Oxygenated gasoline release in the unsaturated zone - Part 1: Source zone behavior

Oxygenates present in gasoline, such as ethanol and MTBE, are a concern in subsurface contamination related to accidental spills. While gasoline hydrocarbon compounds have low solubility, MTBE and ethanol are more soluble, ethanol being completely miscible with water. Consequently, their fate in the subsurface is likely to differ from that of gasoline. To evaluate the fate of gasoline containing oxygenates following a release in the unsaturated zone shielded from rainfall/recharge, a controlled field test was performed at Canadian Forces Base Borden, in Ontario. 200L of a mixture composed of gasoline with 10% ethanol and 4.5% MTBE was released in the unsaturated zone, into a trench 20cm deep, about 32cm above the water table. Based on soil cores, most of the ethanol was retained in the source, above the capillary fringe, and remained there for more than 100 days. Ethanol partitioned from the gasoline to the unsaturated pore-water and was retained, despite the thin unsaturated zone at the site (~35cm from the top of the capillary fringe to ground surface). Due to its lower solubility, most of the MTBE remained within the NAPL as it infiltrated deeper into the unsaturated zone and accumulated with the gasoline on top of the depressed capillary fringe. Only minor changes in the distribution of ethanol were noted following oscillations in the water table. Two methods to estimate the capacity of the unsaturated zone to retain ethanol are explored. It is clear that conceptual models for sites impacted by ethanol-fuels must consider the unsaturated zone.     

Towards optimal sampling schedules for integral pumping tests

Ethanol use as a gasoline additive is increasing, as are the chances of groundwater contamination caused by gasoline releases involving ethanol. To evaluate the impact of ethanol on dissolved hydrocarbon plumes, a field test was performed in which three gasoline residual sources with different ethanol fractions (E0: no ethanol, E10: 10% ethanol and E95: 95% ethanol) were emplaced below the water table. Using the numerical model BIONAPL/3D, the mass discharge rates of benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene were simulated and results compared to those obtained from sampling transects of multilevel samplers. It was shown that ethanol dissolved rapidly and migrated downgradient as a short slug. Mass discharge of the hydrocarbons from the E0 and E10 sources suggested similar first-order hydrocarbon decay rates, indicating that ethanol from E10 had no impact on hydrocarbon degradation. In contrast, the estimated hydrocarbon decay rates were significantly lower when the source was E95. For the E0 and E10 cases, the aquifer did not have enough oxygen to support complete mineralization of the hydrocarbon compounds to the extent suggested by the field-based mass discharge. Introducing a heterogeneous distribution of hydraulic conductivity did little to overcome this discrepancy. A better match between the numerical model and the field data was obtained assuming partial degradation of the hydrocarbons to intermediate compounds. Besides depending on the ethanol concentration, the impact of ethanol on hydrocarbon degradation appears to be highly dependent on the availability of electron acceptors.     

Occurrence and attenuation of specific organic compounds in the groundwater plume at a former gasworks site

The changing contaminant pattern with travelled distance was investigated in the anaerobic groundwater plume downstream from an extended zone containing residual NAPL at a former gas manufacturing plant. With increasing distance, O- and N-heterocyclic aromatic compounds are enriched in the plume relative to the usually assessed coal tar constituents (poly- and monocyclic aromatic compounds). In a first approximation, the overall concentration decrease of the investigated compounds follows a first order overall decay. The half life distance in the plume downgradient from the source varied between 20 m for benzene and up to 167-303 m for alkyl-naphthalenes. Acenaphthene is degraded only within about 50 m downstream from the source area, then its concentration remains constant (ca. 180 microg/l) and far above the legal limit. Dimethyl-benzofurans were the most recalcitrant among all compounds which could be quantified with the analytical method available. The overall groundwater contamination in the plume is seriously underestimated if only BTEX and 16-EPA-PAHs are monitored.     

