Methyl Tert-butyl Ether In Groundwater Research Articles

The in situ treatment of BTEX, MTBE, and TBA in saline groundwater

AbstractA pilot‐scale test was conducted in a saline aquifer to determine if a petroleum hydrocarbon (PHC) plume containing benzene (B), toluene (T), ethylbenzene (E), xylenes (X), methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) could be treated effectively using a sequential treatment approach that employed in situ chemical oxidation (ISCO) and enhanced bioremediation (EBR). Chemical oxidants, such as persulfate, have been shown to be effective in reducing dissolved concentrations of BTEX (B + T + E + X) and additives such as MTBE and TBA in a variety of geochemical environments including saline aquifers. However, the lifespan of the oxidants in saline environments tends to be short‐lived (i.e., hours to days) with their effectiveness being limited by poor delivery, inefficient consumption by nontargeted species, and back‐diffusion processes. Similarly, the addition of electron acceptors has also been shown to be effective at reducing BTEX and associated additives in saline groundwater through EBR, however EBR can be limited by various factors similar to ISCO. To minimize the limitations of both approaches, a pilot test was carried out in a saline unconfined PHC‐impacted aquifer to evaluate the performance of an engineered, combined remedy that employed both approaches in a sequence. The PHC plume had total BTEX, MTBE, and TBA concentrations of up to 4,584; 55,182; and 1,880 μg/L, respectively. The pilot test involved injecting 13,826 L of unactivated persulfate solution (19.4 weight percent (wt.%) sodium persulfate (Na2S2O8) solution into a series of injection wells installed within the PHC plume. Parameters monitored over a 700‐day period included BTEX, MTBE, TBA, sulfate, and sulfate isotope concentrations in the groundwater, and carbon and hydrogen isotopes in benzene and MTBE in the groundwater. The pilot test data indicated that the BTEX, MTBE, and TBA within the PHC plume were treated over time by both chemical oxidation and sulfate reduction. The injection of the unactivated persulfate resulted in short‐term decreases in the concentrations of the BTEX compounds, MTBE, and TBA. The mean total BTEX concentration from the three monitoring wells within the pilot‐test area decreased by up to 91%, whereas MTBE and TBA mean concentrations decreased by up to 39 and 58%, respectively, over the first 50 days postinjection in which detectable concentrations of persulfate remained in groundwater. Concentrations of the BTEX compounds, MTBE, and TBA rebounded at the Day 61 marker, which corresponded to no persulfate being detected in the groundwater. Subsequent monitoring of the groundwater revealed that the concentrations of BTEX continued to decrease with time suggesting that EBR was occurring within the plume. Between Days 51 and 487, BTEX concentrations decreased an additional 84% from the concentration measured on Day 61. Mean concentrations of MTBE showed a reduction during the EBR phase of remediation of 33% while the TBA concentration appeared to decrease initially but then increased as the sulfate concentration decreased as a result of MTBE degradation. Isotope analyses of dissolved sulfate (34S and 18O), and compound‐specific isotope analysis (CSIA) of benzene and MTBE (13C and 2H) supported the conclusions that ISCO and EBR processes were occurring at different stages and locations within the plume over time.

Anaerobic biodegradation of MTBE in a field site above the Israeli Coastal Aquifer: evidence from δ13C compound‐specific isotope analysis

AbstractBACKGROUNDThe fuel additive, methyl tert‐butyl ether (MTBE), is one of the most frequently occurring groundwater pollutants worldwide. The present study focused on assessing microbial degradation of MTBE in groundwater below a gasoline station situated above the Israeli Coastal Aquifer. Groundwater was monitored in six monitoring wells over a time period of 2.5 years.RESULTSThe site water geochemistry indicated that anaerobic conditions prevailed in two of the most contaminated wells. During a year MTBE concentrations declined from 81 to 4.2 mg L−1, concurrently, with a significant change in δ13C from −31.4 to −11.8 ‰ in a source area monitoring well. MTBE biodegradation during microcosm experiments under sulfate reducing and methanogenic conditions resulted in carbon isotopic enrichment factors (ε) of −17.2 ± 1.1 ‰.CONCLUSIONSignificant decrease in MTBE concentrations, along with pronounced changes in carbon isotope composition, indicates in situ degradation of MTBE occurring at the site. This evidence was supported by a microcosm experiment with indigenous microbial cultures. The estimated rate of biodegradation is 0.7 year−1, which is about 70% of the total natural attenuation (NA) processes. © 2016 Society of Chemical Industry

