Review of Quantitative Surveys of the Length and Stability of MTBE,TBA, and Benzene Plumes in Groundwater at UST Sites

Quantitative information regarding the length and stability condition of groundwater plumes of benzene, methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) has been compiled from thousands of underground storage tank (UST) sites in the United States where gasoline fuel releases have occurred. This paper presents a review and summary of 13 published scientific surveys, of which 10 address benzene and/or MTBE plumes only, and 3 address benzene, MTBE, and TBA plumes. These data show the observed lengths of benzene and MTBE plumes to be relatively consistent among various regions and hydrogeologic settings, with median lengths at a delineation limit of 10 µg/L falling into relatively narrow ranges from 101 to 185 feet for benzene and 110 to 178 feet for MTBE. The observed statistical distributions of MTBE and benzene plumes show the two plume types to be of comparable lengths, with 90th percentile MTBE plume lengths moderately exceeding benzene plume lengths by 16% at a 10‐µg/L delineation limit (400 feet vs. 345 feet) and 25% at a 5‐µg/L delineation limit (530 feet vs. 425 feet). Stability analyses for benzene and MTBE plumes found 94 and 93% of these plumes, respectively, to be in a nonexpanding condition, and over 91% of individual monitoring wells to exhibit nonincreasing concentration trends. Three published studies addressing TBA found TBA plumes to be of comparable length to MTBE and benzene plumes, with 86% of wells in one study showing nonincreasing concentration trends.     

An Empirical Evaluation of the Influence of Ethanol on Natural Attenuation of Gasoline Constituents

Since the 1990s, questions have arisen as to whether the release of ethanol‐blended fuel will inhibit natural attenuation of other gasoline constituents in groundwater. This study evaluated the hypothesis that ethanol affects hydrocarbon attenuation and whether the use of ethanol‐blended fuel alters the applicability of monitored natural attenuation (MNA) as an approach for managing risks at fuel‐release sites. Groundwater data from California's GeoTracker database were used to compare attenuation of benzene, toluene, methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) at sites with and without detections of ethanol. Excel‐based tools were developed to conduct attenuation evaluations on thousands of wells simultaneously. Ethanol was detected at least once in 4.5% of the wells and 0.6% of the samples of which it was analyzed. The distribution of Mann‐Kendall concentration trend analysis results and first‐order attenuation rates were essentially the same at sites with or without ethanol detections. Median plume lengths were shorter at sites where ethanol had not been detected compared to sites where ethanol was detected (36 vs. 43 m for benzene; 36 vs. 42 m for toluene; 43 vs. 52 m for MTBE; and 44 vs. 59 m for TBA). However, the distribution of plume lengths was similar irrespective of ethanol concentrations, suggesting other factors may influence plume elongation. Finally, while anaerobic ethanol degradation can result in methane generation, the distributions of methane concentrations were the same at sites with and without ethanol detections. These results suggest that the use of ethanol‐blended fuel should not limit the application of MNA at most biodegrading fuel‐release sites.     

Using DNA‐Stable Isotope Probing to Identify MTBE‐ and TBA‐Degrading Microorganisms in Contaminated Groundwater

Although the anaerobic biodegradation of methyl tert‐butyl ether (MTBE) and tert‐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 ¹³C₅‐MTBE, ¹³C₁‐MTBE (only methoxy carbon labeled), or ¹³C₄‐TBA. ¹³C‐DNA and ¹²C‐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 tert‐butyl group of MTBE and TBA. Results indicated that microorganisms were actively degrading ¹³C‐labeled MTBE and TBA in situ and the ¹³C 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 three ¹³C clone libraries and were likely to be primary degraders at the site. Sequences related to sulfate‐reducing bacteria and iron‐reducers, such as Geobacter and Geothrix, were only detected in the clone libraries where MTBE and TBA were fully labeled with ¹³C, suggesting that they were involved in processing carbon from the tert‐butyl group. Sequences similar to the Pseudomonas genus predominated in the clone library where only the methoxy carbon of MTBE was labeled with ¹³C. It is likely that members of this genus were secondary degraders cross‐feeding on ¹³C‐labeled metabolites such as acetate.     

