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Headspace microdrop analysis--an alternative test method for gasoline diluent and benzene, toluene, ethylbenzene and xylenes in used engine oils.

The primary standard test method used for the determination of gasoline diluent in used engine oils is method D 3525-93 of the American Society for Testing and Materials (ASTM), which involves direct injection of used oil onto a packed GC column and flame ionization detection. Recently, we have utilized a new headspace sampling method: headspace solvent microextraction (HSM), for GC and GC-MS analysis of gasoline diluent in used engine oils. High resolution capillary columns can be used without the necessity for the use of inlet cryogenic cooling or expensive sampling interfaces. This analytical method, which we generically refer to as headspace microdrop analysis yields results comparable to those obtained using the ASTM method, with the added benefit that it allows the quantification of individual volatile diluent components, including benzene, toluene, ethylbenzene and the xylenes.

Benzene↗

Biofiltration of gasoline vapor by compost media.

Gasoline vapor was treated using a compost biofilter operated in upflow mode over 4 months. The gas velocity was 6 m/h, yielding an empty bed retention time (EBRT) of 10 min. Benzene, toluene, ethylbenzene and xylene (BTEX) and total petroleum hydrocarbon (TPH) removal efficiencies remained fairly stable approximately 15 days after biofilter start-up. The average removal efficiencies of TPH and BTEX were 80 and 85%, respectively, during 4 months of stable operation. Biodegradation portions of the treated TPH and BTEX were 60 and 64%, respectively. When the influent concentration of TPH was less than 7800 mg TPH/m3, approximately 50% of TPH in the gas stream was removed in the lower half of the biofilter. When the influent concentration of BTEX was less than 720 mg BTEX/m3, over 75% of BTEX in the gas stream was removed in the lower half of the biofilter. Benzene removal efficiency was the lowest among BTEX. A pressure drop could not be detected over a 1-m bed height at a gas velocity of 6 m/h after approximately 4 months of operation. Results demonstrated that BTEX in gasoline vapor could be treated effectively using a compost biofilter.

Air Pollutants↗

Evaluation of natural attenuation rate at a gasoline spill site.

Contamination of groundwater by gasoline and other petroleum-derived hydrocarbons released from underground storage tanks (USTs) is a serious and widespread environmental problem. Natural attenuation is a passive remedial approach that depends upon natural processes to degrade and dissipate contaminants in soil and groundwater. Currently, in situ column technique, microcosm, and computer modeling have been applied for the natural attenuation rate calculation. However, the subsurface heterogeneity reduces the applicability of these techniques. In this study, a mass flux approach was used to calculate the contaminant mass reduction and field-scale decay rate at a gasoline spill site. The mass flux technique is a simplified mass balance procedure, which is accomplished using the differences in total contaminant mass flux across two cross-sections of the contaminant plume. The mass flux calculation shows that up to 87% of the dissolved total benzene, toluene, ethylbenzene, and xylene (BTEX) isomers removal was observed via natural attenuation at this site. The efficiency of natural biodegradation was evaluated by the in situ tracer method, and the first-order decay model was applied for the natural attenuation/biodegradation rate calculation. Results reveal that natural biodegradation was the major cause of the BTEX mass reduction among the natural attenuation processes, and approximately 88% of the BTEX removal was due to the natural biodegradation process. The calculated total BTEX first-order attenuation and biodegradation rates were 0.036 and 0.025% per day, respectively. Results suggest that the natural attenuation mechanisms can effectively contain the plume, and the mass flux method is useful in assessing the occurrence and efficiency of the natural attenuation process.

Biodegradation, Environmental↗

Five-stage environmental exposure assessment strategy for mixtures: gasoline as a case study.

A five-stage strategy is suggested for conducting an exposure assessment of mixtures that may contain numerous chemical components. The stages are: (1) determination of mixture composition and variability, (2) selection of component groups within the mixture and documentation of criteria used for this selection, (3) compilation of relevant property data for each group, (4) assessment of environmental fate of each group, and (5) assessment of environmental and human exposure to each group and to the mixture as a whole. A subsequent step is the assessment of environmental and/or human risk associated with the individual and aggregate exposure to each group. The approach is illustrated by application to gasoline, which is treated as 24 component groups or hydrocarbon blocks. Focusing on stages 2-4, the illustration shows that the groups display widely different environmental fates as a result of their different physicochemical properties, degradation half-lives, and mode-of-entry into the environment. As a result, the relative proportions of groups in each environmental medium (such as air and water) differ greatly from that of the original mixture. It is thus important to treat gasoline and similar mixtures as a number of component groups instead of as a single substance. A generic procedure is suggested in which the model is run for unit emissions of each component group to air, water, and soil. These results are compiled into matrices that can then be conveniently scaled to actual emission rates without rerunning the model. Methods for determining subsequent exposure and risk are also briefly outlined.