Transport and degradation of ethanol in groundwater

Ethanol is rapidly replacing methyl tert-butyl ether (MtBE), the primary fuel oxygenate in the US, and ethanol releases from spills and leaky underground storage tanks (LUSTs) are anticipated. Ethanol has received little attention as a potential groundwater contaminant. This study investigates the fate and transport of ethanol under transient conditions in a sand and gravel aquifer. A pulse containing approximately 220 mg L-1 ethanol and 16 mg L-1 bromide was injected into the shallow sand and gravel aquifer and monitored to estimate its persistence and transport. The plume was monitored for 2.5 months using downgradient multilevel samplers (MLSs). Values for ethanol retardation were measured from ethanol and bromide breakthrough data and compared to estimates using published Koc values for low carbon aquifer sediments (foc=10 microg C g-1 sediment). Ethanol transport was not retarded (R=0.99). A 3-dimensional model reasonably simulated bromide and ethanol breakthrough curves. An average first-order decay constant was estimated to be 0.32 d-1 (t1/2=2.2 d). At the second fence, 75% of the injected bromide and less than 3% of ethanol remained in the plume. Monitored terminal electron acceptor concentrations demonstrated that the majority of the ethanol was transformed by anaerobic processes other than denitrification and sulfate reduction.     

Progression of natural attenuation processes at a crude-oil spill site: I. Geochemical evolution of the plume

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho-xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume.     

Simulation of the effect of remediation on EDB and 1,2-DCA plumes at sites contaminated by leaded gasoline

An analytical model is used to simulate the effects of partial source removal and plume remediation on ethylene dibromide (EDB) and 1,2-dichloroethane (1,2-DCA) plumes at contaminated underground storage tank (UST) sites. The risk posed by EDB, 1,2-DCA, and commingled gasoline hydrocarbons varies throughout the plume over time. Dissolution from the light nonaqueous phase liquid (LNAPL) determines the concentration of each contaminant near the source, but biological decay in the plume has a greater influence as distance downgradient from the source increases. For this reason, compounds that exceed regulatory standards near the source may not in downgradient plume zones. At UST sites, partial removal of a residual LNAPL source mass may serve as a stand alone remedial technique if dissolved concentrations in the source zone are within several orders of magnitude of the applicable government or remedial standards. This may be the case with 1,2-DCA; however, EDB is likely to be found at concentrations that are orders of magnitude higher than its low Maximum Contaminant Level (MCL) of 0.05 μg/L (micrograms per liter). For sites with significant EDB contamination, even when plume remediation is combined with source depletion, significant timeframes may be required to mitigate the impact of this compound. Benzene and MTBE are commonly the focus of remedial efforts at UST sites, but simulations presented here suggest that EDB, and to a lesser extent 1,2-DCA, could be the critical contaminants to consider in the remediation design process at many sites.     

Chemical modifications of groundwater contaminated by recharge of treated sewage effluent

Long-term monitoring of the chemical composition of recharge sewage effluent and associated contaminated groundwater from the Dan Region Sewage Reclamation Project shows, after 16 years of recharge operation, the presence of a distinct saline plume (up to 400 mg/l Cl), extending 1600 m downgradient in the Coastal Plain aquifer of Israel. The recorded electrolyte composition of groundwater in the vicinity of the recharge area reflects the variations in the compositions of the sewage effluents, as well as water-rock interactions induced by the recharge of treated sewage effluents. The original sewage composition was modified, particularly during early stages of effluent migration in the unsaturated zone, by cation-exchange and adsorption reactions. Since the soil sorption capacity is finite these reactions caused only limited modifications, and once the system reached a steady state the inorganic composition of the contaminated groundwater became similar to that of the recharge water. Decomposition of organic matter in the unsaturated zone resulted in CO₂ generation and dissolution of CaCO₃ minerals in the aquifer. It was shown that chemical and/or bio-degradation of organic matter takes place mainly in the unsaturated (vadose) zone. Hence, monitoring the efficiency of the vadose zone to retain contaminants is essential for evaluating the quality of groundwater since it was shown that organic compounds behave almost conservatively once the effluents enter and flow within the saturated zone.     

Seasonal impact of blending oxygenated organics with gasoline on motor vehicle tailpipe and evaporative emissions.

Emissions from a 1988 GM Corsica with adaptive learning closed loop control were measured with 4 fuels at 40, 75, and 90 degrees F. Evaporative and exhaust emissions were examined from each fuel at each test temperature. Test fuels were unleaded summer grade gasoline; a blend of this gasoline containing 8.1 percent ethanol; a refiner's blend stock; and the blend stock containing 16.2 percent methyl tertiary butyl ether. The ethanol and MTBE blends contained 3.0 percent oxygen by weight. Regulated emissions (total hydrocarbons, carbon monoxide, and oxides of nitrogen), detailed aldehydes, detailed hydrocarbons, ethanol, MTBE, benzene, and 1,3-butadiene were determined. The highest levels of regulated emissions were produced at the lower temperature. Blended fuels produced almost twice the evaporative hydrocarbon emissions at high temperatures as did the base fuels. Benzene emissions varied with fuels and operating temperatures, while 1,3-butadiene emissions decreased slightly with increasing temperatures. Formaldehyde emissions were not sensitive to fuel or temperature changes. Ethanol fuel blend total aldehyde emissions increased by 40 percent due to increased acetaldehyde emissions. Fuel blends had approximately a 3 percent economy decrease. The MTBE fuel blend appeared to offer the most reduction in total hydrocarbon, carbon monoxide, and oxides of nitrogen for the fuels and temperatures tested.     

