Simulated Soil Vapor Intrusion Attenuation Factors Including Biodegradation for Petroleum Hydrocarbons

Aerobic biodegradation can contribute significantly to the attenuation of petroleum hydrocarbons vapors in the unsaturated zone; however, most regulatory guidance for assessing potential human health risks via vapor intrusion to indoor air either neglect biodegradation in developing generic screening levels or allow for only one order of magnitude additional attenuation for aerobically degradable compounds, which may be overly conservative in some cases. This paper describes results from three-dimensional numerical model simulations of vapor intrusion for petroleum hydrocarbons to assess the influence of aerobic biodegradation on the attenuation factor for a variety of source concentrations and depths for residential buildings with basements and slab-on-grade construction. The simulations conducted in this study provide a framework for understanding the degree to which bioattenuation will occur under a variety of scenarios and provide insight into site conditions that will result in significant biodegradation. This improved understanding may be used to improve the conceptual model of contaminant transport, guide field data collection and interpretation, and estimate semi-site-specific attenuation factors for combinations of source concentrations, source depth, oxygen distribution, and building characteristics where site conditions reasonably match the scenarios simulated herein.     

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.     

A Model for Determination of the Phase Distribution of Petroleum Hydrocarbons at Release Sites

A model and computer-based numeric approximation for computing the equilibrium distributions of contaminants at petroleum release sites is presented. A database of contaminant-specific parameters, including solubility and organic-carbon partitioning coefficient, is assembled. Applications and limitations of the model are discussed.     

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.     

Biodegradation of Petroleum Hydrocarbons by Pseudomonas putida Strain MHF 7109

Pseudomonas putida MHF 7109 has been isolated and identified from cow dung microbial consortium for biodegradation of selected petroleum hydrocarbon compounds – benzene, toluene, and o‐xylene (BTX). Each compound was applied separately at concentrations of 50, 100, 250, and 500 mg L^?1 in minimal salt medium to evaluate degradation activity of the identified microbial strain. The results indicated that the strain used has high potential to degrade BTX at a concentration of 50 mg L^?1 within a period of 48, 96, and 168 h, respectively; whereas the concentration of 100 mg L^?1 of benzene and toluene was found to be completely degraded within 120 and 168 h, respectively. Sixty‐two percent of o‐xylene were degraded within 168 h at the 100 mg L^?1 concentration level. The maximum degradation rates for BTX were 1.35, 1.04, and 0.51 mg L^?1 h^?1, respectively. At higher concentrations (250 and 500 mg L^?1) BTX inhibited the activity of microorganisms. The mass spectrometry analysis identified the intermediates as catechol, 2‐hydroxymuconic semialdehyde, 3‐methylcatechol, cis‐2‐hydroxypenta‐2,4‐dienoate, 2‐methylbenzyl alcohol, and 1,2‐dihydroxy‐6‐methylcyclohexa‐3,5‐dienecarboxylate, for BTX, respectively. P. putida MHF 7109 has been found to have high potential for biodegradation of volatile petroleum hydrocarbons.     

Field Study of Soil Vapor Extraction for Reducing Off-Site Vapor Intrusion

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.     

Evidence for Instantaneous Oxygen-Limited Biodegradation of Petroleum Hydrocarbon Vapors in the Subsurface

Petroleum hydrocarbon vapors biodegrade aerobically in the subsurface. Depth profiles of petroleum hydrocarbon vapor and oxygen concentrations from seven locations in sandy and clay soils across four states of Australia are summarized. The data are evaluated to support a simple model of biodegradation that can be used to assess hydrocarbon vapors migrating toward built environments. Multilevel samplers and probes that allow near‐continuous monitoring of oxygen and total volatile organic compounds (VOCs) were used to determine concentration depth profiles and changes over time. Collation of all data across all sites showed distinct separation of oxygen from hydrocarbon vapors, and that most oxygen and hydrocarbon concentration profiles were linear or near linear with depth. The low detection limit on the oxygen probe data and because it is an in situ measurement strengthened the case that little or no overlapping of oxygen and hydrocarbon vapor concentration profiles occurred, and that indeed oxygen and hydrocarbon vapors were largely only coincident near the location where they both decreased to zero. First‐order biodegradation rates determined from all depth profiles were generally lower than other published rates. With lower biodegradation rates, the overlapping of depth profiles might be expected, and yet such overlapping was not observed. A model of rapid (instantaneous) reaction of oxygen and hydrocarbon vapors compared to diffusive transport processes is shown to explain the important aspects of the 13 depth profiles. The model is simply based on the ratio of diffusion coefficients of oxygen and hydrocarbon vapors, the ratio of the maximum concentrations of oxygen and hydrocarbon vapors, the depth to the maximum hydrocarbon source concentration, and the stoichiometry coefficient. Whilst simple, the model offers the potential to incorporate aerobic biodegradation into an oxygen‐limited flux‐reduction approach for vapor intrusion assessments of petroleum hydrocarbon compounds.     

Organic Acid Derivatization Techniques Applied to Petroleum Hydrocarbon Transformations in Subsurface Environments

Evidence for the natural microbial remediation of subsurface fuel contamination situations should include identification and analysis of transformation or degradation products. In this way. u mass balance between fuel constituents and end products may be approached to monitor cleanup progress. Application of advanced organic acid metabolite derivatization techniques to several known sites of organic compounds and fuel mixture contamination provide valuable information on the pathways and progress of microbial transformation. Good correlation between observed metabolites and transformation pathways of aromatic fuel constituents were observed at the sites.     