Progress in Remediation of Groundwater at Petroleum Sites in California

Quantifying the overall progress in remediation of contaminated groundwater has been a significant challenge. We utilized the GeoTracker database to evaluate the progress in groundwater remediation from 2001 to 2011 at over 12,000 sites in California with contaminated groundwater. This paper presents an analysis of analytical results from over 2.1 million groundwater samples representing at least $100 million in laboratory analytical costs. Overall, the evaluation of monitoring data shows a large decrease in groundwater concentrations of gasoline constituents. For benzene, half of the sites showed a decrease in concentration of 85% or more. For methyl tert‐butyl ether (MTBE), this decrease was 96% and for TBE, 87%. At remediation sites in California, the median source attenuation rate was 0.18/year for benzene and 0.36/year for MTBE, corresponding to half‐lives of 3.9 and 1.9 years, respectively. Attenuation rates were positive (i.e., decreasing concentration) for benzene at 76% of sites and for MTBE at 85% of sites. An evaluation of sites with active remediation technologies suggests differences in technology effectiveness. The median attenuation rates for benzene and MTBE are higher at sites with soil vapor extraction or air sparging compared with sites without these technologies. In contrast, there was little difference in attenuation rates at sites with or without soil excavation, dual phase extraction, or in situ enhanced biodegradation. The evaluation of remediation technologies, however, did not evaluate whether specific systems were well designed or implemented and did not control for potential differences in other site factors, such as soil type.     

Field Treatment of MTBE‐Contaminated Groundwater Using Ozone/UV Oxidation

Methyl‐tertiary butyl ether (MTBE) is often found in groundwater as a result of gasoline spills and leaking underground storage tanks. An extrapolation of occurrence data in 2008 estimated at least one detection of MTBE in approximately 165 small and large public water systems serving 896,000 people nationally (United States Environmental Protection Agency [U.S. EPA] 2008). The objective of this collaborative field study was to evaluate a small groundwater treatment system to determine the effectiveness of ultraviolet (UV)/ozone treatment in removing MTBE from contaminated drinking water wells. A pilot‐scale advanced oxidation process (AOP) system was tested to evaluate the oxidation efficiency of MTBE and intermediates under field conditions. This system used ozone as an oxidizer in the presence of UV light at hydraulic retention times varying from 1 to 3 min. MTBE removal efficiencies approaching 97% were possible with this system, even with low retention times. The intermediate t‐butyl alcohol (TBA) was removed to a lesser extent (71%) under the same test conditions. The main intermediate formed in the oxidation process of the contaminated groundwater in these studies was acetone. The concentrations of the other anticipated intermediates t‐butyl formate (TBF), isopropyl alcohol (IPA), methyl acetate (MAc), and possible co‐occurring aromatics (BTEX) in the effluent were negligible.     

Exceptionally Long MTBE Plumes of the Past Have Greatly Diminished

Studies published in the late 1990s and early 2000s identified the presence of exceptionally long methyl tert‐butyl ether (MTBE) plumes (more than 600 m or 2000 feet) in groundwater and have been cited in technical literature as characteristic of MTBE plumes. However, the scientific literature is incomplete in regard to the subsequent behavior and fate of these MTBE plumes over the past decade. To address this gap, this issue paper compiles recent groundwater monitoring records for nine exceptional plumes that were identified in prior studies. These nine sites exhibited maximum historical MTBE groundwater plume lengths ranging from 820 m (2700 feet) to 3200 m (10,500 feet) in length, exceeding the lengths of 99% of MTBE plumes, as characterized in multiple surveys at underground storage tank sites across the United States. Groundwater monitoring data compiled in our review demonstrate that these MTBE plumes have decreased in length over the past decade, with five of the nine plumes exhibiting decreases of 75% or more compared to their historical maximum lengths. MTBE concentrations within these plumes have decreased by 93% to 100%, with two of the nine sites showing significant decreases (98% and 99%) such that the regulatory authority has subsequently designated the site as requiring no further action.     