Review of unsaturated-zone transport and attenuation of volatile organic compound (VOC) plumes leached from shallow source zones

Reliable prediction of the unsaturated zone transport and attenuation of dissolved-phase VOC (volatile organic compound) plumes leached from shallow source zones is a complex, multi-process, environmental problem. It is an important problem as sources, which include solid-waste landfills, aqueous-phase liquid discharge lagoons and NAPL releases partially penetrating the unsaturated zone, may persist for decades. Natural attenuation processes operating in the unsaturated zone that, uniquely for VOCs includes volatilisation, may, however, serve to protect underlying groundwater and potentially reduce the need for expensive remedial actions. Review of the literature indicates that only a few studies have focused upon the overall leached VOC source and plume scenario as a whole. These are mostly modelling studies that often involve high strength, non-aqueous phase liquid (NAPL) sources for which density-induced and diffusive vapour transport is significant. Occasional dissolved-phase aromatic hydrocarbon controlled infiltration field studies also exist. Despite this lack of focus on the overall problem, a wide range of process-based unsaturated zone - VOC research has been conducted that may be collated to build good conceptual model understanding of the scenario, particularly for the much studied aromatic hydrocarbons and chlorinated aliphatic hydrocarbons (CAHs). In general, the former group is likely to be attenuated in the unsaturated zone due to their ready aerobic biodegradation, albeit with rate variability across the literature, whereas the fate of the latter is far less likely to be dominated by a single mechanism and dependent upon the relative importance of the various attenuation processes within individual site - VOC scenarios. Analytical and numerical modelling tools permit effective process representation of the whole scenario, albeit with potential for inclusion of additional processes - e.g., multi-mechanistic sorption phase partitioning, and provide good opportunity for further sensitivity analysis and development to practitioner use. There remains a significant need to obtain intermediate laboratory-scale and particularly field-scale (actual site and controlled release) datasets that address the scenario as a whole and permit validation of the available models. Integrated assessment of the range of simultaneous processes that combine to influence leached plume generation, transport and attenuation in the unsaturated zone is required. Component process research needs are required across the problem scenario and include: the simultaneous volatilisation and dissolution of source zones; development of appropriate field-scale dispersion estimates for the unsaturated zone; assessment of transient VOC exchanges between aqueous, vapour and sorbed phases and their influence upon plume attenuation; development of improved field methods to recognise and quantify biodegradation of CAHs; establishment of the influence of co-contaminants; and, finally, translation of research findings into more robust practitioner practice.     

Seasonal Impact of Blending Oxygenated Organics with Gasoline on Motor Vehicle Tailpipe and Evaporative Emissions

Emissions from a 1988 GM Corsica with adaptive learning closed loop control were measured with 4 fuels at 40, 75, and 90° F. Evaporative and exhaust emissions were examined from each fuel at each test temperature. Test fuels were unleaded summer grade gasoline; a blend of this gasoline containing 8.1 percent ethanol; a refiner’s blend stock; and the blend stock containing 16.2 percent methyl tertiary butyl ether. The ethanol and MTBE blends contained 3.0 percent oxygen by weight. Regulated emissions (total hydrocarbons, carbon monoxide, and oxides of nitrogen), detailed aldehydes, detailed hydrocarbons, ethanol, MTBE, benzene, and 1, 3-butadiene were determined.

The highest levels of regulated emissions were produced at the lower temperature. Blended fuels produced almost twice the evaporative hydrocarbon emissions at high temperatures as did the base fuels. Benzene emissions varied with fuels and operating temperatures, while 1, 3-butadiene emissions decreased slightly with increasing temperatures. Formaldehyde emissions were not sensitive to fuel or temperature changes. Ethanol fuel blend total aldehyde emissions Increased by 40 percent due to increased acetaldehyde emissions.

Fuel blends had approximately a 3 percent economy decrease. The MTBE fuel blend appeared to offer the most reduction in total hydrocarbon, carbon monoxide, and oxides of nitrogen for the fuels and temperatures tested.     