Efficient Quantification of Total Petroleum Hydrocarbons and Applications at Two Contaminated Sites

Characterization and remediation of petroleum contamination are complicated issues due to variable product compositions and site conditions. Generic group analytical methods such as total petroleum hydrocarbon (TPH) methods have played important field screening and regulatory functions for site characterization and cleanup. This study evaluated the application of three TPH methods (a GC/MS method, a spectrometric method EPA 418.1, and a rapid field method PetroFLAG). The results showed that quantification of TPH could be attained efficiently by a combination of rapid field methods (i.e., PetroFLAG) and more sophisticated fraction-specific and target-compound methods. TPH distributions suggested different source release information for two sites with different contaminant mixtures and climate conditions. TPH was also found to correlate with reductive redox capacity (RDC), an important parameter for the design of oxidative remediation schemes. The results indicated that good site specific correlations could be established to better estimate costs of the injection of chemical oxidants if necessary. RDC values varied broadly for both background (83 ˜ 569 meq/kg) and contaminated source (523 ˜ 6044 meq/kg) samples collected from actual sites.     

Dynamics of the Subsurface Temperature Field Caused by Mining-Related Groundwater Management

The subsurface temperature field was studied on a set of 46 borehole logs measured in the vicinity of uranium deposits in the Bohemian Cretaceous Basin. Vertical variations of the steady state temperature and the temperature gradient are governed by thermal conductivity which strongly varies in dependence on lithology. Large departures from undisturbed temperature detected in many holes are associated with uranium mining. A positive anomaly is observed in leaching fields where large amounts of acid are injected into the uranium-bearing Cenomanian. A negative anomaly is linked to the operation of hydraulic barriers which enclose the mining area and helps to contain pollution by pumping clean water into the Cenomanian aquifer. The spatial distribution of the observed temperature anomalies helps to map the migration of the fluids used in both processes. The temperature disturbance is propagated from the Cenomanian aquifer up through overlying impermeable sediments. The good fit of transient conductive models to the measured temperatures rules out heat advection and hence upward water flow towards and contamination of the upper Middle Turonian aquifer in the vicinity of the holes studied.     

Field Evaluation of Arid Soils Wetting Pattern in Subsurface Drip Irrigation Scheme

A field study evaluating wetted radius (Wr), downward depth (Dd), and upward movement (Um) under different emitter discharges and lateral depths was conducted. Four emitter discharges (2, 4, 8, and 16 L/h) and four lateral depths (0, 10, 20, and 30 cm) were tested in a clay loam soil. Relationships were found between the emitter discharge and lateral depth versus Wr, Dd, and Um. Wetting area at the surface occurs under different emitter discharges and lateral depths except at 30 cm lateral depth. At lateral depth of 0 and 10 cm, Wr and emitter discharge were positively correlated. The Dd was not affected by emitter discharge except for laterals installed at 20 cm depth. At 30 cm lateral depth, the correlations between each of Wr, Um, and Dd with emitter discharge were poor. The ratios of Wr/Dd and Um/Dd, with respect to emitter position, were less than unity over different emitter discharges and lateral depths. These results shed some light on the design of subsurface drip irrigation scheme so that the spacing between emitters should be determined based on the lateral depths and discharge of emitters. Evaporation losses were negligible for the 30‐cm‐lateral depth since the upward moisture movement has not reached the soil surface area at all discharge rates tested in the study.     

Field Study of Subsurface Heterogeneity with Steady‐State Hydraulic Tomography

Remediation of subsurface contamination requires an understanding of the contaminant (history, source location, plume extent and concentration, etc.), and, knowledge of the spatial distribution of hydraulic conductivity (K) that governs groundwater flow and solute transport. Many methods exist for characterizing K heterogeneity, but most if not all methods require the collection of a large number of small‐scale data and its interpolation. In this study, we conduct a hydraulic tomography survey at a highly heterogeneous glaciofluvial deposit at the North Campus Research Site (NCRS) located at the University of Waterloo, Waterloo, Ontario, Canada to sequentially interpret four pumping tests using the steady‐state form of the Sequential Successive Linear Estimator (SSLE) ( Yeh and Liu 2000 ). The resulting three‐dimensional (3D) K distribution (or K‐tomogram) is compared against: ( 1 ) K distributions obtained through the inverse modeling of individual pumping tests using SSLE, and ( 2 ) effective hydraulic conductivity (K_eff) estimates obtained by automatically calibrating a groundwater flow model while treating the medium to be homogeneous. Such a K_eff is often used for designing remediation operations, and thus is used as the basis for comparison with the K‐tomogram. Our results clearly show that hydraulic tomography is superior to the inversions of single pumping tests or K_eff estimates. This is particularly significant for contaminated sites where an accurate representation of the flow field is critical for simulating contaminant transport and injection of chemical and biological agents used for active remediation of contaminant source zones and plumes.     

民乐—山丹地震地下流体异常场特征及其成因分析

介绍了2003年10月25日民乐-山丹MS6.1地震前地下流体异常场的时空特征及其演化,分析了地下流体异常场的成因。研究结果表明,民乐-山丹地震地下流体前兆场具有异常时间长、异常项次多、异常范围大的特征,其原因是受青藏块体整体构造和地震活动水平增强以及2001年11月14日昆仑山口西8.1地震的影响。