The Use of Stable Isotopes to Differentiate Specific Source Markers for MTBE

The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the δ¹³C values were observed although the samples had isotopically distinct δ-D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.     

Applications of Anthropogenic Lead ArchaeoStratigraphy (ALAS Model) to Hydrocarbon Remediation

A model, which employs the use of high precision stable lead isotopic analyses, has been developed to estimate the age of hydrocarbon releases. The ALAS Model (Anthropogenic Lead ArchaeoStratigraphy) is based on calibrated, systematic increases in lead isotope ratios of gasolines caused by shifts in sources of lead ores used by the U.S. lead industry, including manufacturers of alkylleads, to more radiogenic Mississippi Valley Type (MVT) deposits. Acquisition of high quality samples (free product, gasoline-impacted soil and groundwater) of known age and subsequent analyses of the hydrocarbon component by high precision lead isotopic analyses by thermal ionization mass spectrometry (TIMS) have produced the ALAS Model calibration curve. Age uncertainties range from - 1 to 2 years for gasoline releases which occurred between 1965 and 1990, the major era of leaded gasoline usage. Analytical methods required to measure lead isotope ratios on ~5 nanograms of lead with precisions and accuracy of < - 0.1% (2 SEM ) are discussed in detail. Published lead isotopic measurements of gasoline-derived anthropogenic lead of samples throughout the United States are used to demonstrate the wide geographic range over which the ALAS Model may be applied. Two representative case studies involving an early 1970s free product release in California and the discrimination of a 1970s from modern unleaded gasoline release in Florida demonstrate the use of the model on single and multiple hydrocarbon releases, respectively, in different geographic regions of the United States. A third investigation focuses on the use of lead isotopes to correlate dissolved phase hydrocarbons with their source, in this case, unleaded (aka low lead) gasoline releases in New Jersey. Dissolved phase hydrocarbons (BTEX/MTBE) are shown to carry the lead isotopic signature of the unleaded gasoline into groundwater, allowing the specific source of the release to be identified. Investigations of lead isotopes as tracers of MTBE in groundwater are ongoing. However, both laboratory and field data indicate MTBE carries the lead isotopic signature of its unleaded gasoline source into groundwater, demonstrating the potential of the lead isotopic system as a discriminant of MTBE sources. Although developed to estimate the age of leaded gasoline releases, the ALAS Model has been successfully applied in studies requiring age dating of jet-A, diesel, kerosene, motor oil, and heating oil. These petroleum distillates are suspected of accidentally acquiring small, yet significant quantities of alkylleads during refining, allowing accurate ALAS Model ages to be determined. When lead levels in these petroleum distillates are within their normal range, typically tens to hundreds of ppb lead, it is possible to use lead isotopic ratios to correlate environmental releases of these products to their source or other releases.     

Applications of Anthropogenic Lead ArchaeoStratigraphy (ALAS Model) to Hydrocarbon Remediation

A model, which employs the use of high precision stable lead isotopic analyses, has been developed to estimate the age of hydrocarbon releases. The ALAS Model (Anthropogenic Lead ArchaeoStratigraphy) is based on calibrated, systematic increases in lead isotope ratios of gasolines caused by shifts in sources of lead ores used by the U.S. lead industry, including manufacturers of alkylleads, to more radiogenic Mississippi Valley Type (MVT) deposits. Acquisition of high quality samples (free product, gasoline-impacted soil and groundwater) of known age and subsequent analyses of the hydrocarbon component by high precision lead isotopic analyses by thermal ionization mass spectrometry (TIMS) have produced the ALAS Model calibration curve. Age uncertainties range from  ± 1 to 2 years for gasoline releases which occurred between 1965 and 1990, the major era of leaded gasoline usage. Analytical methods required to measure lead isotope ratios on ∼5 nanograms of lead with precisions and accuracy of < ± 0.1% (2_SEM) are discussed in detail. Published lead isotopic measurements of gasoline-derived anthropogenic lead of samples throughout the United States are used to demonstrate the wide geographic range over which the ALAS Model may be applied. Two representative case studies involving an early 1970s free product release in California and the discrimination of a 1970s from modern unleaded gasoline release in Florida demonstrate the use of the model on single and multiple hydrocarbon releases, respectively, in different geographic regions of the United States. A third investigation focuses on the use of lead isotopes to correlate dissolved phase hydrocarbons with their source, in this case, unleaded (aka low lead) gasoline releases in New Jersey. Dissolved phase hydrocarbons (BTEX/MTBE) are shown to carry the lead isotopic signature of the unleaded gasoline into groundwater, allowing the specific source of the release to be identified. Investigations of lead isotopes as tracers of MTBE in groundwater are ongoing. However, both laboratory and field data indicate MTBE carries the lead isotopic signature of its unleaded gasoline source into groundwater, demonstrating the potential of the lead isotopic system as a discriminant of MTBE sources. Although developed to estimate the age of leaded gasoline releases, the ALAS Model has been successfully applied in studies requiring age dating of jet-A, diesel, kerosene, motor oil, and heating oil. These petroleum distillates are suspected of accidentally acquiring small, yet significant quantities of alkylleads during refining, allowing accurate ALAS Model ages to be determined. When lead levels in these petroleum distillates are within their normal range, typically tens to hundreds of ppb lead, it is possible to use lead isotopic ratios to correlate environmental releases of these products to their source or other releases.     