Fate of MTBE Relative to Benzene in a Gasoline-Contaminated Aquifer (1993–98)

Methyl tert -butyl ether (MTBE) and benzene have been measured since 1993 in a shallow, sandy aquifer contaminated by a mid-1980s release of gasoline containing fuel oxygenates. In wells downgradient of the release area, MTBK was detected before benzene, reflecting a chromatographic-like separation of these compounds in the direction of ground water flow. Higher concentrations of MTBE and benzene were measured in the deeper sampling ports of multilevel sampling wells located near the release area, and also up to 10 feet (3 m) below the water table surface in nested wells located farther from the release area. This distribution of higher concentrations at depth is caused by recharge events that deflect originally horizontal ground water flowlines. In the laboratory, microcosms containing aquifer material incubated with uniformly labeled ¹⁴C-MTBE under aerobic and anaerobic. Fe(III)-reducing conditions indicated a low but measurable biodegradation potential (<3%¹⁴C-MTBW as ¹⁴CO₂) after a seven-month incubation period, Tert -butyl alcohol (TBA), a proposed microbial-MTBE transformation intermediate, was detected in MTBE-contaminated wells, but TBA was also measured in unsaturated release area sediments. This suggests that TBA may have been present in the original fuel spilled and does not necessarily reflect microbial degradation of MTBE. Combined, these data suggest that milligram per liter to microgram per liter decreases in MTBE concentrations relative to benzene are caused by the natural attenuation processes of dilution and dispersion with less-contaminated ground water in the direction of flow rather than biodegradation at this point source gasoline release site.     

MTBE, TBA, and TAME Attenuation in Diverse Hyporheic Zones

Groundwater contamination by fuel-related compounds such as the fuel oxygenates methyl tert -butyl ether (MTBE), tert -butyl alcohol (TBA), and tert -amyl methyl ether (TAME) presents a significant issue to managers and consumers of groundwater and surface water that receives groundwater discharge. Four sites were investigated on Long Island, New York, characterized by groundwater contaminated with gasoline and fuel oxygenates that ultimately discharge to fresh, brackish, or saline surface water. For each site, contaminated groundwater discharge zones were delineated using pore water geochemistry data from 15 feet (4.5 m) beneath the bottom of the surface water body in the hyporheic zone and seepage-meter tests were conducted to measure discharge rates. These data when combined indicate that MTBE, TBA, and TAME concentrations in groundwater discharge in a 5-foot (1.5-m) thick section of the hyporheic zone were attenuated between 34% and 95%, in contrast to immeasurable attenuation in the shallow aquifer during contaminant transport between 0.1 and 1.5 miles (0.1 to 2.4 km). The attenuation observed in the hyporheic zone occurred primarily by physical processes such as mixing of groundwater and surface water. Biodegradation also occurred as confirmed in laboratory microcosms by the mineralization of U- ¹⁴C-MTBE and U-¹⁴C-TBA to ¹⁴CO₂ and the novel biodegradation of U- ¹⁴C-TAME to ¹⁴CO₂ under oxic and anoxic conditions. The implication of fuel oxygenate attenuation observed in diverse hyporheic zones suggests an assessment of the hyporheic zone attenuation potential (HZAP) merits inclusion as part of site assessment strategies associated with monitored or engineered attenuation.     

A Practical Approach to the Design, Monitoring, and Optimization of In Situ MTBE Aerobic Biobarriers

A paradigm for the design, monitoring, and optimization of in situ methyl tert -butyl ether (MTBE) aerobic biobarriers is presented. In this technology, an oxygen-rich biologically reactive treatment zone (the "biobarrier") is established in situ and downgradient of the source of dissolved MTBE contamination in groundwater, typically gasoline-impacted soils resulting from leaks and spills at service station sites or other fuel storage and distribution facilities. The system is designed so that groundwater containing dissolved MTBE flows to, and through, the biobarrier treatment zone, ideally under natural gradient conditions so that no pumping is necessary. As the groundwater passes through the biobarrier, the MTBE is converted by microorganisms to innocuous by-products. The system also reduces concentrations of other aerobically degradable chemicals dissolved in the groundwater, such as benzene, toluene, xylenes, and tert -butyl alcohol. This design paradigm is based on experience gained while designing, monitoring, and optimizing pilot-scale and full-scale MTBE biobarrier systems. It is largely empirically based, although the design approach does rely on simple engineering calculations. The paradigm emphasizes gas injection–based oxygen delivery schemes, although many of the steps would be common to other methods of delivering oxygen to aquifers.     

