Evidence for MTBE in Heating Oil

"Contamination of heating oil with MTBE could result in increasing the environmental impact of subsurface heating oil releases."     

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.     

MTBE in Drinking Water Production – Occurrence and Efficiency of Treatment Technologies

In Germany, the gasoline additive methyl tert‐butyl ether (MTBE) is almost constantly detected in measurable concentrations in surface waters and is not significantly removed during riverbank filtration. The removal of MTBE from water has been the focus of many studies that mostly were performed at high concentration levels and centred in understanding the mechanisms of elimination. In order to assess the performance of conventional and advanced water treatment technologies for MTBE removal in the low concentration range further studies were undertaken. Laboratory experiments included aeration, granulated activated carbon (GAC) adsorption, ozonation and advanced oxidation processes (AOP). The results show that the removal of MTBE by conventional technologies is not easily achieved. MTBE is only removed by aeration at high expense. Ozonation at neutral pH values did not prove to be effective in eliminating MTBE at all. The use of ozone/H₂O₂ (AOP) may lead to a partly elimination of MTBE. However, the ozone/H₂O₂ concentrations required for a complete removal of MTBE from natural waters is much higher than the ozone levels applied nowadays in waterworks. MTBE is only poorly adsorbed on activated carbon, thus GAC filtration is not efficient in eliminating MTBE. A comparison with real‐life data from German waterworks reveals that if MTBE is detected in the raw water it is most often found in the corresponding drinking water as well due to the poor removal efficiency of conventional treatment steps.     

A Dynamic Model to Simulate Spills of Fuel and Diesel Oil in the Terrestrial Environment during Extreme Fluvial Floods

Extreme fluvial floods may cause severe contamination with fuel oil and diesel, originating from gasoline pipes and tanks in private households and industrial areas, respectively. Geo‐referenced oil spills in the region of Bitterfeld (Germany) after extreme flood events, such as in August 2002, were simulated using the two‐dimensional (2D) Finite Element model system Telemac2D, which is subdivided into a hydrodynamic (Telemac‐2D) and a transport module (Subief2D). Fuel oil settled via adhesion showed a thickness of less than 1.0 mm. Fuel oil concentrations on the flood wave amounted up to 80 g m^–3 in the vicinity of the point sources. At a distance of several hundred meters downstream of the point sources, the fuel oil concentrations were calculated to be zero. Settled areas were only partially contaminated with fuel oil. While one village experienced severe oil contamination, the town of Bitterfeld was almost unaffected by oil spills. It was demonstrated that the 2D transport model applied is capable of simulating fuel oil spills during extreme high waters in the terrestrial environment. Such simulations of fuel oil spills will feed into a GIS‐based decision support system of flood protection.     

Potential Occurrence of MTBE and BTEX in Groundwater Resources of Amman–Zarqa Basin,Jordan

This study investigates potential occurrence, distribution, and sources of the newly added gasoline oxygenate, methyl‐tert‐butyl ether (MTBE) and the petroleum derivatives benzene, toluene, ethylbenzene, and xylenes called collectively, BTEX, in Jordan's heavily populated Amman–Zarqa Basin (AZB). It presents the first data on the levels of MTBE and BTEX in the aquifers of this basin. One hundred and seventy‐nine (179) groundwater wells were sampled near petrol service stations, oil refinery storage tanks, car wrecks, bus stations, and chemical industries at different locations in the basin. Headspace GC and purge and trap GC–MS were utilized to determine the target substances in the samples. Concentrations of BTEX varied between no‐detection (minimum) for all of them to 6.6 µg/L (maximum) for ethylbenzene. MTBE was found in few samples but none has exceeded the regulated levels; its concentrations ranged between no‐detection to 4.1 µg/L. However, though the contamination levels are very low they should be considered alarming.     

