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Methyl tert-butyl ether (MTBE), the most common gasoline oxygenate, is frequently detected in surface water and groundwater. The aim of this study was to evaluate the potential of compound-specific isotope analysis to assess in situ biodegradation of MTBE in groundwater. For that purpose, the effect of relevant physical and biological processes on carbon isotope ratios of MTBE was evaluated in laboratory studies. Carbon isotope fractionation during organic phase/gas-phase partitioning (0.50 ± 0.15‰), aqueous phase/gas-phase partitioning (0.17 ± 0.05‰), and organic phase/aqueous-phase partitioning (0.18 ± 0.24‰) was small in comparison to carbon isotope fractionation measured during biodegradation of MTBE in microcosms based on aquifer sediments of the Borden site. In experiments with MTBE as the only substrate and a cometabolic experiment with 3-methypentane as primary substrate, MTBE became enriched in 13C by 5.1 to 6.9‰ after 95 to 97% degradation. For both experiments, similar isotopic enrichment factors were obtained (-1.52 ± 0.06 to -1.97 ± 0.05‰). Biodegradation of TBA, which accumulated transiently in the cometabolic microcosms, was also accompanied by carbon isotope fractionation, with an isotopic enrichment factor of -4.21 ± 0.07‰. This study suggests that carbon isotope analysis is a potential tool to trace in situ biodegradation of MTBE and TBA and thus to better understand the fate of these contaminants in the environment.

Mainly due to intrinsic biodegradation, monitored natural attenuation can be an effective and inexpensive remediation strategy at petroleum release sites. However, gasoline additives such as methyl tert-butyl ether (MTBE) can jeopardize this strategy because these compounds often degrade, if at all, at a slower rate than the collectively benzene, toluene, ethylbenzene and the xylene (BTEX) compounds. Investigation of whether a compound degrades under certain conditions, and at what rate, is therefore important to the assessment of the intrinsic remediation potential of aquifers. A natural gradient experiment with dissolved MTBE-containing gasoline in the shallow, aerobic sand aquifer at Canadian Forces Base (CFB) Borden (Ontario, Canada) from 1988 to 1996 suggested that biodegradation was the main cause of attenuation for MTBE within the aquifer. This laboratory study demonstrates biologically catalyzed MTBE degradation in Borden aquifer-like environments, and so supports the idea that attenuation due to biodegradation may have occurred in the natural gradient experiment. In an experiment with batch microcosms of aquifer material, three of the microcosms ultimately degraded MTBE to below detection, although this required more than 189 days (or >300 days in one case). Failure to detect the daughter product tert-butyl alcohol (TBA) in the field and the batch experiments could be because TBA was more readily degradable than MTBE under Borden conditions.

[1] The effect of ethanol on the persistence of benzene in gasoline-contaminated aquifers is simulated using a multicomponent reactive transport model. The conceptual model includes a residual gasoline source which is dissolving at the water table into an aquifer containing a limited amount of dissolved oxygen. The coupled processes include nonaqueous phase liquid (NAPL) source dissolution, transport of the dissolved components, and competitive aerobic biodegradation. Comparisons are made between dissolved benzene plumes from a gasoline spill and those from an otherwise equivalent spill containing 10% ethanol (gasohol). Simulations have shown that under some conditions a 10% ethanol component in gasoline can extend the travel distance of a benzene plume by up to 150% relative to that from an equivalent ethanol-free gasoline spill. The increase occurs because ethanol preferentially consumes oxygen, which reduces the biodegradation rate of benzene. The impact is limited, however, because sufficient oxygen disperses behind the ethanol plume into the slightly retarded benzene plume. A sensitivity analysis for two common spill scenarios showed that background oxygen concentrations and benzene retardation have the most significant influence on ethanol-induced benzene persistence. The results are highly relevant in light of the increasing use of ethanol-enhanced fuels throughout the world and the forthcoming ban of methyl tertiary-butyl-ether (MTBE) in California and its probable replacement by ethanol by the end of 2002.

A multicomponent reactive transport model (BIONAPL/3D) is used to simulate the effect of ethanol on the persistence of benzene in gasoline-contaminated aquifers. The model is used to compare the travel distance of benzene plumes dissolving from equivalent gasoline and 10% ethanol-gasoline (gasohol) sources. Under some conditions, the presence of ethanol increases the migration distance of the benzene plume by a factor of 3 relative to an ethanol-free spill. Benzene becomes more persistent in the presence of ethanol because ethanol preferentially consumes oxygen, which reduces the biodegradation rate of benzene. The impact is limited, however, because the non-retarded ethanol eventually advances beyond the retarded benzene plume, exposing benzene to higher background oxygen concentrations.

Biodegradation of organic contaminants in groundwater is a microscale process which is often observed on scales of 100s of metres or larger. Unfortunately, there are no known equivalent parameters for characterizing the biodegradation process at the macroscale as there are, for example, in the case of hydrodynamic dispersion. Zero- and first-order degradation rates estimated at the laboratory scale by model fitting generally overpredict the rate of biodegradation when applied to the field scale because limited electron acceptor availability and microbial growth are not considered. On the other hand, field-estimated zero- and first-order rates are often not suitable for predicting plume development because they may oversimplify or neglect several key field scale processes, phenomena and characteristics. This study uses the numerical model BIO3D to link the laboratory and field scales by applying laboratory-derived Monod kinetic degradation parameters to simulate a dissolved gasoline field experiment at the Canadian Forces Base (CFB) Borden. All input parameters were derived from independent laboratory and field measurements or taken from the literature a priori to the simulations. The simulated results match the experimental results reasonably well without model calibration. A sensitivity analysis on the most uncertain input parameters showed only a minor influence on the simulation results. Furthermore, it is shown that the flow field, the amount of electron acceptor (oxygen) available, and the Monod kinetic parameters have a significant influence on the simulated results. It is concluded that laboratory-derived Monod kinetic parameters can adequately describe field scale degradation, provided all controlling factors are incorporated in the field scale model. These factors include advective–dispersive transport of multiple contaminants and electron acceptors and large-scale spatial heterogeneities.

Methyl tert-butyl ether (MTBE), the most common gasoline oxygenate, is frequently detected in surface water and groundwater. The aim of this study was to evaluate the potential of compound-specific isotope analysis to assess in situ biodegradation of MTBE in groundwater. For that purpose, the effect of relevant physical and biological processes on carbon isotope ratios of MTBE was evaluated in laboratory studies. Carbon isotope fractionation during organic phase/gas-phase partitioning (0.50 ± 0.15‰), aqueous phase/gas-phase partitioning (0.17 ± 0.05‰), and organic phase/aqueous-phase partitioning (0.18 ± 0.24‰) was small in comparison to carbon isotope fractionation measured during biodegradation of MTBE in microcosms based on aquifer sediments of the Borden site. In experiments with MTBE as the only substrate and a cometabolic experiment with 3-methypentane as primary substrate, MTBE became enriched in 13C by 5.1 to 6.9‰ after 95 to 97% degradation. For both experiments, similar isotopic enrichment factors were obtained (-1.52 ± 0.06 to -1.97 ± 0.05‰). Biodegradation of TBA, which accumulated transiently in the cometabolic microcosms, was also accompanied by carbon isotope fractionation, with an isotopic enrichment factor of -4.21 ± 0.07‰. This study suggests that carbon isotope analysis is a potential tool to trace in situ biodegradation of MTBE and TBA and thus to better understand the fate of these contaminants in the environment.