In Situ Biotreatment of TBA with Recirculation/Oxygenation

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. In the first experiment, a single recirculating well pair with bromide tracer and oxygen amendment successfully delivered oxygen to the subsurface for 42 d. 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 d 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.     

Evaluation of Seasonal Factors on Petroleum Hydrocarbon Vapor Biodegradation and Intrusion Potential in a Cold Climate

A detailed seasonal study of soil vapor intrusion at a cold climate site with average yearly temperature of 1.9 °C was conducted at a house with a crawlspace that overlay a shallow dissolved‐phase petroleum hydrocarbon (gasoline) plume in North Battleford, Saskatchewan, Canada. This research was conducted primarily to assess if winter conditions, including snow/frost cover, and cold soil temperatures, influence aerobic biodegradation of petroleum vapors in soil and the potential for vapor intrusion. Continuous time‐series data for oxygen, pressure differentials, soil temperature, soil moisture, and weather conditions were collected from a high‐resolution monitoring network. Seasonal monitoring of groundwater, soil vapor, crawlspace air, and indoor air was also undertaken. Petroleum hydrocarbon vapor attenuation and biodegradation rates were not significantly reduced during low temperature winter months and there was no evidence for a significant capping effect of snow or frost cover that would limit oxygen ingress from the atmosphere. In the residual light nonaqueous phase liquid (LNAPL) source area adjacent to the house, evidence for biodegradation included rapid attenuation of hydrocarbon vapor concentrations over a vertical interval of approximately 0.9 m, and a corresponding decrease in oxygen to less than 1.5% v/v. In comparison, hydrocarbon vapor concentrations above the dissolved plume and below the house were much lower and decreased sharply within a few tens of centimeters above the groundwater source. Corresponding oxygen concentrations in soil gas were at least 10% v/v. A reactive transport model (MIN3P‐DUSTY) was initially calibrated to data from vertical profiles at the site to obtain biodegradation rates, and then used to simulate the observed soil vapor distribution. The calibrated model indicated that soil vapor transport was dominated by diffusion and aerobic biodegradation, and that crawlspace pressures and soil gas advection had little influence on soil vapor concentrations.     

222Rn as Natural Tracer for LNAPL Recovery in a Crude Oil‐Contaminated Aquifer

The objective of this study was to investigate whether ²²²Rn in groundwater can be used as a tracer for light non‐aqueous phase liquid (LNAPL) quantification at a field site treated by dual‐phase LNAPL removal. After the break of a pipeline, 5 ha of soil in the nature reserve Coussouls de Crau in southern France was contaminated by 5100 m³ of crude oil. Part of this oil seeped into the underlying gravel aquifer and formed a floating oil body of about 3.9 ha. The remediation consists of plume management by hydraulic groundwater barriers and LNAPL extraction in the source zone. ²²²Rn measurements were performed in 21 wells in and outside the source zone during 15 months. In uncontaminated groundwater, the radon activity was relatively constant and remained always >11 Bq/L. The variability of radon activity measurements in wells affected by the pump‐and‐skim system was consistent with the measurements in wells that were not impacted by the system. The mean activities in wells in the source zone were, in general, significantly lower than in wells upgradient of the source zone, owing to partitioning of ²²²Rn into the oil phase. The lowest activities were found in zones with high non‐aqueous phase liquid (NAPL) recovery. LNAPL saturations around each recovery well were furthermore calculated during a period of high groundwater level, using a laboratory‐determined crude oil–water partitioning coefficient of 38.5 ± 2.9. This yielded an estimated volume of residual crude oil of 309 ± 93 m³ below the capillary fringe. We find that ²²²Rn is a useful and cheap groundwater tracer for finding zones of good LNAPL recovery in an aquifer treated by dual‐phase LNAPL removal, but that quantification of NAPL saturation using Rn is highly uncertain.     