Air↗

Applications of contaminant fate and bioaccumulation models in assessing ecological risks of chemicals: a case study for gasoline hydrocarbons.

Mass balance models of chemical fate and transport can be applied in ecological risk assessments for quantitative estimation of concentrations in air, water, soil, and sediment. These concentrations can, in turn, be used to estimate organism exposures and ultimately internal tissue concentrations that can be compared to mode-of-action-based critical body residues that induce toxic effects. From this comparison, risks to the exposed organism can be evaluated. To demonstrate the use of fate models in ecological risk assessment, we combine the EQuilibrium Criterion (EQC) environmental fate model with a simple screening level biouptake model for three representative organisms: a bird, a mammal, and a fish. This effort yields estimates of internal body concentrations that can be compared with levels known to elicit toxic effects. As an illustration, we present an analysis of 24 hydrocarbon components of gasoline that differ in properties but are assumed to elicit toxicity by a common narcotic mode of action. Results demonstrate that differences in chemical properties and mode of entry into the environment lead to profound differences in the efficiency of transport from emission to target biota. We discussthe implications of these results and draw attention to the insights gained about regional fate and ecological risks associated with gasoline. This approach is suitable for assessing single chemicals or mixtures that have similar modes of action. We conclude that the model-based methodologies presented are widely applicable for screening level ecological risk assessments that support effective chemicals management.

Animals↗

Anaerobic biodegradation of BTEX and gasoline in various aquatic sediments.

We examined the extent of biodegradation of benzene, toluene, ethylbenzene and the three isomers of xylene (BTEX) as a mixture and from gasoline in four different sediments: the New York/New Jersey Harbor estuary (polluted); Tuckerton, N.J. (pristine); Onondaga Lake, N.Y. (polluted) and Blue Mtn. Lake, N.Y. (pristine). Enrichment cultures were established with each sediment using denitrifying, sulfidogenic, methanogenic and iron reducing media, as well as site water. BTEX loss, as measured by GC-FID, was extensive in the sediments which had a long history of pollution, with all compounds being utilized within 21-91 days in the most active cultures, and was very slight or non-existent in the pristine sediments. Also, the pattern of loss was different under the various reducing conditions within each sediment and between sediments. For example benzene loss was only observed in sulfidogenic cultures from the NY/NJ Harbor sediments while toluene was degraded under all redox conditions. The loss of BTEX was correlated to the reduction of the various electron acceptors. In cultures amended with gasoline the degradation was much slower and incomplete. These results show that the fate of the different BTEX components in anoxic sediments is dependent on the prevailing redox conditions as well as on the characteristics and pollution history of the sediment.

Anaerobiosis↗

Manganese exposures in Toronto during use of the gasoline additive, methylcyclopentadienyl manganese tricarbonyl.

