper focuses on two major factors that may be subject to significant transients in vapor intrusion situations, including the indoor air pressure and the air exchange rate in the subject building. A three-dimensional finite element model was employed with consideration of daily and seasonal variations in these factors. From the results, the variations of indoor air pressure and air exchange rate are seen to contribute to significant variations in indoor air contaminant vapor concentrations. Depending upon the assumptions regarding the variations in these parameters, the results are only sometimes consistent with the reports of several orders of magnitude in indoor air concentration variations from field studies. The results point to the need to examine more carefully the interplay of these factors in order to quantitatively understand the variations in potential indoor air exposures.

Comparison between PVI2D and Abreu-Johnson's Model for Petroleum Vapor Intrusion Assessment.

Recently, we have developed a two-dimensional analytical petroleum vapor intrusion model, PVI2D (petroleum vapor intrusion, two-dimensional), which can help users to easily visualize soil gas concentration profiles and indoor concentrations as a function of site-specific conditions such as source strength and depth, reaction rate constant, soil characteristics, and building features. In this study, we made a full comparison of the results returned by PVI2D and those obtained using Abreu and Johnson's three-dimensional numerical model (AJM). These comparisons, examined as a function of the source strength, source depth, and reaction rate constant, show that PVI2D can provide similar soil gas concentration profiles and source-to-indoor air attenuation factors (within one order of magnitude difference) as those by the AJM. The differences between the two models can be ascribed to some simplifying assumptions used in PVI2D and to some numerical limitations of the AJM in simulating strictly piecewise aerobic biodegradation and no-flux boundary conditions. Overall, the obtained results show that for cases involving homogenous source and soil, PVI2D can represent a valid alternative to more rigorous three-dimensional numerical models.

A two-dimensional analytical model of petroleum vapor intrusion.

In this study we present an analytical solution of a two-dimensional petroleum vapor intrusion model, which incorporates a steady-state diffusion-dominated vapor transport in a homogeneous soil and piecewise first-order aerobic biodegradation limited by oxygen availability. This new model can help practitioners to easily generate two-dimensional soil gas concentration profiles for both hydrocarbons and oxygen and estimate hydrocarbon indoor air concentrations as a function of site-specific conditions such as source strength and depth, reaction rate constant, soil characteristics and building features. The soil gas concentration profiles generated by this new model are shown in good agreement with three-dimensional numerical simulations and two-dimensional measured soil gas data from a field study. This implies that for cases involving diffusion dominated soil gas transport, steady state conditions and homogenous source and soil, this analytical model can be used as a fast and easy-to-use risk screening tool by replicating the results of 3-D numerical simulations but with much less computational effort.

A Petroleum Vapor Intrusion Model Involving Upward Advective Soil Gas Flow Due to Methane Generation.

At petroleum vapor intrusion (PVI) sites at which there is significant methane generation, upward advective soil gas transport may be observed. To evaluate the health and explosion risks that may exist under such scenarios, a one-dimensional analytical model describing these processes is introduced in this study. This new model accounts for both advective and diffusive transport in soil gas and couples this with a piecewise first-order aerobic biodegradation model, limited by oxygen availability. The predicted results from the new model are shown to be in good agreement with the simulation results obtained from a three-dimensional numerical model. These results suggest that this analytical model is suitable for describing cases involving open ground surface beyond the foundation edge, serving as the primary oxygen source. This new analytical model indicates that the major contribution of upward advection to indoor air concentration could be limited to the increase of soil gas entry rate, since the oxygen in soil might already be depleted owing to the associated high methane source vapor concentration.

Evaluation of site-specific lateral inclusion zone for vapor intrusion based on an analytical approach.