A Mass Balance Approach to Resolving LNAPL Stability

This article explores the hypothesis that natural losses of light nonaqueous phase liquids (LNAPLs) through dissolution and evaporation can control the overall extent of LNAPL bodies and LNAPL fluxes observed within LNAPL bodies. First, a proof‐of‐concept sand tank experiment is presented. An LNAPL (methyl tert‐butyl ether) was injected into a sand tank at five constant injection rates that were increased stepwise. Initially, for each injection rate the LNAPL bodies expanded quickly. With time the rate of expansion of the LNAPL bodies slowed and at extended times the extent of the LNAPL became constant. Attainment of a stable LNAPL extent is attributed to rates of LNAPL addition being equal to rates of LNAPL losses through dissolution and evaporation. Secondly, analytical solutions are developed to extrapolate the processes observed in the proof‐of‐concept experiment to dimensions and time frames that are consistent with field‐scale LNAPL bodies. Three LNAPL body geometries that are representative of common field conditions are considered including one‐dimensional, circular, and oblong shapes. Using idealized conditions, the solutions describe volumetric LNAPL fluxes as a function of position in LNAPL bodies and the overall extent of LNAPL bodies as a function of time. Results from both the proof‐of‐concept experiment and the mathematical developments illustrate that natural losses of LNAPL can play an important role in governing LNAPL fluxes within LNAPL bodies and the overall extent of LNAPL bodies.     

Arsenic Cycling in Hydrocarbon Plumes: Secondary Effects of Natural Attenuation

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe‐hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude‐oil‐contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe‐hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe‐hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction.     

Evaluation of volatilization as a natural attenuation pathway for MTBE

Volatilization and diffusion through the unsaturated zone can be an important pathway for natural attenuation remediation of methyl tert-butyl ether (MTBE) at gasoline spill sites. The significance of this pathway depends primarily on the distribution of immiscible product within the unsaturated zone and the relative magnitude of aqueous-phase advection (ground water recharge) to gaseous-phase diffusion. At a gasoline spill site in Laurel Bay, South Carolina, rates of MTBE volatilization from ground water downgradient from the source are estimated by analyzing the distribution of MTBE in the unsaturated zone above a solute plume. Volatilization rates of MTBE from ground water determined by transport modeling ranged from 0.0020 to 0.0042 g m(-2)/year, depending on the assumed rate of ground water recharge. Although diffusive conditions at the Laurel Bay site are favorable for volatilization, mass loss of MTBE is insignificant over the length (230 m) of the solute plume. Based on this analysis, significant volatilization of MTBE from ground water downgradient from source areas at other sites is not likely. In contrast, model results indicate that volatilization coupled with diffusion to the atmosphere could be a significant mass loss pathway for MTBE in source areas where residual product resides above the capillary zone. Although not documented, mass loss of MTBE at the Laurel Bay site due to volatilization and diffusion to the atmosphere are predicted to be two to three times greater than mass loading of MTBE to ground water due to dissolution and recharge. This result would imply that volatilization in the source zone may be the critical natural attenuation pathway for MTBE at gasoline spill sites, especially when considering capillary zone limitations on volatilization of MTBE from ground water and the relative recalcitrance of MTBE to biodegradation.     

Removal of Volatile Organic Compounds in Vertical Flow Filters: Predictions from Reactive Transport Modeling

Vertical flow filters are containers filled with porous medium that are recharged from top and drained at the bottom, and are operated at partly saturated conditions. They have recently been suggested as treatment technology for groundwater containing volatile organic compounds (VOCs). Numerical reactive transport simulations were performed to investigate the relevance of different filter operation modes on biodegradation and/or volatilization of the contaminants and to evaluate the potential limitation of such remediation mean due to volatile emissions. On the basis of the data from a pilot‐scale vertical flow filter intermittently fed with domestic waste water, model predictions on the system’s performance for the treatment of contaminated groundwater were derived. These simulations considered the transport and aerobic degradation of ammonium and two VOCs, benzene and methyl tertiary butyl ether (MTBE). In addition, the advective‐diffusive gas‐phase transport of volatile compounds as well as oxygen was simulated. Model predictions addressed the influence of depth and frequency of the intermittent groundwater injection, degradation rate kinetics, and the composition of the filter material. Simulation results show that for unfavorable operation conditions significant VOC emissions have to be considered and that operation modes limiting VOC emissions may limit aerobic biodegradation. However, a suitable combination of injection depth and composition of the filter material does facilitate high biodegradation rates while only little VOC emissions take place. Using such optimized operation modes would allow using vertical flow filter systems as remediation technology suitable for groundwater contaminated with volatile compounds.     