Monitoring In Situ Biodegradation of MTBE Using Multiple Rounds of Compound‐Specific Stable Carbon Isotope Analysis

AbstractAt a large industrial facility, methyl tert‐butyl ether (MTBE) was released to the subsurface and dispersed into the light, non‐aqueous phase liquids (LNAPL), in the first aquifer, with the LNAPL serving as a continuous source of MTBE in groundwater. Compound‐specific isotope analysis was conducted on both MTBE and tert‐butyl alcohol (TBA) in groundwater samples collected in 2008, 2011, and 2013 from wells located along and off the center line of the MTBE plume. The study demonstrated the onset and progress of biodegradation of MTBE between 2008 and 2013. The TBA observed in 2008 appears to be derived only in part from MTBE transformation while a significant portion of TBA might be contributed directly from LNAPL sources. In 2011 to 2013, the dominant source of TBA in the mid‐gradient plume was MTBE transformation. A contribution of an offsite LNAPL source, in particular to the down‐gradient area of the plume, is possible but could not be unequivocally confirmed. The time series provided direct evidence for MTBE biodegradation, but also a valuable insight on the sources of TBA.

Nanotechnology in environmental remediation: degradation of volatile organic compounds (VOCs) over visible-light-active nanostructured materials

Volatile organic compounds (VOCs) are major pollutants and are considered to be one of the most important contaminants generated by human beings living in urban and industrial areas. Methyl tert-butyl ether (MTBE) is a VOC that has been widely used as a gasoline additive to reduce VOC emissions from motor vehicles. However, new gasoline additives like MTBE are having negative environmental impacts. Recent survey reports clearly show that groundwater is often polluted owing to leakage of petroleum products from underground storage tanks. MTBE is highly soluble in water (e.g., 0.35-0.71 M) and has been detected at high concentrations in groundwater. The presence of MTBE in groundwater poses a potential health problem. The documented effects of MTBE exposure are headaches, vomiting, diarrhea, fever, cough, muscle aches, sleepiness, disorientation, dizziness, and skin and eye irritation. To address these problems, photocatalytic treatment is the preferred treatment for polluted water. In the present work, a simple and template-free solution phase synthesis method has been developed for the preparation of novel cadmium sulfide (CdS) hollow microspheres using cadmium nitrate and thioacetamide precursors. The synthesized products have been characterized by a variety of methods, including X-ray powder diffraction, high-resolution scanning electron microscopy (HR-SEM), X-ray photoelectron spectroscopy, and UV-visible diffused reflectance spectroscopy. The HR-SEM measurements revealed the spherical morphology of the CdS microspheres, which evolved by the oriented aggregation of the primary CdS nanocrystals. Furthermore, studies of photocatalytic activity revealed that the synthesized CdS hollow microspheres exhibit an excellent photocatalytic performance in rapidly degrading MTBE in aqueous solution under visible light illumination. These results suggest that CdS microspheres will be an interesting candidate for photocatalytic detoxification studies under visible light radiation.

Regulation of Electrochemically Generated Ferrous Ions from an Iron Cathode for Pd-Catalytic Transformation of MTBE in Groundwater

A novel Pd-based electro-Fenton (E-Fenton) process has recently been developed to transform organic contaminants in groundwater. However, it only produces H2O2 and requires addition of Fe(2+). In this study, an innovative approach is developed to effectively regulate the generation of Fe(2+) from an iron cathode in a three-electrode system in addition to H2O2 production. The Fe(2+) is then used for the Pd-catalytic transformation of methyl tert-butyl ether (MTBE) in groundwater. Results from batch experiments suggest Fe(2+) accumulation follows pseudo-first-order kinetics with rate quantitatively regulated by current and pH, and MTBE can be completely transformed. In a specially configured three-electrode column using iron as the first cathode, the localized acidic conditions develop automatically in the iron cathode and Pd zone by partitioning the current between the two cathodes, leading to controllable generation of Fe(2+) and H2O2. Effects of electrolyte concentrations and types as well as humic acid on MTBE transformation are slight. The stable transformation (~70%) in a long-term study (20 days) suggests this improved Pd-based E-Fenton process is sustainable to produce Fe(2+), H2O2, and appropriate pH conditions simultaneously for transforming organic contaminants. This study presents a new concept of generating Fe(2+) from an iron cathode for the processes requiring Fe(2+).