Used Motor Oil as a Source of MTBE, TAME, and BTEX to Ground Water

Methyl tert-butyl ether (MTBE), the widely used gasoline oxygenate, has been identified as a common ground water contaminant, and BTEX compounds (benzene, toluene, ethylbenzene, and xylenes) have long been associated with gasoline spills. Because not all instances of ground water contamination by MTBE and BTEX can be attributed to spills or leaking storage tanks, other potential sources need to be considered. In this study, used motor oil was investigated as a potential source of these contaminants. MTBE in oil was measured directly by methanol extraction and gas chromatography using a flame ionization detector (GC/FID). Water was equilibrated with oil samples and analyzed for MTBE, BTEX, and the oxygenate tert-amyl methyl ether (TAME) by purge- and-trap concentration followed by GC/FID analysis. Raoult's law was used to calculate oil-phase concentrations of MTBE, BTEX, and TAME from aqueous-phase concentrations. MTBE, TAME, and BTEX were not detected in any of five new motor oil samples, whereas these compounds were found at significant concentrations in all six samples of the used motor oil tested for MTBE and all four samples tested for TAME and BTEX. MTBE concentrations in used motor oil were on the order of 100 mg/L. TAME concentrations ranged from 2.2 to 87 mg/L. Concentrations of benzene were 29 to 66 mg/L, but those of other BTEX compounds were higher, typically 500 to 2000 mg/L.     

Method for Determining the Age of Diesel Oil Spills in the Soil

This study evaluates the changes in the composition of diesel oil as a function of the time during which the oil has been present in the vadose zone. The study also develops a reliable method for determining the age of diesel oil in the subsurface soil environment at service stations, oil terminals, and similar locations where the diesel is protected from direct exposure to factors increasing the rate of microbial activity.
Analyses demonstrate that n-alkanes are the dominant components of fresh diesel oil and isoprenoids the dominant components of degraded diesel oil. The analyses also show that the composition of fresh diesel oil produced in 1992 and that produced in 1974 is basically the same.
The difference in composition between fresh and degraded oil is the basis for defining a degradation ratio or rate of alteration in the composition of the diesel oil expressed in terms of a ratio between n-alkanes and isoprenoids. At 12 test locations where the date of property damage was known, the C₁₇/pristane ratio had by far the highest correlation factor (.89) with the residence time of the diesel based on the average degradation ratio for each location. Based on this high correlation factor, the C₁₇/pristane ratio can be used to estimate the age of a diesel oil spill. The standard error of such an estimate is approximately two years.     

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.     

MTBE, TBA, and TAME Attenuation in Diverse Hyporheic Zones

Groundwater contamination by fuel-related compounds such as the fuel oxygenates methyl tert -butyl ether (MTBE), tert -butyl alcohol (TBA), and tert -amyl methyl ether (TAME) presents a significant issue to managers and consumers of groundwater and surface water that receives groundwater discharge. Four sites were investigated on Long Island, New York, characterized by groundwater contaminated with gasoline and fuel oxygenates that ultimately discharge to fresh, brackish, or saline surface water. For each site, contaminated groundwater discharge zones were delineated using pore water geochemistry data from 15 feet (4.5 m) beneath the bottom of the surface water body in the hyporheic zone and seepage-meter tests were conducted to measure discharge rates. These data when combined indicate that MTBE, TBA, and TAME concentrations in groundwater discharge in a 5-foot (1.5-m) thick section of the hyporheic zone were attenuated between 34% and 95%, in contrast to immeasurable attenuation in the shallow aquifer during contaminant transport between 0.1 and 1.5 miles (0.1 to 2.4 km). The attenuation observed in the hyporheic zone occurred primarily by physical processes such as mixing of groundwater and surface water. Biodegradation also occurred as confirmed in laboratory microcosms by the mineralization of U- ¹⁴C-MTBE and U-¹⁴C-TBA to ¹⁴CO₂ and the novel biodegradation of U- ¹⁴C-TAME to ¹⁴CO₂ under oxic and anoxic conditions. The implication of fuel oxygenate attenuation observed in diverse hyporheic zones suggests an assessment of the hyporheic zone attenuation potential (HZAP) merits inclusion as part of site assessment strategies associated with monitored or engineered attenuation.     