Modeling the partitioning of BTEX in water-reformulated gasoline systems containing ethanol

The objectives of this research were to quantify the extent of cosolvency for water–gasoline mixtures containing ethanol and to identify appropriate modeling tools for predicting the equilibrium partitioning of BTEX compounds and ethanol between an ethanol-bearing gasoline and water. Batch-equilibrium experiments were performed to measure ethanol and BTEX partitioning between a gasoline and aqueous phase. The experiments incorporated simple binary and multicomponent organic mixtures comprised of as many as eight compounds as well as highly complex commercial gasolines where the composition of the organic phase was not completely defined. At high ethanol volume fractions, the measured partition coefficients displayed an approximate linear relationship when plotted on semi-log scale as a function of ethanol volume fraction. At lower concentrations, however, there was a distinctly different trend which is attributed to a change in solubilization mechanisms at these concentrations. Three mathematical models were compared with or fit to the experimental results. Log-linear and UNIFAC-based models were used in a predictive capacity and were capable of representing the overall increase in partition coefficients as a function of increasing ethanol content in the aqueous phase. However, neither of these predicted the observed two-part curve. A piecewise model comprised of a linear relationship for low ethanol volume fractions and a log-linear model for higher concentrations was fit to data for a surrogate gasoline comprised of eight compounds and was then used to predict BTEX concentrations in the aqueous phase equilibrated with three different commercial gasolines. This model was superior to the UNIFAC predictions, especially at the low aqueous ethanol concentrations.     

Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation

This paper concludes that back diffusion from one or a few thin clayey beds in a sand aquifer can cause contaminant persistence above MCLs in a sand aquifer long after the source zone initially causing the plume is isolated or removed. This conclusion is based on an intensive case study of a TCE contaminated site in Florida, with the processes evaluated using numerical modeling. At this site, the TCE DNAPL zone formed decades ago, and was hydraulically isolated by means of an innovative system performing groundwater extraction, treatment and re-injection. Treated water is re-injected in a row of injection wells situated a short distance downgradient of the extraction wells, creating a clean-water displacement front to efficiently flush the downgradient plume. This scheme avoids the creation of stagnation zones typical of most groundwater pump-and-treat systems, thereby minimizing the time for aquifer flushing and therefore downgradient cleanup. The system began operation in August 2002 and although the performance monitoring shows substantial declines in concentrations, detectable levels of TCE and degradation products persist downgradient of the re-injection wells, long after the TCE should have disappeared based on calculations assuming a nearly homogenous sand aquifer. Three hypotheses were assessed for this plume persistence: 1) incomplete source-zone capture, 2) DNAPL occurrence downgradient of the re-injection wells, and 3) back diffusion from one or more thin clay beds in the aquifer. After careful consideration, the first two hypotheses were eliminated, leaving back diffusion as the only plausible hypothesis, supported by detailed measurements of VOC concentrations within and near the clay beds and also by numerical model simulations that closely represent the field site hydrogeologic conditions. The model was also used to simulate a more generalized, hypothetical situation where more thin clayey beds occur in a sand aquifer with an underlying aquitard. While there is no doubt that DNAPL source mass reduction can eventually improve downgradient groundwater quality, the magnitude and time scale over which the improvement occurs is the major uncertainty given current characterization approaches. This study shows that even one thin clay bed, less than 0.2 m thick, can cause plume persistence due to back diffusion for several years or even decades after the flux from the source is completely isolated. Thin clay beds, which have a large storage capacity for dissolved and sorbed contaminant mass, are common in many types of sandy aquifers. However, without careful inspection of continuous cores and sampling, such thin clay beds, and their potential for causing long-term back-diffusion effects, can easily go unnoticed during site characterization.     

Groundwater-surface water interaction and its role on TCE groundwater plume attenuation