A year-long population-weighted study of personal exposures to particulate matter (PM2.5) was conducted in Toronto while the manganese-containing additive, methylcyclopentadienyl manganese tricarbonyl (MMT), was present in gasoline at an average level of 11.9 mg Mn/l, which was higher than the maximum of 8.3 mg Mn/l allowed in the U.S. In this study, 925 three-day personal samples of PM2.5 (air concentration of aerosol with an aerodynamic diameter of less than 2.5 microm) were collected, along with a record of participants' occupations, personal habits, surroundings, and activities during sampling. Stationary samples of PM2.5 were collected indoors and outdoors at a subset of participants' homes over the same 3-day periods. Three-day samples of PM2.5 were also collected at fixed locations. Personal exposures to PM2.5 were highly influenced by exposure to tobacco smoke, and were poorly correlated with outdoor levels (Kendall's tau=0.13). The mean concentration of PM2.5 in homes (21 microg/m3) was significantly higher than the mean outdoor level (15 microg/m3). By contrast, the mean PM2.5 Mn concentration (air concentration of Mn in PM2.5) was higher outdoors (9.7 ng/m3) than indoors (5.5 ng/m3). Other than from tobacco smoke, there were no indications of significant indoor sources of PM2.5 Mn in homes. The most important predictor of exposure to PM2.5 was time spent in the subway, and a high level (428 ng/m3) of PM2.5 Mn was measured in the subway. The source of this Mn was hypothesized to be friction erosion of subway rails. Small, but statistically significant correlations were present between personal exposures to PM2.5 Mn and several traffic-related variables (time spent in transit, in a motor vehicle, near a roadway with traffic, and in a parking garage). However, in a stepwise regression that adjusted for weather and personal activities, time in a motor vehicle was the only traffic-related variable significantly associated with PM2.5 Mn, and it was only the 10th most important personal activity variable in the final model. Concentrations of PM2.5 Mn were higher at two fixed locations than outside of participants' homes, which were likely further from high traffic areas than the fixed sites. Likewise, outdoor and fixed site samples collected during periods that included weekend days contained lower air concentrations of Mn than samples collected during weekdays when traffic was heavier. On the other hand, the monthly average concentration of Mn in gasoline was negatively correlated with both outdoor and personal PM2.5 Mn, which suggests that traffic-related sources of Mn other than MMT may be present. After omitting participants with exposure to Mn from certain identifiable non-MMT sources (subway riders, metal workers and persons exposed to tobacco smoke), the average (median) personal exposure of the remaining 325 participants to PM2.5 Mn was reduced from 14 ng/m3 (8.5 ng/m3 ) to 8.3 ng/m3 (7.0 ng/m3). Potential sources of this residual Mn exposure include, in addition to MMT, naturally occurring Mn in the earth's crust, other occupational exposure, airborne release of Mn from industrial operations, and friction erosion of Mn from steel-containing products. Taken together, these facts (elimination of participants with Mn exposure from known non-MMT sources reduced average exposures by 40%, the existence of multiple non-MMT sources of the remaining Mn exposure, and the negative correlation between MMT usage and PM2.5 Mn) suggest that the preponderance of personal Mn exposure was from non-MMT sources.

Adolescent↗

Selection of microbial populations degrading recalcitrant hydrocarbons of gasoline by monitoring of culture-headspace composition.

A methodology was devised and was found useful for the selection of populations degrading recalcitrant hydrocarbons. The work was part of a programme aiming at developing knowledge of the intrinsic capacities of autochtonous microflorae of the environment for gasoline biodegradation. The methodology involved monitoring the progress of degradation in enrichment liquid cultures on the selected hydrocarbon by gas chromatographic analysis of CO2 production and O2 consumption. Populations degrading in particular o-xylene, 1,2,4-trimethylbenzene, cyclohexane were obtained. Concerning 2,2,4-trimethylpentane (isooctane), one microflora (and a pure strain derived from it) growing on this hydrocarbon were obtained from gasoline-polluted water.

Bacteria↗

Visits to physicians after the oxygenation of gasoline in Philadelphia.

During the period between 1992 and 1997, there was an increase in levels of methyl tertiary butyl ether (MTBE) in gasoline in the Philadelphia, Pennsylvania, area. In this study, the authors analyzed billing records from clinical practices that were extensions of the University of Pennsylvania. The authors based their selections on the International Classification of Diseases-9 diagnostic codes, which were determined from (1) previous studies of methyl tertiary butyl ether conducted by the Centers for Disease Control; (2) respiratory symptoms, including asthma and wheezing; and (3) symptoms associated anecdotally with methyl tertiary butyl ether levels in gasoline. The authors normalized all data by the total number of office visits. The incidences of headache, throat irritation, allergic rhinitis, cough, nausea, dizziness, upper respiratory infections, wheezing, otitis media, skin rash, anxiety, insomnia, palpitations, generalized allergy, and malaise were increased during the period studied. Large increases occurred during the winters of 1993-1994 and 1994-1995 (during which there were high levels of MTBE), but not in the preceding summers (during which there were low levels of MTBE). This was especially true for asthma and wheezing. During the summers of 1995, 1996, and 1997, the incidences of the aforementioned symptoms increased greatly.

Adult↗

Identification of gasoline lead in children's blood using isotopic analysis.

The isotopic composition and concentrations of lead were measured, using mass spectrometric analysis, in blood drawn from 14 young children who lived in Washington, D.C. The isotopic composition of lead in ambient air, which reflects the changing sources of gasoline lead, was also determined for the period of sampling. Blood lead concentrations ranged from 4.38 to 24.7 micrograms/100 g blood. Based on linear patterns that involved ratios of all four isotopes consistent with two component mixing, we estimate a minimum contribution of recent gasoline lead ranging from 0 to 57% of the blood lead burden.

Air Pollutants↗

Exposure to methyl tertiary-butyl ether from oxygenated gasoline in Stamford, Connecticut.