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.     

Treatment of groundwater contaminated with gasoline components by an ozone/UV process

In this paper, the treatment of real groundwater samples contaminated with gasoline components, such as benzene, toluene, ethylbenzene, and xylene (BTEX), methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), and other gasoline constituents in terms of total petroleum hydrocarbons as gasoline (TPHg) by an ozone/UV process was investigated. The treatment was conducted in a semi-batch reactor under different experimental conditions by varying ozone gas dosage and incident UV light intensity. The groundwater samples contained BTEX compounds, MTBE, TBA, and TPHg in the ranges of 5-10000, 3000-5500, 80-1400, and 2400-20000mugl(-1), respectively. The ozone/UV process was very effective compared to ozonation in the removal of the gasoline components from the groundwater samples. For the various gasoline constituents, more than 99% removal efficiency was achieved for the ozone/UV process and the removal efficiency for ozonation was as low as 27%. The net ozone consumed per mol of organic carbon (from BTEX, MTBE, and TBA) oxidized varied in the range of 5-60 for different types of groundwater samples treated by the ozone/UV process. In ozonation experiments, it was observed that the presence of sufficient amount of iron in groundwater samples improved the removal of BTEX, MTBE, TBA, and TPHg.     

Using the Gasoline Additive MTBE in Forensic Environmental Investigations

A variety of additives are used in gasoline, and they can sometimes be used to help identify the source, timing, or number of gasoline spills at a site. The physicochemical characteristics of the additive MTBE, and its historical use pattern in the United States since 1979, make it a key compound to study when conducting forensic investigations of gasoline spills. MTBE's low octanol: water distribution coefficient and high solubility cause it to dissolve into groundwater more readily than other gasoline components. Thus, the initial appearance of MTBE in the groundwater is often a good indicator of a recent gasoline spill. MTBE's very low retardation and minimal biodegradation in groundwater can be used with transport rate calculations to establish relatively accurate estimates of spill timing. Because MTBE moves faster in groundwater than BTEX compounds, if a gasoline spill site has a BTEX plume that is longer than the MTBE plume, it is certain that at least two distinctly different gasoline releases have occurred. This allows for the identification of new gasoline spills, even when substantial subsurface petroleum contamination already exists. An example application is reviewed to demonstrate the use of MTBE data in forensic investigations.     

Quantifying MTBE biodegradation in the Vandenberg Air Force Base ethanol release study using stable carbon isotopes

Compound-specific isotope analysis (CSIA) was used to assess biodegradation of MTBE and TBA during an ethanol release study at Vandenberg Air Force Base. Two continuous side-by-side field releases were conducted within a preexisting MTBE plume to form two lanes. The first involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene ("No ethanol lane"), while the other involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene and ethanol ("With ethanol lane"). The delta(13)C of MTBE for all wells in the "No ethanol lane" remained constant during the experiment with a mean value of -31.3 +/- 0.5 per thousand (n=40), suggesting the absence of any substantial MTBE biodegradation in this lane. In contrast, substantial enrichment in (13)C of MTBE by 40.6 per thousand, was measured in the "With ethanol lane", consistent with the effects of biodegradation. A substantial amount of TBA (up to 1200 microg/L) was produced by the biodegradation of MTBE in the "With ethanol lane". The mean value of delta(13)C for TBA in groundwater samples in the "With ethanol lane" was -26.0 +/- 1.0 per thousand (n=32). Uniform delta(13)C TBA values through space and time in this lane suggest that substantial anaerobic biodegradation of TBA did not occur during the experiment. Using the reported range in isotopic enrichment factors for MTBE of -9.2 per thousand to -15.6 per thousand, and values of delta(13)C of MTBE in groundwater samples, MTBE first-order biodegradation rates in the "With ethanol lane" were 12.0 to 20.3 year(-1) (n=18). The isotope-derived rate constants are in good agreement with the previously published rate constant of 16.8 year(-1) calculated using contaminant mass-discharge for the "With ethanol lane".     