A field investigation of a TCE plume in a surficial sand aquifer shows that groundwater-surface water interactions strongly influence apparent plume attenuation. At the site, a former industrial facility in Connecticut, depth-discrete monitoring along three cross-sections (transects) perpendicular to groundwater flow shows a persistent VOC plume extending 700 m from the DNAPL source zone to a mid-size river. Maximum TCE concentrations along a transect 280 m from the source were in the 1000s of microg/L with minimal degradation products. Beyond this, the land surface drops abruptly to a lower terrace where a shallow pond and small streams occur. Two transects along the lower terrace, one midway between the facility and river just downgradient of the pond and one along the edge of the river, give the appearance that the plume has strongly attenuated. At the river, maximum TCE concentrations in the 10s of microg/L and similar levels of its degradation product cis-DCE show direct plume discharge from groundwater to the river is negligible. Although degradation plays a role in the strong plume attenuation, the major attenuation factor is partial groundwater plume discharge to surface water (i.e. the pond and small streams), where some mass loss occurs via water-air exchange. Groundwater and stream mass discharge estimates show that more than half of the plume mass discharge crossing the first transect, before surface water interactions occur, reaches the river directly via streamflow, although river concentrations were below detection due to dilution. This study shows that groundwater and surface water concentration measurements together provide greater confidence in identifying and quantifying natural attenuation processes at this site, rather than groundwater measurements alone.     

Persistence of LNAPL sources: relationship between risk reduction and LNAPL recovery

Light nonaqueous phase liquids (LNAPLs), such as fuels, are the source of much soil and groundwater contamination. Though the mobility of LNAPLs is limited in many environments, dissolved-phase components, such as benzene, can produce groundwater plumes that are more mobile than the LNAPL source. In such a setting, it is commonly assumed that recovery of the LNAPL will result in a reduction in risk associated with the dissolved phase. This paper synthesizes several existing multiphase and chemical transport solutions into a single linked methodology that predicts concentrations of soluble constituents within and downgradient of LNAPL source zones from dissolution of those constituents into groundwater flowing through and below LNAPL sources. This approach has been applied to a variety of LNAPL spill conditions. For biodegradable compounds, these analyses show that the period of time where the dissolved-phase plume is expanding is very small compared to the duration of most LNAPL sources, and that the downgradient extent is generally less than about 100 m for BTEX compounds. Therefore, the risk to receptors, as measured by the maximum downgradient extent of dissolved-phase plume or the maximum concentration of these compounds at a downgradient receptor, is generally unrelated to the longevity of the LNAPL sources. The maximum downgradient extent of the dissolved-phase plume is determined almost entirely by the groundwater velocity and the biodegradation rate. These analyses further demonstrate that recovery of LNAPL by hydraulic methods is often ineffective at reducing risk. Except in coarse-grained soils or intermediate soils with significant LNAPL saturations, free-product recovery approaches do not result in significant reductions in the longevity of downgradient dissolved-phase contamination. Further, for biodegradable constituents, remediation does not result in a near-term decrease in the downgradient extent of contamination. Cleanup methods that act to change the composition of the LNAPL source are more effective at reducing the downgradient concentrations, particularly for fine-grained soils or when LNAPL saturations are low.     

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.     

Effect of water-table fluctuation on dissolution and biodegradation of a multi-component, light nonaqueous-phase liquid

Light nonaqueous-phase liquids (LNAPLs) such as gasoline and diesel fuel are among the most common causes of soil and groundwater contamination. Dissolution and subsequent advective transport of LNAPL components can negatively impact water supplies, while biodegradation is thought to be an important sink for this class of contaminants. We present a laboratory investigation of the effect of a water-table fluctuation on dissolution and biodegradation of a multi-component LNAPL (85% hexadecane, 5% toluene, 5% ethylbenzene, and 5% 2-methylnapthalene on a molar basis) in a pair of similar model aquifers (80 cm x 50 cm x 3 cm), one of which was subjected to a water-table fluctuation. Water-table fluctuation resulted in LNAPL and air entrapment below the water table, an increase in the vertical extent of the LNAPL source zone (by factor 6.7), and an increase in the volume of water passing through the source zone (by factor ~18). Effluent concentrations of dissolved LNAPL components were substantially higher and those of dissolved nitrate lower in the model aquifer where a fluctuation had been induced. Thus, water-table fluctuation led to enhanced biodegradation activity (28.3 mmol of nitrate consumed compared to 16.3 mmol in the model without fluctuation) as well as enhanced dissolution of LNAPL components. Despite the increased biodegradation, fluctuation led to increased elution of dissolved LNAPL components from the system (by factors 10-20). Hence, water-table fluctuations in LNAPL-contaminated aquifers might be expected to result in increased exposure of downgradient receptors to LNAPL components. Accordingly, water-table fluctuations in contaminated aquifers are probably undesirable unless the LNAPL is of minimal solubility or the dissolved-phase plume is not expected to reach a receptor due to distance or the presence of some form of containment.     