The Occurrence and Persistence of MTBE in Groundwater in Windham, Maine, USA

A study was conducted from July 1998 through November 2007 on the occurrence and distribution of the fuel oxygenate methyl tert‐butyl ether (MTBE) in a large sand and gravel aquifer located in southern Maine. MTBE was detected in 44% of 129 water samples collected from monitoring wells in concentrations up to 38.7 µg/L (reporting limit = 0.1 µg/L). The number of wells with detectable quantities of MTBE declined slightly between 1999 and 2007, but in general MTBE persisted throughout the period of study. Overall, MTBE was detected more frequently in the shallow and more transmissive parts of the aquifer. There was a statistically significant difference (p < 0.001) for MTBE concentrations relative to nearby land uses. MTBE was detected in 83% of the samples collected from wells in low‐density residential areas, in 50% of samples from urban areas, and in 60% of samples from undeveloped areas. The concentrations of MTBE in the test wells were compared across the sample dates for trends and seven wells had a positive trend (Mann–Kendall statistic), but none was significant at p < 0.05. Nine wells had a negative trend, but only one was significant at p < 0.05. Three wells had no trend. The absence of strong or even consistent trends indicates that MTBE persists in shallow groundwater, even after gasoline formulations were changed to reduce or eliminate MTBE.

Degradation of methyl tert-butyl ether by gel immobilized Methylibium petroleiphilum PM1

Cells of Methylibium petroleiphilum PM1 were immobilized in gel beads to degrade methyl tert-butyl ether (MTBE). Calcium alginate, agar, polyacrylamide and polyvinvyl alcohol were screened as suitable immobilization matrices, with calcium alginate demonstrating the fastest MTBE-degradation rate. The rate was accelerated by 1.8-fold when the beads had been treated in physiological saline for 24 h at 28 °C. MTBE degradation in mineral salts medium (MSM) was accompanied by the increase of biomass. The half-life of MTBE-degradation activity for the encapsulated cells stored at 28 °C was about 120 h, which was obviously longer than that of free cells (approximately 36 h). Efficient reusability of the beads up to 30 batches was achieved in poor nutrition solution as compared to only 6 batches in MSM. The immobilized cells could be operated in a packed-bed reactor for degradation of 10 mg L −1 MTBE in groundwater with more than 99% removal efficiency at hydraulic retention time of 20 min. These results suggested that immobilized cells of PM1 in bioreactor might be applicable to a groundwater treatment system for the removal of MTBE.

Evaluation of TCE and MTBE in situ Biodegradation: Integrating Stable Isotope, Metabolic Intermediate, and Microbial Lines of Evidence

AbstractCompound specific isotope analysis (CSIA) was used to investigate biodegradation of trichloroethene (TCE) and methyl tert‐butyl ether (MTBE) at contaminated field sites in Alaska and New York State, respectively. At both sites, geochemical conditions and the presence of metabolic intermediates (cis‐1‐2‐dichloroethene and tert‐butyl alcohol [TBA]) suggested the potential for biodegradation of TCE and MTBE, respectively. Given that in both cases these metabolic intermediates could also have been present as cocontaminants in the source zone, CSIA was undertaken to evaluate the possibility of in situ biodegradation. At the TCE‐contaminated field site in Alaska, δ13C values of TCE in ground water determined in this study showed no evidence of biodegradation (mean δ13C of −27.0 ± 1.0‰ for nine wells), and quantitative‐polymerase chain reaction analyses of ground water from four wells found no evidence of dechlorinator Dehalococcoides sp. at this site. At the MTBE‐contaminated field site in New York, TBA was present in the ground water but was not present in gasoline sampled from underground storage tanks (UST) on‐site, suggesting that at this site, TBA was potentially a metabolite of MTBE biodegradation rather than a cocontaminant. However, at all sampling times and locations, δ13C and δ2H values of MTBE in ground water were within range of published values for undegraded MTBE in gasoline. While the occurrence of a small extent of in situ MTBE biodegradation cannot be ruled out, the findings suggest that it is more likely that multiple gasoline spills occurred through time, and while present day USTs do not contain TBA as a cocontaminant, gasoline spilled at the site in the past may have. At both contaminated field sites, CSIA, chemical, and microbiological lines of evidence suggest that biodegradation was not a significant attenuation process. The results of these two studies underscore the need for an integrated approach to site assessment that draws on measurements of metabolic intermediates, analysis of stable isotopes, and microbial evidence to give a reliable assessment of in situ biodegradation at contaminated field sites.