Structural health monitoring of bridges in the State of Connecticut

A joint effort between the Connecticut Department of Transportation and the University of Connecticut has been underway for more than 20 years to utilize various structural monitoring approaches to assess different bridges in Connecticut. This has been done to determine the performance of existing bridges, refine techniques needed to evaluate different bridge components, and develop approaches that can be used to provide a continuous status of a bridge＇s structural integrity. This paper briefly introduces the background of these studies, with emphasis on recent research and the development of structural health monitoring concepts. This paper presents the results from three different bridge types： a post-tensioned curved concrete box girder bridge, a curved steel box-girder bridge, and a steel multi-girder bridge. The structural health monitoring approaches to be discussed have been successfully tested using field data collected during multi-year monitoring periods, and are based on vibrations, rotations and strains. The goal has been to develop cost-effective strategies to provide critical information needed to manage the State of Connecticut＇s bridge infrastructure.     

Laboratory and Numerical Investigations of Air Sparging Using MTBE as a Tracer

Air sparging experiments were conducted in a laboratory column to investigate air flow and mass transfer behavior in different types of sand at different air injection rates. Methyl tertiary butyl ether (MTBE) was applied as a tracer, and by measuring the volatilization and the mean air content during the experiments, the air flow pattern and its influence on mass transfer were assessed. The experimental results showed large differences among the sand types. In fine sand, the mean air content was high and the volatilization of MTBE was rapid with total recovery after a few hours. In coarse sand, the mean air content was low and the volatilization of MTBE was limited. The results indicate two different air flow distributions. In fine-grained materials, a uniform air distribution can be expected compared to coarse-grained materials where isolated air channels will limit the mass transfer. Afterwards, the experiments were simulated using the numerical multiphase flow code T2VOC, and the results compared to those obtained in the laboratory. The experiments with fine sand were simulated well, while for coarser sand types the volatilization was highly overestimated. The differences between model and laboratory results were mainly attributed to the nonuniformity of the air saturation and the neglection of kinetics in the mass transfer formulation.     

A Study of Long-Term MTBE Attenuation in the Borden Aquifer, Ontario, Canada

In 1988 and 1989, a natural gradient tracer test was performed in the shallow, aerobic and aquifer at Canadian Forces Base (CFB) Borden. A mixture of ground water containing dissolved oxygenated gasoline was injected below the water table along with chloride (Cl-) as a conservative tracer. The migration of BTEX, MTBE, and Cl was monitored in detail for 16 moths. The mass of BTEX compounds in the plume diminished significantly with time due to intrinsic aerobic biodegradation, while MTBE showed only a small decrease in mass over the 16-month period. In 1995/96, a comprehensive ground water sampling program was undertaken to define the mass of MTBE still present in the aquifer. Since the plume had migrated into an unmonitored section of the Borden Aquifer, numerical modeling and geostatistical methods were applied to define an optimal sampling grid and to improve the level of confidence in the results. A drive point profiling system was used to obtain ground water samples. Numerical modeling with no consideration of degradation pedicted maximum concentrations in excess of 3000 μg/L; field sampling found maximum concentrations of less than 200 μg/L. A mass balance for the remaining MTBE mass in the aquifer eight years after injection showed that only 3% of the original mass remained. Sorption, volatilization, a biotic degradation, and plant uptake are not considered significant attenuation processes for the field conditions. Therefore, we suggest that biodegradation may have played a major role in the attenuation of MTBE within the Borden Aquifer.     

Concentrations of methyl- tert-butyl ether (MTBE) in inputs and receiving waters of Southern California.