Partitioning of aromatic and oxygenated constituents into water from regular and ethanol-blended gasolines

Variability in gasoline-water partitioning of major aromatic constituents (benzene, toluene, ethylbenzene, and xylenes (BTEX)) and methyl tert-butyl ether (MTBE) were examined for regular and ethanol-blended gasolines. By use of a two-phase liquid-liquid equilibrium model, the distribution of nonpolar solutes between fuel phase and water was related to principles of equilibrium. The models derived using Raoult's law convention for activity coefficients and liquid solubility is presented. The observed inverse log-log linear dependence of K_fw values on aqueous solubility, could be well predicted by assuming gasoline to be an ideal solvent mixture. Oxygenated additives (i.e., ethanol and MTBE), in the low percent range (below 5%), were shown to have minimal or negligible cosolvent effects on hydrocarbon partitioning. In the case of high fuel-to-water ratio (e.g., 1:1) or near contaminant source zone, the cosolvent effect of oxygenated gasoline with high content of ethanol (e.g., E85) will be environmentally significant.     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

Transport of hydrocarbons from an emplaced fuel source experiment in the vadose zone at Airbase Vaerløse, Denmark

An emplaced hydrocarbon source field experiment was conducted in the relatively homogeneous sandy geology of the vadose zone at Airbase Vaerl?se, Denmark. The source (10.2 l of NAPL) consisted of 13 hydrocarbons (n-, iso- and cyclo-alkanes and aromates) and CFC-113 as a tracer. Monitoring in the 107 soil gas probes placed out to 20 m from the centre of the source showed spreading of all the compounds in the pore air and all compounds were measured in the pore air within a few hours after source emplacement. Seven of the fourteen compounds were depleted from the source within the 1 year of monitoring. The organic vapours in the pore air migrated radially from the source. The CFC-113 concentrations seemed to be higher in the deeper soil gas probes compared with the hydrocarbons, indicating a high loss of CFC-113 to the atmosphere and the lack of degradation of CFC-113. For the first days after source emplacement, the transport of CFC-113, hexane and toluene was successfully simulated using a radial gas-phase diffusion model for the unsaturated zone. Groundwater pollution caused by the vadose zone hydrocarbon vapours was only detected in the upper 30 cm of the underlying groundwater and only during the first 3 months of the experiment. Only the most water-soluble compounds were detected in the groundwater and concentrations decreased sharply with depth (approximately one order of magnitude within 10 cm depth) to non-detect at 30 cm depth. The groundwater table varied more than 1 m within the measurement period. However that did not influence the direction of the groundwater flow. Approximately 7 months after source emplacement the groundwater table rose more than 1 m within 1 month. That did not cause additional pollution of the groundwater.     

An assessment of natural biotransformation of petroleum hydrocarbons and chlorinated solvents at an aquifer plume transect

Field biogeochemical characterization and laboratory microcosm studies were performed to assess the potential for future biotransformation of trichloroethylene (TCE) and toluene in a plume containing petroleum hydrocarbons and chlorinated solvents at the former Wurtsmith Air Force Base in Oscoda, MI. In situ terminal electron accepting processes (TEAPs), contaminant composition and microbial phylogeny were studied at a plume transect 100 m downgradient of the source. The presence of reduced electron acceptors, relevant microbial communities, and elevated dissolved methane and carbon dioxide concentrations at the transect, as well as downgradient accumulation of BTEX metabolites and dechlorination products, indicated that past or current reductive dechlorination at the transect was likely driven by BTEX biodegradation in the methanogenic zone. However, TCE and toluene mineralization in sediment-groundwater microcosms without added electron acceptors did not exceed 5% during 300 days of incubation and was nearly invariant with original sediment TEAP, even following amendments of nitrogen and phosphorus. Mineralization rates were on the order of 0.0015-0.03 mumol/g day. After 8 months, microcosms showed evidence of methanogenesis, but CH4 and CO2 production arose from the degradation of contaminants other than toluene. Cis-dichloroethylene was observed in only one methanogenic microcosm after more than 500 days. It appears likely that spatially and temporally dynamic redox zonation at the plume transect will prevent future sustained reductive dehalogenation of highly chlorinated solvents, for during the course of a year, the predominant TEAP at the highly contaminated water table shifted from methanogenesis to iron- and sulfate-reduction. It is recommended that biotransformation studies combine considerations of long-term, spatially relevant changes in redox zonation with laboratory-scale studies of electron donor utilization and cometabolic substrate transformation to yield a more accurate assessment of natural bioattenuation of specific pollutants in aquifers contaminated by undefined organic waste mixtures.