Using the Gasoline Additive MTBE in Forensic Environmental Investigations

A variety of additives are used in gasoline, and they can sometimes be used to help identify the source, timing, or number of gasoline spills at a site. The physicochemical characteristics of the additive MTBE, and its historical use pattern in the United States since 1979, make it a key compound to study when conducting forensic investigations of gasoline spills. MTBE's low octanol : water distribution coefficient and high solubility cause it to dissolve into groundwater more readily than other gasoline components. Thus, the initial appearance of MTBE in the groundwater is often a good indicator of a recent gasoline spill. MTBE's very low retardation and minimal biodegradation in groundwater can be used with transport rate calculations to establish relatively accurate estimates of spill timing. Because MTBE moves faster in groundwater than BTEX compounds, if a gasoline spill site has a BTEX plume that is longer than the MTBE plume, it is certain that at least two distinctly different gasoline releases have occurred. This allows for the identification of new gasoline spills, even when substantial subsurface petroleum contamination already exists. An example application is reviewed to demonstrate the use of MTBE data in forensic investigations.     

The Use of the Isotopic Composition of Individual Compounds for Correlating Spilled Oils and Refined Products in the Environment with Suspected Sources

Correlation of crude oils, or refined products, in the environment with suspected sources is typically undertaken through the use of GC and GCMS and in certain cases bulk carbon isotope compositions. However, with crude condensates, or refined products in particular, the absence, or low concentration, of biomarkers precludes their successful use for making unique correlations. An alternative and, sometimes, complimentary technique for correlation of such products is evolving through the use of combined gas chromatography–isotope ratio mass spectrometry (GCIRMS). This approach permits determination of the carbon and hydrogen isotopic composition of individual compounds in the crude oil or refined product to produce isotopic fingerprints for use in correlation studies. In this paper, it is proposed to review applications of GCIRMS to the correlation of various spilled products with their suspected sources in different environments. Whilst not proposing that this technique will replace GC or GCMS; it is proposed that GCIRMS is a very powerful tool to be used in conjunction with GC and GCMS to make such correlations. Although isotopic fractionation has been observed in some of the lighter components such as benzene and toluene, higher carbon numbered compounds, say above C₁₀, do not appear to undergo any significant isotopic fractionation as a result of weathering. Furthermore with refined products, isotopic fractionation of the lighter components has the potential to demonstrate the onset of natural attenuation of refined products in the environment.     

Evaluation of combustion by-products of MTBE as a component of reformulated gasoline

Methyl tertiary-butyl ether (MTBE) is a gasoline oxygenate that is widely used throughout the US and Europe as an octane-booster and as a means of reducing automotive carbon monoxide (CO) emissions. The combustion by-products of pure MTBE have been evaluated in previous laboratory studies, but little attention has been paid to the combustion by-products of MTBE as a component of gasoline. MTBE is often used in reformulated gasoline (RFG), which has chemical and physical characteristics distinct from conventional gasoline. The formation of MTBE by-products in RFG is not well-understood, especially under "worst-case" vehicle emission scenarios such as fuel-rich operations, cold-starts or malfunctioning emission control systems, conditions which have not been studied extensively. Engine-out automotive dynamometer studies have compared RFG with MTBE to non-oxygenated RFG. Their findings suggest that adding MTBE to reformulated gasoline does not impact the high temperature flame chemistry in cylinder combustion processes. Comparison of tailpipe and exhaust emission studies indicate that reactions in the catalytic converter are quite effective in destroying most hydrocarbon MTBE by-product species. Since important reaction by-products are formed in the post-flame region, understanding changes in this region will contribute to the understanding of fuel-related changes in emissions.     

Organic and inorganic components of aerosols over the central Himalayas: winter and summer variations in stable carbon and nitrogen isotopic composition

The aerosol samples were collected from a high elevation mountain site, Nainital, in India (1958 m asl) during September 2006 to June 2007 and were analyzed for water-soluble inorganic species, total carbon, nitrogen, and their isotopic composition (δ¹³C and δ¹⁵N, respectively). The chemical and isotopic composition of aerosols revealed significant anthropogenic influence over this remote free-troposphere site. The amount of total carbon and nitrogen and their isotopic composition suggest a considerable contribution of biomass burning to the aerosols during winter. On the other hand, fossil fuel combustion sources are found to be dominant during summer. The carbon aerosol in winter is characterized by greater isotope ratios (av. ?24.0?‰), mostly originated from biomass burning of C₄ plants. On the contrary, the aerosols in summer showed smaller δ¹³C values (?26.0?‰), indicating that they are originated from vascular plants (mostly of C₃ plants). The secondary ions (i.e., SO₄ ^2?, NH₄ ⁺, and NO₃ ^?) were abundant due to the atmospheric reactions during long-range transport in both seasons. The water-soluble organic and inorganic compositions revealed that they are aged in winter but comparatively fresh in summer. This study validates that the pollutants generated from far distant sources could reach high altitudes over the Himalayan region under favorable meteorological conditions.     

