A Comparative Plume Study of DRO,GRO, Benzene,and MTBE: Implications for Risk Management

Groundwater remediation and no-further action decision making at petroleum underground storage tank (UST) sites has largely been based on an understanding of plume length, plume stability, and attenuation rates for key hydrocarbon constituents. Regulatory guidance to support and guide such decisions is based in part on plume studies involving individual hydrocarbon constituents, namely benzene and methyl tert-butyl ether (MTBE). Questions remain regarding whether current guidance is applicable to chemical mixtures such as gasoline range organics (GRO), diesel range organics (DRO), and oxygen containing organic compounds (OCOCs) resulting from hydrocarbon biodegradation. To help address this concern, data from California's GeoTracker database were used to estimate maximum plume lengths, plume stability, and attenuation rates of DRO (which can be used as an analytical surrogate for OCOCs) and GRO relative to benzene and MTBE. The distributions of maximum plume lengths were similar for the four constituents with medians ranging from 27 to 32 m. The fraction of monitoring wells with a decreasing concentration trend ranged from 19% for DRO to 40% for MTBE, while fewer than 7% of the wells had an increasing concentration trend for any of the constituents. Median attenuation rates ranged from 0.10% day⁻¹ for DRO to 0.17% day⁻¹ for MTBE. The results suggest attenuation based risk management is appropriate for DRO and GRO plumes at most petroleum UST sites.     

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.     

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.     

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.     

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.     

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.     

Empirically Derived California Vapor Intrusion Attenuation Factors

The California Department of Toxic Substances Control (DTSC) gathered empirical data from sites contaminated with chlorinated volatile organic compounds and generated a vapor intrusion database. The database includes 52 sites across California with 213 buildings, of which, 53% are residential, and 47% are commercial/industrial (nonresidential). DTSC's objective is to improve its knowledge and understanding of vapor intrusion and derive empirical attenuation factors that are representative of the climatic conditions and types of buildings commonly found in the state. Filtering was applied to remove data of suspect quality that were potentially affected by background sources. After filtering to 600 pairs from 32 sites across California, a subslab attenuation factor (AF) was calculated yielding a 95th percentile of 0.005. After filtering to 2926 paired measurements from 39 sites across California, a soil vapor AF was calculated yielding a 95th percentile of 0.0009. The groundwater data was not analyzed due to the small size of the dataset. The AFs from this study are similar to AFs in a California-specific study by Lahvis and Ettinger (2021). Accordingly, converging lines of evidence suggest that vapor attenuation in California is different from what is observed nationwide by the United States Environmental Protection Agency (USEPA), where an AF of 0.03 was empirically derived and later recommended for initial screening of buildings for potential vapor intrusion exposure (USEPA, 2015).     

Evaluation of BTEX Remediation by Natural Attenuation at a Coastal Facility

Natural attenuation has emerged as a potential alternative for remediating sites contaminated with fuel hydrocarbons. This paper examines the viability of using attenuation through natural processes to remediate ground water at an industrial facility. The research combined field assessments with data analysis and modeling to evaluate plume stability and predict remediation times. Field data on natural attenuation indicate that BTEX contamination at the site is being attenuated at rates that vary within the range of 0.0001 to 0.0073/day. Stability analyses confirm that the BTEX plume has reached steady state. An analysis on mass flux showed that between 1979 and 1996, 95,000 pounds of BTEX were lost via biodegradation, while 8000 pounds were lost through other mechanisms. A first-order biodegradation rate of 0.0002/day for BTEX was obtained from the change in the total mass of dissolved BTEX with time. Cleanup times in excess of 200 years for the site were estimated using analytical modeling of natural attenuation, which agreed well with the remediation times estimated using the attenuation rates calculated for the site.     

Groundwater remediation: the next 30 years

Groundwater remediation technologies are designed, installed, and operated based on the conceptual models of contaminant hydrogeology that are accepted at that time. However, conceptual models of remediation can change as new research, new technologies, and new performance data become available. Over the past few years, results from multiple-site remediation performance studies have shown that achieving drinking water standards (i.e., Maximum Contaminant Levels, MCLs) at contaminated groundwater sites is very difficult. Recent groundwater research has shown that the process of matrix diffusion is one key constraint. New developments, such as mass discharge, orders of magnitude (OoMs), and SMART objectives are now being discussed more frequently by the groundwater remediation community. In this paper, the authors provide their perspectives on the existing "reach MCLs" approach that has historically guided groundwater remediation projects, and advocate a new approach built around the concepts of OoMs and mass discharge.     

