Vapor Intrusion Investigations and Decision-Making: A Critical Review.

At sites impacted by volatile organic compounds (VOCs), vapor intrusion (VI) is the pathway with the greatest potential to result in actual human exposure. Since sites with VI were first widely publicized in late 1990s, the scientific understanding of VI has evolved considerably. The VI conceptual model has been extended beyond relatively simple scenarios to include nuances, such as biological and hydrogeological factors that may limit the potential for VI and alternative pathways, such as preferential pathways and direct building contact/infiltration that may enhance VI in some cases. Regulatory guidance documents typically recommend initial concentration- or distance-based screening to evaluate whether VI may be a concern, followed by a multiple-lines-of-evidence (MLE) investigation approach for sites that do not screen out. These recommendations for detailed evaluation of VI currently focus on monitoring of VOC concentrations in groundwater, soil gas, and indoor air and can be supplemented by other lines of evidence. In this Critical Review, we summarize key elements important to VI site characterization, provide the status and current understanding, and highlight data interpretation challenges, as well as innovative tools developed to help overcome the challenges. Although there have been significant advances in the understanding of VI in the past 20 years, limitations and knowledge gaps in screening, investigation methods, and modeling approaches still exist. Potential areas for further research include improved initial screening methods that account for the site-specific role of barriers, improved understanding of preferential pathways, and systematic study of buildings and infrastructure other than single-family residences.

A source depletion model for vapor intrusion involving the influence of building characteristics.

If volatile organic compound (VOC)-contaminated soil exists underneath a building, vapors may migrate upwards and intrude into the interior air of the building. Most previous models used to simulate vapor intrusion (VI) were developed by assuming that the source was constant, although a few recent models, such as the Risk-Based Corrective Action (RBCA) Tool Kit (TK) model, have been developed to consider source depletion (SD). However, the RBCA TK model ignores the effects of building characteristics due to its assumption that the ground is not covered by the actual building it models, which leads to incorrect results since the presence of the building affects the SD. In this study, a SD model is developed based on the three processes of VI while considering the impact of key building parameters on SD. The proposed model (i.e., the SD model) still follows the law of mass conservation, and the sensitivity analysis shows that the soil-building pressure differential (dP) is an important building characteristic that affects SD. Taking trichloroethylene (TCE) for simulation in the case of a soil concentration below the saturation concentration, as the soil permeability decreases, the differences in the results between the SD model and RBCA TK model decrease; as the Peclet number decreases, the effect of the dP on the results of the SD model decreases. The new model only accounts for the migration of contaminants at the source of depletion; therefore, the model is more applicable for these contaminants, which are considered to have low-biodegradable characteristics. Furthermore, since the model emphasizes the impact of buildings on the source, it is applicable when there is a considerable building area above the source, such as large commercial buildings or residential communities with underground parking lots, which exist in most cities.

Improved exposure estimation in soil screening and cleanup criteria for volatile organic chemicals.

Soil cleanup criteria define acceptable concentrations of organic chemical constituents for exposed humans. These criteria sum the estimated soil exposure over multiple pathways. Assumptions for ingestion, dermal contact, and dust exposure generally presume a chemical persists in surface soils at a constant concentration level for the entire exposure duration. For volatile chemicals, this is an unrealistic assumption. A calculation method is presented for surficial soil criteria that include volatile depletion of chemical for these uptake pathways. The depletion estimates compare favorably with measured concentration profiles and with field measurements of soil concentration. Corresponding volatilization estimates compare favorably with measured data for a wide range of volatile and semivolatile chemicals, including instances with and without the presence of a mixed-chemical residual phase. Selected examples show application of the revised factors in estimating screening levels for benzene in surficial soils. Integr Environ Assess Manag 2017;13:861-869. © 2017 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Numerical model investigation for potential methane explosion and benzene vapor intrusion associated with high-ethanol blend releases.