In 2002, U.S. EPA proposed a general buffer zone of approximately 100 feet (30 m) laterally to determine which buildings to include in vapor intrusion (VI) investigations. However, this screening distance can be threatened by factors such as extensive surface pavements. Under such circumstances, EPA recommended investigating soil vapor migration distance on a site-specific basis. To serve this purpose, we present an analytical model (AAMLPH) as an alternative to estimate lateral VI screening distances at chlorinated compound-contaminated sites. Based on a previously introduced model (AAML), AAMLPH is developed by considering the effects of impervious surface cover and soil geology heterogeneities, providing predictions consistent with the three-dimensional (3-D) numerical simulated results. By employing risk-based and contribution-based screening levels of subslab concentrations (50 and 500 µg/m(3), respectively) and source-to-subslab attenuation factor (0.001 and 0.01, respectively), AAMLPH suggests that buildings greater than 30 m from a plume boundary can still be affected by VI in the presence of any two of the three factors, which are high source vapor concentration, shallow source and significant surface cover. This finding justifies the concern that EPA has expressed about the application of the 30 m lateral separation distance in the presence of physical barriers (e.g., asphalt covers or ice) at the ground surface.

Vapor intrusion attenuation factors relative to subslab and source, reconsidered in light of background data.

The basis upon which recommended attenuation factors for vapor intrusion (VI) have been derived are reconsidered. By making a fitting curve to the plot showing the dependence of observed indoor air concentration (c(in)) on subslab concentration (c(ss)) for residences in EPA database, an analytical equation is obtained to identify the relationship among c(in), css and the averaged background level. The new relationship indicates that subslab measurements may serve as a useful guide only if c(ss) is above 500 µg/m(3). Otherwise, c(in) is independent of c(ss), with a distribution in good agreements with other studies of background levels. Therefore, employing this screening value (500 µg/m(3)), new contaminant concentration attenuation factors are proposed for VI, and the values for groundwater-to-indoor and subslab-to-indoor air concentration attenuation factors are 0.004 and 0.02, respectively. The former is applied to examining the reported temporal variations of c(in) obtained during a long-term monitoring study. The results show that using this new groundwater-to-indoor air concentration attenuation factor also provides a reasonably conservative estimate of c(in).

Thermodynamic study of (anthracene + phenanthrene) solid state mixtures.

Polycyclic aromatic hydrocarbons (PAH) are common components of many materials, such as petroleum and various types of tars. They are generally present in mixtures, occurring both naturally and as byproducts of fuel processing operations. It is important to understand the thermodynamic properties of such mixtures in order to understand better and predict their behavior (i.e., fate and transport) in the environment and in industrial operations. To characterize better the thermodynamic behavior of PAH mixtures, the phase behavior of a binary (anthracene + phenanthrene) system was studied by differential scanning calorimetry, X-ray diffraction, and the Knudsen effusion technique. Mixtures of (anthracene + phenanthrene) exhibit non-ideal mixture behavior. They form a lower-melting, phenanthrene-rich phase with an initial melting temperature of 372 K (identical to the melting temperature of pure phenanthrene) and a vapor pressure of roughly lnP/Pa = -2.38. The phenanthrene-rich phase coexists with an anthracene-rich phase when the mole fraction of phenanthrene (xP) in the mixture is less than or equal to 0.80. Mixtures initially at xP = 0.90 consist entirely of the phenanthrene-rich phase and sublime at nearly constant vapor pressure and composition, consistent with azeotrope-like behavior. Quasi-azeotropy was also observed for very high-content anthracene mixtures (2.5 < xP < 5) indicating that anthracene may accommodate very low levels of phenanthrene in its crystal structure.

Estimation of contaminant subslab concentration in petroleum vapor intrusion.

In this study, the development and partial validation are presented for an analytical approximation method for prediction of subslab contaminant concentrations in PVI. The method involves combining an analytic approximation to soil vapor transport with a piecewise first-order biodegradation model (together called the Analytic Approximation Method, including Biodegradation, AAMB), the result of which calculation provides an estimate of contaminant subslab concentrations, independent of building operation conditions. Comparisons with three-dimensional (3-D) simulations and another PVI screening tool, BioVapor, show that the AAMB is suitable for application in a scenario involving a building with an impermeable foundation surrounded by open ground surface, where the atmosphere is regarded as the primary oxygen source. Predictions from the AAMB can be used to determine the required vertical source-building separation, given a subslab screening concentration, allowing identification of buildings at risk for PVI. This equation shows that the "vertical screening distance" suggested by U.S. EPA is sufficient in most cases, as long as the total petroleum hydrocarbon (TPH) soil gas concentration at the vapor source does not exceed 50-100mg/L. When the TPH soil gas concentration of the vapor source approaches a typical limit, i.e. 400mg/L, the "vertical screening distance" required would be much greater.