Sorption of methyl tert-butyl ether and benzene in fine-grained materials from northern Illinois and the Chalco Basin, Mexico

Methyl tert-butyl ether (MTBE) is a gasoline oxygenate additive used to enhance gasoline combustion by lowering carbon monoxide and hydrocarbon emissions, thus reducing air pollution. However, it has been identified as the second most common volatile organic contaminant of urban aquifers in the United States. Methyl tert-butyl ether has also been blended into two types of gasoline sold in Mexico by the state oil company (Petrleos Mexicanos) but is currently not monitored in groundwater. Early research on MTBE determined that it is unable to sorb to soils and sediments. The objective of this study is to determine if fine-grained materials with high organic matter (0.25–15.3%) have the potential for sorption of MTBE. The experiment consisted of sorption isotherms of loess from DeKalb, Illinois, and lacustrine sediments from Chalco, Mexico. Experiments were performed with various concentrations of MTBE and benzene (10, 50, 100, 500, and 1000 g/L) at 25C and 10C. Methyl tert-butyl ether showed a retardation factor (R) as high as 1.856 0.0130 for lacustrine sediments and 1.095 0.0010 for loess at 25C. Benzene showed retardation factors as high as 1.996 0.0150 in lacustrine sediments and 1.775 0.0050 in loess at 25C. These results showed that sorption, and therefore, the retardation of MTBE in groundwater, is possible in fine-grained materials especially with high organic matter. This research increases the understanding of the fate and transport of MTBE and improves the knowledge to implement the optimal remediation method for sites contaminated by MTBE.

Low‐Temperature MTBE Biodegradation in Aquifer Sediments with a History of Low, Seasonal Ground Water Temperatures

AbstractSediments from two shallow, methyl tert‐butyl ether (MTBE)–contaminated aquifers, with mean ground water temperatures ∼10°C, demonstrated significant mineralization of [U‐14C] MTBE to 14CO2 at incubation temperatures as low as 4°C. These results indicate that microbial degradation can continue to contribute to the attenuation of MTBE in ground water under wintertime, low‐temperature conditions.

MTBE and Gasoline Hydrocarbons in Ground Water of the United States

The occurrence of methyl tert-butyl ether (MTBE) and gasoline hydrocarbons was examined in three types of studies of ground water conducted by the U.S. Geological Survey: major aquifer surveys, urban land-use studies, and agricultural land-use studies. The detection frequency of MTBE was dependent on the study type, with the highest detection frequency in urban land-use studies. Only 13 ground water samples from all study types, or 0.3%, had concentrations of MTBE that exceeded the lower limit of the U.S. EPA's Drinking-Water Advisory. The detection frequency of MTBE was highest in monitoring wells located in urban areas and in public supply wells. The detection frequency of any gasoline hydrocarbon also was dependent on study type and generally was less than the detection frequency of MTBE. The probability of detecting MTBE in ground water was strongly associated with population density, use of MTBE in gasoline, and recharge. Ground water in areas with high population density, in areas where MTBE is used as a gasoline oxygenate, and in areas with high recharge rates had a greater probability of MTBE occurrence. Also, ground water from public supply wells and shallow ground water underlying urban land-use areas had a greater probability of MTBE occurrence compared to ground water from domestic wells and ground water underlying rural land-use areas. The probability of detecting MTBE in ground water was weakly associated with the density of leaking underground storage tanks, soil permeability, and aquifer consolidation, and only concentrations of MTBE >0.5 microg/L were associated with dissolved oxygen.