The occurrence and concentration of the fuel additive methyl-tert-butyl ether (MTBE) were measured in dry weather runoff, municipal wastewater and industrial effluents, and coastal receiving waters in southern California. Combined, refineries and sewage treatment plants release approximately 214 kg day(-1) of MTBE into the marine environment, with Santa Monica Bay receiving most (98%) of this discharge. Dry weather urban runoff was analysed for samples collected from 25 streams and rivers, and accounted for less than 0.5% of the mass of MTBE discharged to coastal waters. Receiving water samples were collected from 23 stations in Santa Monica Bay, Los Angeles Harbour and Mission Bay or San Diego Bay. MTBE was detected at low concentrations near effluent discharges, however there was no evidence of baywide MTBE contamination related to these outfalls. Marinas and areas used intensively for recreational boating had the highest average MTBE concentration (8.8 microg l(-1)). Surface water contamination was most widespread in San Diego Bay and Mission Bay, areas with no refinery or sewage treatment plant inputs.     

Occurrence and concentration of caffeine in Oregon coastal waters

Caffeine, a biologically active drug, is recognized as a contaminant of freshwater and marine systems. We quantified caffeine concentrations in Oregon's coastal ocean to determine whether levels correlated with proximity to caffeine pollution sources. Caffeine was analyzed at 14 coastal locations, stratified between populated areas with sources of caffeine pollution and sparsely populated areas with no major caffeine pollution sources. Caffeine concentrations were measured in major water bodies discharging near sampling locations. Caffeine in seawater ranged from below the reporting limit (8.5 ng/L) to 44.7 ng/L. Caffeine occurrence and concentrations in seawater did not correspond with pollution threats from population density and point and non-point sources, but did correspond with storm event occurrence. Caffeine concentrations in rivers and estuaries draining to the coast ranged from below the reporting limit to 152.2 ng/L. This study establishes the occurrence of caffeine in Oregon's coastal waters, yet relative importance of sources, seasonal variability, and processes affecting caffeine transport into the coastal ocean require further research.     

Fate of MTBE Relative to Benzene in a Gasoline-Contaminated Aquifer (1993–98)

Methyl tert -butyl ether (MTBE) and benzene have been measured since 1993 in a shallow, sandy aquifer contaminated by a mid-1980s release of gasoline containing fuel oxygenates. In wells downgradient of the release area, MTBK was detected before benzene, reflecting a chromatographic-like separation of these compounds in the direction of ground water flow. Higher concentrations of MTBE and benzene were measured in the deeper sampling ports of multilevel sampling wells located near the release area, and also up to 10 feet (3 m) below the water table surface in nested wells located farther from the release area. This distribution of higher concentrations at depth is caused by recharge events that deflect originally horizontal ground water flowlines. In the laboratory, microcosms containing aquifer material incubated with uniformly labeled ¹⁴C-MTBE under aerobic and anaerobic. Fe(III)-reducing conditions indicated a low but measurable biodegradation potential (<3%¹⁴C-MTBW as ¹⁴CO₂) after a seven-month incubation period, Tert -butyl alcohol (TBA), a proposed microbial-MTBE transformation intermediate, was detected in MTBE-contaminated wells, but TBA was also measured in unsaturated release area sediments. This suggests that TBA may have been present in the original fuel spilled and does not necessarily reflect microbial degradation of MTBE. Combined, these data suggest that milligram per liter to microgram per liter decreases in MTBE concentrations relative to benzene are caused by the natural attenuation processes of dilution and dispersion with less-contaminated ground water in the direction of flow rather than biodegradation at this point source gasoline release site.     

Occurrence of selected estrogens in mangrove sediments

This paper presents results related to the occurrence and distribution of estrogens along the Brazilian coast. Three mangrove areas were chosen to evaluate the presence of estrogens in surface sediments of mangrove forests. The presence of estrogens was observed in all studied sites. 17-α-Ethinylestradiol (EE2), a synthetic estrogen, was the most common and has been found in higher concentration (0.45-129.78 ng/g) compared to 17-β-estradiol (E1) and estrone (E2) (both being natural estrogens). The concentrations of E1 and E2 ranged from 0.02 to 49.27 ng/g and 0.03 to 39.77 ng/g, respectively. Theoretically, under anaerobic conditions EE2 can be reduced to E1 even in environments such as sediments of mangrove forests, which are essentially anaerobic. Even if the concentrations of estrogens seem to be insignificant in some samples, the effects remain uncertain.