In 1993, state health officials in Connecticut invited the Centers for Disease Control and Prevention (CDC) to assist in an investigation of exposure to methyl tertiary-butyl ether in oxygenated gasoline in Stamford, Connecticut. Venous blood samples were collected from 14 commuters and from 30 other persons who worked in the vicinity of traffic or automobiles, and the samples were analyzed for methyl tertiary-butyl ether, tertiary-butyl alcohol, benzene, m-/p-xylene, o-xylene, and toluene. The highest levels of methyl tertiary-butyl ether in blood were measured among gasoline service station attendants (median = 15 micrograms/l, range = 7.6-28.9 micrograms/l). Blood levels of methyl tertiary-butyl ether were highly variable among persons who worked in car-repair shops (median = 1.73 micrograms/l, range = 0.17-36.7 micrograms/l) and were generally lowest among commuters (median = 0.11 micrograms/l, range = < 0.05-2.60 micrograms/l). Blood levels of methyl tertiary-butyl ether were correlated strongly with personal-breathing-zone samples of methyl tertiary-butyl ether and blood levels of other volatile organic compounds. This exposure information should prove useful to a future risk analysis of this high-volume chemical.

Air Pollutants↗

Effects of kerosene cleaning on the formation of DNA adducts in the skin and lung tissues of mice dermally exposed to used gasoline engine oil.

Used gasoline engine oils (UGEO) are carcinogenic and/or mutagenic in long-term studies and capable of increasing the number of mutagen- or carcinogen-DNA adducts when applied dermally to mice. The carcinogenic or mutagenic risk of UGEO has been attributed to the concentration of polycyclic aromatic compounds (PAC) that accumulate in the lubricating system during combustion of gasoline. When dermal exposure to UGEO takes place, the use of hand cleansers, solvent- or d-limonene-based, is commonly recommended for washing, In this study, female mice aged 4-6 wk (12-17 g) were utilized to evaluate the efficiency of kerosene, as solvent-based cleanser, to remove UGEO following dermal exposure. Using a 32P postlabeling technique, the total levels of DNA adducts in skin and lung were significantly increased in kerosene-treated mice. Application of UGEO followed by kerosene washing significantly decreased skin DNA adduct levels but increased lung adduct levels after 8 h. The observed lower DNA adduct skin levels may reflect greater UGEO skin penetration and absorption in the presence of kerosene cleanser.

Administration, Topical↗

Skin cleaning with kerosene facilitates passage of carcinogens to the lungs of animals treated with used gasoline engine oil.

Solvents such as kerosene or gasoline may be used by workers to clean their skin following contact with oily materials. This practice is not recommended, as it is well known that the solvent will defat the skin. Many also suspect that solvent washing may increase exposure by carrying materials through the skin; however, there is little documentation of this. Auto mechanics may be exposed to used gasoline engine oil (UGEO), an animal carcinogen which forms carcinogen-DNA adducts in skin and lung following topical application. This study was designed to determine if cleaning with kerosene following exposure to UGEO altered absorption of carcinogens from this material. UGEO or new oil (NO) was applied to the shaved skins of groups of HSD-ICR mice for five days. At 1 or 8 hours after application, the treated skins were cleaned with either kerosene or a commercial cleaner, or were not cleaned. Animals were sacrificed 24 hours after the last application, skins and lungs harvested, and DNA analyzed for carcinogen-DNA adducts by 32P-postlabeling. Five applications of UGEO significantly increased carcinogen-DNA adduct levels in both lungs and skin compared to animals treated with NO. DNA adduct levels in the skin were reduced significantly in groups washed with kerosene or commercial cleaner. Washing at one as opposed to eight hours after UGEO application resulted in lower adduct levels regardless of cleaner. DNA adduct levels in the lung were reduced when the commercial cleaner was used, again in a time-related fashion. However, cleaning with kerosene resulted in mean carcinogen-DNA adduct levels in the lung which were significantly higher than even the positive controls, regardless of cleaning time. This is the first demonstration that kerosene cleaning facilitates passage of carcinogens through the skin, resulting in higher levels of genetic damage in a critical internal organ.

Administration, Cutaneous↗

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

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

Air Pollutants, Occupational↗

Particle mass emission rates from current-technology, light-duty gasoline vehicles.