Investigation of methyl tert-butyl ether levels in river-, ground-, and sewage-waters analyzed using a purge-and-trap interfaced to a gas chromatograph–mass spectrometer

River water collected from 27 sites in 21 rivers, groundwater from 66 sites in 34 cities, and 2 sewage plants in the Niigata Prefecture, Japan (total 301 samples) were analyzed for methyl tert-butyl ether (MTBE) using an improved purge-and-trap-GC–MS method. The amount of MTBE found in water samples from the 27 river sites ranged from 0.003 to 5.3 μg l −1. MTBE was found in all 27 sites during winter but it was found at only 9 sites and 14 sites, respectively, during the summer. MTBE was found most frequently (in 21 sites) at levels ranging from 0.003 to 0.009 μg l −1 during February. The highest levels of MTBE were always found in the samples collected from the same site. The amount of MTBE found in sewage water samples ranged from <0.003 to 0.025 μg l −1. No significant differences were observed between the amounts of MTBE recovered from inflow and outflow waters. Relatively high levels (0.02–0.034 μg l −1) of MTBE were found in January at two sites, which were located on the upper course of the Shinano River. MTBE levels ranged from 0.004 to 0.035 μg l −1 and from 0.005 to 0.041 μg l −1 at the mouths of the Shinano River and Agano River, respectively. The levels of MTBE in groundwater collected from 66 sites in 34 cities in Niigata Prefecture ranged from <0.003 to 5.9 μg l −1.

The sonolytic destruction of methyl tert-butyl ether present in contaminated groundwater.

Ultrasonic irradiation in the presence of ozone was used to efficiently eliminate methyl tert-butyl ether (MTBE) from groundwater. The sonolytic degradation of MTBE was investigated in three different reactor configurations and frequencies: vibrating-plate reactor (VPR, 358 kHz), near-field acoustical processor (NAP 20 and 16 kHz), and radial-tube resonator (RTR. 20 kHz). The sonochemical reactors can be ordered in terms of their efficiency with respect to the degradation of MTBE in the following way: VPR > RTR > NAP. The higher elimination rates of MTBE in groundwater by combined ultrasound-ozone systems are attributed to the effective conversion of ozone to the OH radical, even in the presence of high alkalinity. Carbonate radicals, which were formed from the oxidation of bicarbonate by hydroxyl radicals, are shown to react with MTBE via a hydrogen-atom abstraction pathway. Methyl-tert-butyl ether was also rapidly eliminated from the groundwater underlying a major intemational airport by direct chemical oxidation with a mixture of hydrogen peroxide and ozone.

Review of Natural Attenuation of BTEX and MTBE in Groundwater

Monitored natural attenuation has become accepted as an appropriate “technology” for treating petroleum hydrocarbon-contaminated groundwater. Commonly, the monoaromatic compounds benzene, toluene, ethylbenzene, and xylenes (BTEX) and oxygenated additives, e.g., methyl tert-butyl ether (MTBE), are the major constituents of regulatory importance. Although a variety of naturally occurring attenuation mechanisms may reduce BTEX and MTBE concentrations, intrinsic biodegradation is the primary destructive mechanism. Attenuation by anaerobic biodegradation is important for BTEX compounds because of the relative abundance of anaerobic electron acceptors as compared with dissolved oxygen. Field studies indicate that MTBE is also biodegradable in shallow aquifers, but at a slower rate relative to BTEX compounds; thus, dispersion and dilution may also be important MTBE attenuation mechanisms. To demonstrate that natural attenuation is occurring, it is critical to document the proposed natural attenuation processes in the field. These processes often cause measurable “footprints.” At a large number of petroleum-hydrocarbon release sites, natural attenuation processes have been observed and documented and found to control the extent of migration of BTEX contaminants. Although the presence of MTBE may compromise the use of natural attenuation at some sites due to the greater mobility and persistence of MTBE compared to BTEX, some data indicate that MTBE plumes do eventually stabilize.