In situ biodegradation determined by carbon isotope fractionation of aromatic hydrocarbons in an anaerobic landfill leachate plume (Vejen,Denmark)

Concentrations and isotopic compositions (13C/12C) of aromatic hydrocarbons were determined in eight samples obtained from the strongly anoxic part of the leachate plume downgradient from the Vejen Landfill (Denmark), where methanogenic, sulfate-reducing and iron-reducing conditions were observed. Despite the heterogeneous distribution of the compounds in the plume, the isotope fractionation proved that ethylbenzene and m/p-xylene were subject to significant biodegradation within the strongly anoxic plume. The isotope fractionation factors (alphaC) for the degradation of the m/p-xylene (1.0015) and ethylbenzene (1.0021) obtained from the field observations were similar to factors previously determined for the anaerobic degradation of toluene and o-xylene in laboratory experiments, and suggest that in situ biodegradation is one major process controlling the fate of these contaminants in this aquifer. The isotope fractionation determined for 1,2,4-trimethylbenzene and 2-ethyltoluene suggested in situ biodegradation; however, the isotopic composition did not correlate well with the respective concentration as expressed by the Rayleigh equation. Some other compounds (1,2,3-trimethylbenzene, o-xylene, naphthalene and fenchone) did not show significant enrichments in delta13C values along the flow path. The compound concentrations were too low for accurate isotope analyses of benzene, toluene, 1- and 2-methylnaphthalene, while interferences in the chromatography made it impossible to evaluate the isotopic composition for 4-ethyltoluene, 1,3,5-trimethylbenzene and camphor.In addition to demonstrating the potential of assessing isotopic fractionation as a means for documenting the in situ biodegradation of complex mixtures of aromatic hydrocarbons in leachate plumes, this study also illustrates the difficulties for data interpretation in complex plumes and high analytical uncertainties for isotope analysis of organic compounds in low concentration ranges.     

Alveolar Breath Sampling and Analysis to Assess Exposures to Methyl Tertiary Butyl Ether (MTBE) During Motor Vehicle Refueling

Abstract

Methyl tertiary butyl ether (MTBE) is added to gasoline (15% by volume) in many areas of the U.S. to help control carbon monoxide emissions from motor vehicles. In this study we present a sampling and analytical methodology that can be used to assess consumers' exposures to MTBE that may result from routine vehicle refueling operations. The method is based on the collection of alveolar breath samples using evacuated one-liter stainless steel canisters and analysis using a gas chromatograph-mass spectrometer equipped with a patented "valveless" cryogenic preconcentrator.

To demonstrate the utility of this approach, a series of breath samples was collected from two individuals (the person pumping the fuel and a nearby observer) immediately before and for 64 min after a vehicle was refueled with premium grade gasoline. Results demonstrate low levels of MTBE in both subjects' breaths before refueling, and levels that increased by a factor of 35 to 100 after the exposure. Breath elimination models fitted to the post exposure measurements indicate that the half-life of MTBE in the first physiological compartment was between 1.3 and 2.9 min. Analysis of the resulting models suggests that breath elimination of MTBE during the 64 min monitoring period was approximately 115 jug for the refueling subject while it was only 30 ug for the nearby observer. This analysis also shows that the post exposure breath elimination of other gasoline constituents was consistent with previously published observations.

These results demonstrate that this new methodology can be used effectively in studies designed to assess exposures to MTBE. The method can be used to objectively demonstrate recent exposures, the relative magnitude of an exposure, and the approximate duration of the resulting bloodborne dose. Once a blood/breath partition coefficient for MTBE has been firmly established, the bloodborne concentration of the absorbed material can be determined using these techniques as well.     