Ethanol-blended fuel releases usually stimulate methanogenesis in the subsurface, which could pose an explosion risk if methane accumulates in a confined space above the ground where ignitable conditions exist. Ethanol-derived methane may also increase the vapor intrusion potential of toxic fuel hydrocarbons by stimulating the depletion of oxygen by methanotrophs, and thus inhibiting aerobic biodegradation of hydrocarbon vapors. To assess these processes, a three-dimensional numerical vapor intrusion model was used to simulate the degradation, migration, and intrusion pathway of methane and benzene under different site conditions. Simulations show that methane is unlikely to build up to pose an explosion hazard (5% v/v) if diffusion is the only mass transport mechanism through the deeper vadose zone. However, if methanogenic activity near the source zone is sufficiently high to cause advective gas transport, then the methane indoor concentration may exceed the flammable threshold under simulated conditions. During subsurface migration, methane biodegradation could consume soil oxygen that would otherwise be available to support hydrocarbon degradation, and increase the vapor intrusion potential for benzene. Vapor intrusion would also be exacerbated if methanogenic activity results in sufficiently high pressure to cause advective gas transport in the unsaturated zone. Overall, our simulations show that current approaches to manage the vapor intrusion risk for conventional fuel released might need to be modified when dealing with some high ethanol blend fuel (i.e., E20 up to E95) releases.

Methane bioattenuation and implications for explosion risk reduction along the groundwater to soil surface pathway above a plume of dissolved ethanol.

Fuel ethanol releases can stimulate methanogenesis in impacted aquifers, which could pose an explosion risk if methane migrates into enclosed spaces where ignitable conditions exist. To assess this potential risk, a flux chamber was emplaced on a pilot-scale aquifer exposed to continuous release (21 months) of an ethanol solution (10% v:v) that was introduced 22.5 cm below the water table. Despite methane concentrations within the ethanol plume reaching saturated levels (20-23 mg/L), the maximum methane concentration reaching the chamber (21 ppm(v)) was far below the lower explosion limit in air (50,000 ppm(v)). The low concentrations of methane observed in the chamber are attributed to methanotrophic activity, which was highest in the capillary fringe. This was indicated by methane degradation assays in microcosms prepared with soil samples from different depths, as well as by PCR measurements of pmoA, which is a widely used functional gene biomarker for methanotrophs. Simulations with the analytical vapor intrusion model "Biovapor" corroborated the low explosion risk associated with ethanol fuel releases under more generic conditions. Model simulations also indicated that depending on site-specific conditions, methane oxidation in the unsaturated zone could deplete the available oxygen and hinder aerobic benzene biodegradation, thus increasing benzene vapor intrusion potential. Overall, this study shows the importance of methanotrophic activity near the water table to attenuate methane generated from dissolved ethanol plumes and reduce its potential to migrate and accumulate at the surface.

Indoor vapor intrusion with oxygen-limited biodegradation for a subsurface gasoline source.

Development and results are presented for a subsurface soil to indoor air chemical vapor intrusion model that includes oxygen-limited biodegradation. The algebraic model incorporates a steady-state subsurface gasoline vapor source, diffusion-dominated soil vapor transport in a homogeneous subsurface soil layer, and mixing within a building enclosure. The soil is divided into a shallow aerobic layer including biodegradation and a deeper anaerobic layer in which biodegradation is neglected. Biodegradation of multiple chemicals is included, with aerobic first-order reaction kinetics estimated from measured data. Oxygen is supplied at the soil surface below the building foundation. Oxygen demand is attributed to a sum of multiple biodegrading chemicals and to baseline respiration of native soil organic matter. The model is solved by iteratively varying the aerobic depth to match oxygen demand to oxygen supply. Model results are calculated for ranges of source concentrations, unsaturated soil characteristics, and building parameters. Results indicate vapor intrusion of petroleum hydrocarbons can be significantly less than indicated by estimates that neglect biodegradation.