Methyl tert‐butyl ether degradation in the unsaturated zone and the relation between MTBE in the atmosphere and shallow groundwater

Atmospheric methyl tert‐butyl ether (MTBE) concentrations in southern New Jersey generally exceeded concentrations in samples taken from the unsaturated zone. A simple unsaturated zone transport model indicates that MTBE degradation can explain the attenuation with half‐lives from a few months to a couple of years. Tert‐butyl alcohol (TBA), a possible degradation product of MTBE, was detected in unsaturated‐zone samples at concentrations exceeding atmospheric levels at some sites, suggesting the possible conversion of MTBE to TBA. At sites where MTBE was detected in shallow groundwater, the concentration was typically higher than the overlying unsaturated‐zone concentration. This observation is consistent with outgassing from the aquifer and combined with the unsaturated‐zone attenuation suggests some of the MTBE detections in shallow groundwater are nonatmospheric in origin, coming from leaking tanks, road runoff, or other sources. The identification of sources of MTBE in groundwater and attenuation mechanisms through the hydrologic cycle is critical in developing an understanding of the long‐term effect of MTBE releases.

Monitoring biodegradation of methyl tert-butyl ether (MTBE) using compound-specific carbon isotope analysis.

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@1000), aqueous phase/gas-phase partitioning (0.17 +/- 0.05@1000), and organic phase/aqueous-phase partitioning (0.18 +/- 0.24@1000) 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@1000 after 95 to 97% degradation. For both experiments, similar isotopic enrichment factors were obtained (-1.52 +/- 0.06 to -1.97 +/- 0.05@1000). 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@1000. 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.

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 15ppb 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 13ppb. 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.

Trace analysis of ethanol, MTBE, and related oxygenate compounds in water using solid-phase microextraction and gas chromatography/mass spectrometry.

Solid-phase microextraction (SPME) and gas chromatography/mass spectrometry have been combined for trace-level determination of very polar compounds in water, including the widely used gasoline oxygenates ethanol and methyl tert-butyl ether (MTBE). A relatively simple extraction method using a divinylbenzene/Carboxen/poly(dimethylsiloxane) SPME fiber was optimized for the routine analysis of ethanol and MTBE in groundwater and reagent water. A sodium chloride concentration of 25% (w/w) combined with an extraction time of 25 min provided the greatest sensitivity while maintaining analytical efficiency. Replicate analyses in fortified reagent and groundwater spiked with microgram per liter concentrations of ethanol and MTBE indicate quantitative and reproducible recovery of these and related oxygenate compounds. Method detection limits were 15 microg L(-1) for ethanol, 1.8 microg L(-1) for tert-butyl alcohol, 0.038 microg L(-1) for tert-amyl methyl ether, 0.025 microg L(-1) for ethyl-tert-butyl ether, and 0.008 microg L(-1) for MTBE.

Preliminary Assessment of the Occurrence and Possible Sources of MTBE in Groundwater in the United States, 1993−1994

The 1990 Clean Air Act Amendments require fuel oxygenates to be added to gasoline used in some metropolitan areas to reduce atmospheric concentrations of carbon monoxide or ozone. Methyl tert-butyl ether (MTBE) is the most commonly used fuel oxygenate and is a relatively new gasoline additive. Nevertheless, out of 60 volatile organic chemicals analyzed, MTBE was the second most frequently detected chemical in samples of shallow ambient groundwater from urban areas that were collected during 1993-1994 as part of the U.S. Geological Survey's National Water-Quality Assessment program. Samples were collected from five drinking water wells, 12 springs, and 193 monitoring wells in urban areas. No MTBE was detected in drinking water wells. At a reporting level of 0.2 μg/L, MTBE was detected most frequently in shallow groundwater from urban areas (27% of 210 wells and springs sampled in eight areas) as compared to shallow groundwater from agricultural areas (1.3% of 549 wells sampled in 21 areas) or deeper groundwater from major aquifers (1.0% of 412 wells sampled in nine areas). Only 3% of the shallow wells sampled in urban areas had concentrations of MTBE that exceed 20 μg/L, which is the estimated lower limit of the United States Environmental Protection Agency draft drinking water health advisory. Because MTBE is persistent and mobile in groundwater, it can move from shallow to deeper aquifers with time. In shallow urban groundwater, MTBE generally was not found with benzene, toluene, ethylbenzene, or xylene (BTEX) compounds, which commonly are associated with gasoline spills. This disassociation causes uncertainty as to the source of MTBE. Possible sources of MTBE in groundwater include point sources, such as leaking storage tanks, and non-point sources, such as recharge of precipitation and stormwater runoff.