Methodology for comparing source and plume remediation alternatives

It is often difficult at contaminated sites to decide whether remediation effort should be focused on the contaminant source, the dissolved plume, or on both zones. The decision process at these sites is hampered by a lack of quantitative tools for comparing remediation alternatives. A new screening-level mass balance approach is developed for simulating the transient effects of simultaneous ground water source and plume remediation. The contaminant source model is based on a power function relationship between source mass and source discharge, and it can consider partial source remediation at any time after the initial release. The source model serves as a time-dependent mass flux boundary condition to a new analytical plume model, where flow is assumed to be one dimensional, with three-dimensional dispersion. The plume model simulates first-order sequential decay and production of several species, and the decay rates and parent/daughter yield coefficients are variable functions of time and distance. This new method allows for flexible simulation of natural attenuation or remediation efforts that enhance plume degradation. The plume remediation effort may be temporary or delayed in time, limited in space, and it may have different chemical effects on different contaminant species in the decay chain.     

A Fuzzy Rule Based Remedial Priority Ranking System for Contaminated Sites

Contaminated site remediation is generally difficult, time consuming, and expensive. As a result ranking may aid in efficient allocation of resources. In order to rank the priorities of contaminated sites, input parameters relevant to contaminant fate and transport, and exposure assessment should be as accurate as possible. Yet, in most cases these parameters are vague or not precise. Most of the current remediation priority ranking methodologies overlook the vagueness in parameter values or do not go beyond assigning a contaminated site to a risk class. The main objective of this study is to develop an alternative remedial priority ranking system (RPRS) for contaminated sites in which vagueness in parameter values is considered. RPRS aims to evaluate potential human health risks due to contamination using sufficiently comprehensive and readily available parameters in describing the fate and transport of contaminants in air, soil, and groundwater. Vagueness in parameter values is considered by means of fuzzy set theory. A fuzzy expert system is proposed for the evaluation of contaminated sites and a software (ConSiteRPRS) is developed in Microsoft Office Excel 2007 platform. Rankings are employed for hypothetical and real sites. Results show that RPRS is successful in distinguishing between the higher and lower risk cases.     

Temperature as a Tool to Evaluate Aerobic Biodegradation in Hydrocarbon Contaminated Soil

This study evaluates the theory, and some practical aspects of using temperature measurements to assess aerobic biodegradation in hydrocarbon contaminated soil. The method provides an easily applicable alternative for quantifying the rate of biodegradation and/or evaluating the performance of in situ remediation systems. The method involves two nonintrusive procedures for measuring vertical temperature profiles down existing monitoring wells; one using a thermistor on a cable for one‐time measurements and the other using compact temperature data loggers deployed for 3‐month to 1‐year period. These vertical temperature profile measurements are used to identify the depth and lateral extent of biodegradation as well as to monitor seasonal temperature changes throughout the year. The basic theory for using temperature measurements to estimate the minimum rate of biodegradation will be developed, and used to evaluate field measurements from sites in California where biodegradation of spilled petroleum hydrocarbons is due to natural processes. Following, temperature data will be used to evaluate the relative rates of biodegradation due to natural processes and soil vapor extraction (SVE) at a former refinery site in the North‐Central United States. The results from this study show that the temperature method can be a simple, cost effective tool for assessing biodegradation in the soil, and optimizing remediation systems at a wide variety of hydrocarbon spill sites.     

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.     

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.     

Remediation of NAPL source zones: lessons learned from field studies at Hill and Dover AFB

Innovative remediation studies were conducted between 1994 and 2004 at sites contaminated by nonaqueous phase liquids (NAPLs) at Hill and Dover AFB, and included technologies that mobilize, solubilize, and volatilize NAPL: air sparging (AS), surfactant flushing, cosolvent flooding, and flushing with a complexing-sugar solution. The experiments proved that aggressive remedial efforts tailored to the contaminant can remove more than 90% of the NAPL-phase contaminant mass. Site-characterization methods were tested as part of these field efforts, including partitioning tracer tests, biotracer tests, and mass-flux measurements. A significant reduction in the groundwater contaminant mass flux was achieved despite incomplete removal of the source. The effectiveness of soil, groundwater, and tracer based characterization methods may be site and technology specific. Employing multiple methods can improve characterization. The studies elucidated the importance of small-scale heterogeneities on remediation effectiveness, and fomented research on enhanced-delivery methods. Most contaminant removal occurs in hydraulically accessible zones, and complete removal is limited by contaminant mass stored in inaccessible zones. These studies illustrated the importance of understanding the fluid dynamics and interfacial behavior of injected fluids on remediation design and implementation. The importance of understanding the dynamics of NAPL-mixture dissolution and removal was highlighted. The results from these studies helped researchers better understand what processes and scales are most important to include in mathematical models used for design and data analysis. Finally, the work at these sites emphasized the importance and feasibility of recycling and reusing chemical agents, and enabled the implementation and success of follow-on full-scale efforts.     

