Aerobic biodegradation and volatilization near the water table constitute a coupled pathway that contributes significantly to the natural attenuation of hydrocarbons at gasoline spill sites. Rates of hydrocarbon biodegradation and volatilization were quantified by analyzing vapor transport in the unsaturated zone at a gasoline spill site in Beaufort, South Carolina. Aerobic biodgradation rates decreased with distance above the water table, ranging from 0.20 to 1.5 g m−3 d−1 for toluene, from 0.24 to 0.38 g m−3 d−1 for xylene, from 0.09 to 0.24 g m−3 d−1 for cyclohexene, from 0.05 to 0.22 g m−3 d−1 for ethylbenzene, and from 0.02 to 0.08 g m−3 d−1 for benzene. Rates were highest in the capillary zone, where 68% of the total hydrocarbon mass that volatilized from the water table was estimated to have been biodegraded. Hydrocarbons were nearly completely degraded within 1m above the water table. This large loss underscores the importance of aerobic biodradation in limiting the transport of hydrocarbon vapors in the unsaturated zone and implies that vapor‐plume migration to basements and other points of contact may only be significant if a source of free product is present. Furthermore, because transport of the hydrocarbon in the unsaturated zone can be limited relative to that of oxygen and carbon dioxide, soil‐gas surveys conducted at hydrocarbon‐spill sites would benefit by the inclusion of oxygen‐ and carbon‐dioxide‐gas concentration measurements. Aerobic degradation kinetics in the unsaturated zone were approximately first‐order. First‐order rate constants near the water table were highest for cyclohexene (0.21–0.65 d−1) and nearly equivalent for ethylbenzene (0.11–0.31 d−1), xylenes (0.10–0.31 d−1), toluene (0.09–0.30 d−1), and benzene (0.07–0.31 d−1). Hydrocarbon mass loss rates at the water table resulting from the coupled aerobic biodgradation and volatilization process were determined by extrapolating gas transport rates through the capillary zone. Mass loss rates from groundwater were highest for toluene (0.20–0.84 g m−2 d−1), followed by xylenes (0.12–0.69 g m−2 d−1), cyclohexene (0.05–0.15 g m−2 d−1), ethylbenzene (0.02–0.12 g m−2 d−1), and benzene (0.01–0.04 g m−2 d−1). These rates exceed predicted rates of solubilization to groundwater, demonstrating the effectiveness of aerobic biodgradation and volatilization as a combined natural attenuation pathway.

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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.

The distribution of oxygen and carbon dioxide gases in the unsaturated zone provides a geochemical signature of aerobic hydrocarbon degradation at petroleum product spill sites. The fluxes of these gases are proportional to the rate of aerobic biodegradation and are quantified by calibrating a mathematical transport model to the oxygen and carbon dioxide gas concentration data. Reaction stoichiometry is assumed to convert the gas fluxes to a corresponding rate of hydrocarbon degradation. The method is applied at a gasoline spill site in Galloway Township, New Jersey, to determine the rate of aerobic degradation of hydrocarbons associated with passive and bioventing remediation field experiments. At the site, microbial degradation of hydrocarbons near the water table limits the migration of hydrocarbon solutes in groundwater and prevents hydrocarbon volatilization into the unsaturated zone. In the passive remediation experiment a site‐wide degradation rate estimate of 34,400 g yr−1 (11.7 gal. yr−1) of hydrocarbon was obtained by model calibration to carbon dioxide gas concentration data collected in December 1989. In the bioventing experiment, degradation rate estimates of 46.0 and 47.9 g m−2 yr−1(1.45 × 10−3 and 1.51 × 10−3 gal. ft.−2yr−1) of hydrocarbon were obtained by model calibration to oxygen and carbon dioxide gas concentration data, respectively. Method application was successful in quantifying the significance of a naturally occurring process that can effectively contribute to plume stabilization.

Vapor intrusion (VI) involves migration of volatile contaminants from subsurface through unsaturated soil into overlying buildings. In 2015, the US EPA recommended an approach for screening VI risks associated with gasoline releases from underground storage tank (UST) sites. Additional assessment of the VI risk from petroleum hydrocarbons was deemed unnecessary for buildings separated from vapor sources by more than recommended vertical screening distances. However, these vertical screening distances did not apply to potential VI risks associated with releases of former leaded gasoline containing 1,2‐dichloroethane (1,2‐DCA), because of a lack of empirical data on the attenuation of 1,2‐DCA in soil gas. This study empirically evaluated 144 paired measurements of 1,2‐DCA concentrations in soil gas and groundwater collected at 47 petroleum UST sites combined with BioVapor modeling. This included (1) assessing the frequency of 1,2‐DCA detections in soil gas below 10−6 risk‐based screening levels at different vertical separation distances and (2) comparing the US EPA recommended vertical screening distances with those predicted by BioVapor modeling. Vertical screening distances were predicted for different soil types using aerobic biodegradation rate constants estimated from the measured soil‐gas data combined with conservative estimates of source concentrations. The modeling indicates that the vertical screening distance of 6 feet (1.8 m) recommended for dissolved‐phase sources is applicable for 1,2‐DCA below certain threshold concentrations in groundwater, while 15 feet (4.6 m) recommended for light nonaqueous phase liquid (LNAPL) sources is applicable for sites with clay and loam soils in the vadose zone, but not sand, if 1,2‐DCA concentrations in groundwater exceed 150 μg/L. This dependence of the predicted vertical screening distances on soil type places added emphasis on proper soil characterization for VI screening at sites with 1,2‐DCA sources. The soil‐gas data suggests that a vertical screening distance of 15 feet (4.6 m) is necessary for both dissolved‐phase and LNAPL sources.