Now that the U.S. Environmental Protection Agency has promulgated new National Ambient Air Quality Standards for PM2.5, work will begin on generating the data required to determine the sources of ambient PM2.5 and the magnitude of their contributions to air pollution. This paper summarizes the results of an Environmental Research Consortium program, carried out under the auspices of the U.S. Council for Automotive Research. The program focused on particulate matter (PM) emissions from representative, current-technology, light-duty gasoline vehicles produced by DaimlerChrysler Corp., Ford Motor Co., and General Motors Corp. The vehicles, for the most part taken from the manufacturer's certification and durability fleets, were dynamometer-tested using the three-phase Federal Test Procedure in the companies' laboratories. The test fleet was made up of a mixture of both low-mileage (2K-35K miles) and high-mileage (60K-150K miles) cars, vans, sport utility vehicles, and light trucks. For each vehicle tested, PM emissions were accumulated over 4 cold-start tests, which were run on successive days. PM emission rates from the entire fleet (22 vehicles total) averaged less than 2 mg/mile. All 18 vehicles tested using California Phase 2 reformulated gasoline had PM emission rates less than 2 mg/mile at both low and high mileages.

Air Pollution↗

Impact of unleaded gasoline introduction on the concentration of lead in the air of Dhaka, Bangladesh.

Airborne particulate matter (APM) samples collected at a semiresidential area in Dhaka, Bangladesh, during the periods of 1994 and 1997-2000 have been studied to assess the impact of the use of unleaded gasoline in Bangladesh. According to scanning electron microscopy/ energy-dispersive X-ray microanalyzer studies, lead (Pb) was found as Pb sulfates and Pb halides in motor-vehicle exhaust particles, whose diameters were some hundreds of nanometers. No significant changes in the annual averages of APM mass and black carbon concentrations have been observed over the period. The yearly average Pb concentration reached a maximum value of 370 ng/m3 in the particulate matter with an aerodynamic diameter < 2.5 microm fraction in 1998. In 2000, the concentration decreased to approximately one-third (106 ng/m3) of the high earlier values after the introduction of unleaded gasoline in 1999. A significant lowering of the blood Pb level of the population over next few years is expected as a result of this great decrease in Pb concentration.

Air Pollutants↗

Impact of engine lubricant properties on regulated gaseous emissions of 2000-2001 model-year gasoline vehicles.

The impact of the sulfur (S) content in lubricating oil was evaluated for four ultra-low-emission vehicles and two super-ultra-low-emission vehicles, all with low mileage. The S content in the lube oils ranged from 0.01 to 0.76%, while the S content of the gasoline was fixed at 0.2 ppmw. Vehicles were configured with aged catalysts and tested over the Federal Test Procedure, at idle and at 50-mph cruise conditions. In all testing modes, variations in the S level of the lubricant did not significantly affect the regulated gas-phase tailpipe emissions. In addition to the regulated gas-phase emissions, a key element of the research was measuring the engine-out sulfur dioxide (SO2) in near-real-time. This research used a new methodology based on a differential optical absorption spectrometer (DOAS) to measure SO2 from the lubricants used in this study. With the DOAS, the contribution of SO2 emissions for the highest-S lubricant was found to range from less than 1 to 6 ppm on a gasoline S equivalent basis over the range of vehicles and test cycles used. The development and operation of the DOAS is discussed in this paper.

Air Pollutants↗

Methyl tertiary hexyl ether and methyl tertiary octyl ether as gasoline oxygenates: assessing risks from atmospheric dispersion and deposition.

Methyl tertiary hexyl ether (MtHxE) and methyl tertiary octyl ether (MtOcE) are currently being developed as replacement oxygenates for methyl tertiary butyl ether (MtBE) in gasoline. As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their introduction into the environment as well. In this study, a screening-level risk assessment was performed by comparing predicted environmental concentrations (PEC) of these ethers to concentrations that might cause adverse effects to humans or ecosystems. A simple box model that has successfully estimated urban air concentrations of MtBE was adapted to predict atmospheric concentrations of MtHxE and MtOcE. Expected atmospheric concentrations of these ethers were also estimated using the European Union System for the Evaluation of Substances (EUSES) multimedia fate model, which simultaneously calculates PECs in the various environmental compartments of air, water, soil, and sediment. Because little or no data are available on the physicochemical, environmental, and toxicological properties of MtHxE and MtOcE, estimation methods were used in conjunction with EUSES to predict both the PECs and the concentrations at which these ethers might pose a threat. The results suggest that these ethers would contaminate the air of a moderately sized U.S. city (Boston, MA) at levels similar to those found previously for MtBE. The risk assessment module in EUSES predicted risk characterization ratios of 10(-3) and 10(-2) for MtHxE and MtOcE, respectively, in Boston, and 10(-2) and 10(-1) in very large urban centers, suggesting that these ethers pose only a minimal threat to ecosystems at the anticipated environmental concentrations. The assessment also indicates that these compounds are possible human carcinogens and that they may be present in urban air at concentrations that pose an unacceptable cancer risk. Therefore, testing of the toxicological properties of these compounds is recommended before they replace MtBE in gasoline.

Animals↗