Emission and fate assessment of methyl tertiary butyl ether in the Boston area airshed using a simple multimedia box model: comparison with urban air measurements

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 microg/m3 MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 microg/m3 and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (*OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

The Use of the Isotopic Composition of Individual Compounds for Correlating Spilled Oils and Refined Products in the Environment with Suspected Sources

Correlation of crude oils, or refined products, in the environment with suspected sources is typically undertaken through the use of GC and GCMS and in certain cases bulk carbon isotope compositions. However, with crude condensates, or refined products in particular, the absence, or low concentration, of biomarkers precludes their successful use for making unique correlations. An alternative and, sometimes, complimentary technique for correlation of such products is evolving through the use of combined gas chromatography-isotope ratio mass spectrometry (GCIRMS). This approach permits determination of the carbon and hydrogen isotopic composition of individual compounds in the crude oil or refined product to produce isotopic fingerprints for use in correlation studies. In this paper, it is proposed to review applications of GCIRMS to the correlation of various spilled products with their suspected sources in different environments. Whilst not proposing that this technique will replace GC or GCMS; it is proposed that GCIRMS is a very powerful tool to be used in conjunction with GC and GCMS to make such correlations. Although isotopic fractionation has been observed in some of the lighter components such as benzene and toluene, higher carbon numbered compounds, say above C 10 , do not appear to undergo any significant isotopic fractionation as a result of weathering. Furthermore with refined products, isotopic fractionation of the lighter components has the potential to demonstrate the onset of natural attenuation of refined products in the environment.     

Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone

The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.     

Emission and Fate Assessment of Methyl Tertiary Butyl Ether in the Boston Area Airshed Using a Simple Multimedia Box Model: Comparison with Urban Air Measurements

Abstract

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 [H9262]g/m³ MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 μg/m³ and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (.OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. >9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and delta13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched delta13C values compared to the upgradient mean. In addition, delta13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.     

Determination of naturally occurring MTBE biodegradation by analysing metabolites and biodegradation by-products

Methyl tert-butyl ether (MTBE) is one of the main additives in gasoline. Its degradation is known to be difficult in natural environments. In this study, significant MTBE degradation is demonstrated at a contaminated site in Leuna (eastern Germany). Since the extent of the plume appeared to be constant over the last 5 years, an extended study was performed to elucidate the degradation processes. Special attention was paid to the production, accumulation and degradation of metabolites and by-products. Groundwater samples from 105 monitoring wells were used to measure 20 different substances. During the degradation process, several intermediates such as tert-butyl alcohol (TBA), tert-butyl formate, formate and lactate were produced. However, the potentially carcinogenic by-product methacrylate was not detected in several hundred samples. At the Leuna site, MTBE degradation occurred under microaerobic conditions. In contrast to hydrocarbons and BTEX, there was no evidence for anaerobic MTBE degradation. Among the degradation products, TBA was found to be a useful intermediate to identify MTBE degradation, at least under microaerobic conditions. TBA accumulation was strongly correlated to MTBE degradation according to the kinetic properties of both degradation processes. Since maximum degradation rates (v(max)) and k(m) values were higher for MTBE (v(max)=2.3 mg/l/d and k(m)=3.2 mg/l) than for TBA (v(max)=1.35 mg/l/d and k(m)=0.05 mg/l), TBA significantly accumulated as an intermediate by-product. The field results were supported by bench scale model aquifer experiments.     

MTBE in California Drinking Water: An Analysis of Patterns and Trends

Over the past decade, there has been much publicity surrounding the impact of Methyl tert -butyl ether (MTBE) on drinking water supplies in the United States. In California, the presence of MTBE in groundwater and drinking water has led to a ban on the future use of MTBE in gasoline. Other states, such as those in the northeast, are also seeking ways to reduce or eliminate the use of MTBE due to perceived threats to the environment and public health. Despite claims about the incidence of MTBE in drinking water, no comprehensive characterization has been conducted on the available drinking water monitoring data. This paper provides a detailed analysis of the MTBE drinking water data compiled by the California Department of Health Services (CDHS) from 1995 to 2000. We find that MTBE was detected in about 1.3% of all drinking water samples, 2.5% of drinking water sources, and 3.7% of drinking water systems in California over this 6-year period. Our analysis reveals that many drinking water sources are not sampled routinely for MTBE, and in those sources that appear to be affected by MTBE, the compound is not consistently detected. The majority of MTBE detections are also concentrated in several geographic areas, which contain about 9-21% of the total California population. Average detected MTBE concentrations have decreased significantly since 1995 and 1996, ranging from 5 to 15 ppb over the last 3 years depending on the outcome of interest. Of the samples in which MTBE was present above the analytical detection limit, the concentrations in approximately 73% of drinking water samples and 86% of drinking water sources and systems were below the State's primary health-based standard of 13 ppb. Our findings suggest that, although some drinking water supplies in California have been affected by MTBE, the majority of drinking water sources and systems either have not been affected at all or contain MTBE at concentrations below levels that are likely to be of health concern.