Analytical and Numerical Modeling of Solute Intrusion,Recovery, and Rebound in Fractured Bedrock

Contaminated groundwater in fractured bedrock can expose ecosystems to undesired levels of risk for extended periods due to prolonged back-diffusion from rock matrix to permeable fractures. Therefore, it is key to characterize the diffusive mass loading (intrusion) of contaminants into the rock matrix for successful management of contaminated bedrock sites. Even the most detailed site characterization techniques often fail to delineate contamination in rock matrix. This study presents a set of analytical solutions to estimate diffusive mass intrusion into matrix blocks, it is recovered by pumping and concentration rebound when pumping ceases. The analytical models were validated by comparing the results with (1) numerical model results using the same model parameters and (2) observed chloride mass recovery, rebound concentration, and concentration in pumped groundwater at a highly fractured bedrock site in Alberta, Canada. It is also demonstrated that the analytical solutions can be used to estimate the total mass stored in the fractured bedrock prior to any remediation thereby providing insights into site contamination history. The predictive results of the analytical models clearly show that successful remediation by pumping depends largely on diffusive intrusion period. The results of initial mass from the analytical model was used to successfully calibrate a three-dimensional discrete fracture network numerical model further highlighting the utility of the simple analytical solutions in supplementing the more detailed site numerical modeling. Overall, the study shows the utility of simple analytical methods to support long-term management of a contaminated fractured bedrock site including site investigations and complex numerical modeling.     

Impact of Temperature on Groundwater Source Attenuation Rates at Hydrocarbon Sites

The temperature sensitivity of microbial populations is reflected in measured source attenuation rates at hydrocarbon‐impacted sites. The objective of this study was to evaluate the correlation between temperature and source attenuation rates (concentration vs. time attenuation rate over many years) of benzene and toluene by analyzing groundwater monitoring data from >2000 hydrocarbon sites. Historical monitoring records were obtained from three databases, processed to yield long‐term multiyear source attenuation rates, and then compared with representative temperatures at each site. Statistically significant and positive relationships between temperature and source attenuation rates were established for benzene and toluene, indicating that temperature does impact hydrocarbon degradation, but is one of many factors that contribute to source attenuation. There was an observed 1.1 to 1.6 times increase in attenuation rates per 10 °C increase in temperature, which is less than the rate increases predicted by the Arrhenius equation. The temperature dependence on attenuation rate is consistent with several lines of evidence that methanogenesis plays a key role in the rate of hydrocarbon source zone attenuation rather than being controlled strictly by the availability of electron acceptors. First, methanogenesis is known to be strongly influenced by temperature, with significantly higher rates up to about 35 °C. Second, the temperature‐degradation rate relationship was stronger at sites with deeper water tables (>30 ft) that are less susceptible to oxygen influx than sites with shallow water tables (<15 ft). Third, dissolved methane concentrations were higher at sites with warmer temperatures. Overall, these results provide indirect support for a conceptual model where methanogenesis is a key degradation process at hydrocarbon sites, and that attenuation of these source zones is temperature‐sensitive.     

Optimizing the Environmental Performance of In Situ Thermal Remediation Technologies Using Life Cycle Assessment

In situ thermal remediation technologies provide efficient and reliable cleanup of contaminated soil and groundwater, but at a high cost of environmental impacts and resource depletion due to the large amounts of energy and materials consumed. This study provides a detailed investigation of four in situ thermal remediation technologies (steam enhanced extraction, thermal conduction heating, electrical resistance heating, and radio frequency heating) in order to (1) compare the life‐cycle environmental impacts and resource consumption associated with each thermal technology, and (2) identify options to reduce these adverse effects. The study identifies a number of options for environmental optimization of in situ thermal remediation. In general, environmental optimization can be achieved by increasing the percentage of heating supplied in off peak electricity demand periods as this reduces the pressure on coal‐based electricity and thereby reduces the environmental impacts due to electricity production by up to 10%. Furthermore, reducing the amount of concrete in the vapor cap by using a concrete sandwich construction can potentially reduce the environmental impacts due to the vapor cap by up to 75%. Moreover, a number of technology‐specific improvements were identified, for instance by the substitution of stainless steel types in wells, heaters, and liners used in thermal conduction heating, thus reducing the nickel consumption by 45%. The combined effect of introducing all the suggested improvements is a 10 to 21% decrease in environmental impacts and an 8 to 20% decrease in resource depletion depending on the thermal remediation technology considered. The energy consumption was found to be the main contributor to most types of environmental impacts; this will, however, depend on the electricity production mix in the studied region. The combined improvement potential is therefore to a large extent controlled by the reduction/improvement of energy consumption.     

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.     

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.