Use of Single‐Well Tracer Dilution Tests to Evaluate LNAPL Flux at Seven Field Sites

Petroleum liquids, referred to as light non‐aqueous phase liquids (LNAPLs), are commonly found beneath petroleum facilities. Concerns with LNAPLs include migration into clean soils, migration beyond property boundaries, and discharges to surface water. Single‐well tracer dilution techniques were used to measure LNAPL fluxes through 50 wells at 7 field sites. A hydrophobic tracer was mixed into LNAPL in a well. Intensities of fluorescence associated with the tracer were measured over time using a spectrometer and a fiber optic cable. LNAPL fluxes were estimated using observed changes in the tracer concentrations over time. Measured LNAPL fluxes range from 0.006 to 2.6 m/year with a mean and median of 0.15 and 0.064 m/year, respectively. Measured LNAPL fluxes are two to four orders of magnitude smaller than a common groundwater flux of 30 m/year. Relationships between LNAPL fluxes and possible governing parameters were evaluated. Observed LNAPL fluxes are largely independent of LNAPL thickness in wells. Natural losses of LNAPL through dissolution, evaporation, and subsequent biodegradation, were estimated using a simple mass balance, measured LNAPL fluxes in wells, and an assumed stable LNAPL extent. The mean and median of the calculated loss rates were found to be 24.0 and 5.0 m³/ha/year, respectively. Mean and median losses are similar to values reported by others. Coupling observed LNAPL fluxes to observed rates of natural LNAPL depletion suggests that natural losses of LNAPL may be an important parameter controlling the overall extent of LNAPL bodies.     

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.     

Free-product plume distribution and recovery modeling prediction in a diesel-contaminated volcanic aquifer

Light non-aqueous phase liquids (LNAPL) represent one of the most serious problems in aquifers contaminated with petroleum hydrocarbons liquids. To design an appropriate remediation strategy it is essential to understand the behavior of the plume. The aim of this paper is threefold: (1) to characterize the fluid distribution of an LNAPL plume detected in a volcanic low-conductivity aquifer (∼0.4 m/day from slug tests interpretation), (2) to simulate the recovery processes of the free-product contamination and (3) to evaluate the primary recovery efficiency of the following alternatives: skimming, dual-phase extraction, Bioslurping and multi-phase extraction wells. The API/Charbeneau analytical model was used to investigate the recovery feasibility based on the geological properties and hydrogeological conditions with a multi-phase (water, air, LNAPL) transport approach in the vadose zone. The modeling performed in this research, in terms of LNAPL distribution in the subsurface, show that oil saturation is 7% in the air–oil interface, with a maximum value of 70% in the capillary fringe. Equilibrium between water and LNAPL phases is reached at a depth of 1.80 m from the air–oil interface. On the other hand, the LNAPL recovery model results suggest a remarkable enhancement of the free-product recovery when simultaneous extra-phase extraction was simulated from wells, in addition to the LNAPL lens. Recovery efficiencies were 27%, 65%, 66% and 67% for skimming, dual-phase extraction, Bioslurping and multi-phase extraction, respectively. During a 3-year simulation, skimmer wells and multi-phase extraction showed the lowest and highest LNAPL recovery rates, with expected values from 207 to 163 and 2305 to 707 l-LNAPL/day, respectively. At a field level we are proposing a well distribution arrangement that alternates pairs of dual-phase well-Bioslurping well. This not only improves the recovery of the free-product plume, but also pumps the dissolve plume and enhances in situ biodegradation in the vadose zone. Thus, aquifer and soil remediation can be achieved at a shorter time. Rough calculations suggest that LNAPL can be recovered at an approximate cost of $6–$10/l.