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Assessment of the genotoxic potential of unleaded gasoline and 2,2,4-trimethylpentane in human lymphoblasts in vitro.

The potential of unleaded gasoline and 2,2,4-trimethylpentane to induce gene locus mutation and sister-chromatid exchange in human lymphoblasts in vitro was determined. Neither unleaded gasoline, at its maximum tolerated concentration in the medium, nor 2,2,4-trimethylpentane, at its limit of solubility, induced mutation at the thymidine kinase locus. Negative results were seen both in the presence and absence of a rat liver homogenate metabolizing system. Sister-chromatid exchange analyses of the cultures treated with unleaded gasoline and 2,2,4-trimethylpentane were also negative. Therefore the carcinogenicity and nephrotoxicity of unleaded gasoline and 2,2,4-trimethylpentane observed in vivo are not correlated with any marked genotoxicity in these in vitro tests.

Animals↗

Analysis of aromatic compounds in gasoline with flow-switching comprehensive two-dimensional gas chromatography.

A comprehensive two-dimensional gas chromatography (GC x GC) instrument has been created by coupling a flow-switching modulator and a standard gas chromatograph. The instrument was used to characterize the aromatic composition of gasoline. The high-resolution separation produced by flow-switching GC x GC allowed gasoline aromatics to be fully resolved from saturated components. The aromatic compounds were further separated into groups having the same carbon number. A standard gasoline sample was analyzed to evaluate the quantitative accuracy and precision of this technique. The data show that flow-switching GC x GC produces results that are comparable to gas chromatography-mass spectrometry (GC-MS) and thermal modulation GC x GC. The simple, low-cost, and robust nature of flow-switching GC x GC makes it an ideal technique for the routine analysis of aromatic compounds in gasoline.

Chromatography, Gas↗

Simultaneous determination of methyl tert-butyl ether, its degradation products and other gasoline additives in soil samples by closed-system purge-and-trap gas chromatography-mass spectrometry.

A new protocol for the simultaneous determination of methyl tert-butyl ether (MTBE); its main degradation products: tert-butyl alcohol (TBA) and tert-butyl formate (TBF); other gasoline additives, oxygenate dialkyl ethers: ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME) and diisopropyl ether (DIPE); aromatics: benzene, toluene, ethylbenzene and xylenes (BTEX) and other compounds causing odour events such as dicyclopentadiene (DCPD) and trichloroethylene (TCE) in soils has been developed. On the basis of US Environmental Protection Agency (EPA) method 5035A, a fully automated closed-system purge-and-trap coupled to gas chromatography/mass spectrometry (P&T-GC/MS) was optimised and permitted to detect microg/kg concentrations in solid matrices avoiding losses of volatile compounds during operation processes. Parameters optimised were the sampling procedure, sample preservation and storage, purging temperature, matrix effects and quantification mode. Using 5 g of sample, detection limits were between 0.02 and 1.63 microg/kg and acceptable method precision and accuracy was obtained provided quantification was performed using adequate internal standards. Soil samples should be analysed as soon as possible after collection, stored under -15 degrees C for not longer than 7 days if degradation products have to be analysed. The non-preservative alternative (empty vial) provided good recoveries of the most analytes when freezing the samples up to 7 day holding time, however, if biologically active soil are analysed the preservation with trisodium phosphate dodecahydrate (Na(3)PO(4).12H(2)O or TSP) is strongly recommended more than sodium bisulphate (NaHSO(4)). The method was finally applied to provide threshold and background levels of several gasoline additives in a point source and in sites not influenced by gasoline spills. The proposed method provides the directions for the future application on real samples in current monitoring programs at gasoline pollution risk sites where till now little monitoring data for MTBE in soils are available.

Benzene↗

Case study: flame arresters and exploding gasoline containers.

This paper describes the case study of a portable plastic gasoline container explosion and fire. While working at home on a science project to determine the burn rates of different types of wood fuel, a 14-year-old boy was severely burned after flames traveled back up into the portable gasoline container and exploded. A witness heard the explosion and reports that the flames went perhaps 10 ft in the air. It is shown by experimentation that a flame arrester installed in the pour opening of the portable gasoline container would have prevented an explosion inside the gasoline container.

Accidents, Home↗

Simultaneous determination of methyl tert.-butyl ether and its degradation products, other gasoline oxygenates and benzene, toluene, ethylbenzene and xylenes in Catalonian groundwater by purge-and-trap-gas chromatography-mass spectrometry.

In Catalonia (northeast Spain), a monitoring program was carried out to determine methyl tert.-butyl ether (MTBE), its main degradation products, tert.-butyl alcohol (TBA), tert.-butyl formate (TBF), and other gasoline additives, the oxygenate dialkyl ethers ethyl tert.-butyl ether, tert.-amyl methyl ether and diisopropyl ether and the aromatic compounds benzene, toluene, ethylbenzene and xylene (BTEX) in 21 groundwater wells that were located near different gasoline point sources (a gasoline spill and underground storage tank leakage). Purge-and-trap coupled to gas chromatography-mass spectrometry was optimised for the simultaneous determination of the above mentioned compounds and enabled to detect concentrations at ng/l or sub-microg/l concentrations. Special attention was given to the determination of polar MTBE degradation products, TBA and TBF, since not much data on method performance and environmental levels are given on these compounds in groundwater. All samples analysed contained MTBE at levels between 0.3 and 70 microg/l. Seven contaminated hot spots were identified with levels up to US Environmental Protection Agency drinking water advisory (20-40 microg/l) and a maximum concentration of 670 microg/l (doubling the Danish suggested toxicity level of 350 microg/l). Samples with high levels of MTBE contained 0.1-60 microg/l of TBA, indicating (but not proving) in situ degradation of parent compound. In all cases, BTEX was at low concentrations or not detected showing less solubility and persistence than MTBE. This fact confirms the suitability of MTBE as a tracer or indicator of long-term gasoline contamination than the historically used BTEX.

Benzene↗

Evaluation of environmental levels of aromatic hydrocarbons in gasoline service stations by gas chromatography.

The volume of gasoline sold in refuelling operations and the ambient temperature, can increase significantly the environmental levels of aromatic hydrocarbon vapours and subsequently, the occupational risk of gasoline service station attendants, specially in the case of benzene. We have evaluated the occupational exposure to aromatic hydrocarbons by means of personal-breathing-zone samples of gasoline vapours in a service station attendant population. This evaluation was carried out using diffusive samplers, in two periods at quite different temperatures (March and July). A significant relationship between the volume of gasoline sold during the shift and the ambient concentration of benzene, toluene, and xylenes was found for each worker sampled. Furthermore a significant difference was found between the time-weighted average concentration of aromatic compounds measured in March, with ambient temperatures of 14-15 degrees C and July, with temperatures of 28-30 degrees C. In addition, 20% of the population sampled in the last period were exposed to a time-weighted average concentration of benzene above the proposed Threshold Limit Value of 960 micrograms/m(3) of the American Conference of Governmental Industrial Hygienists (ACGIH).

Air Pollutants, Occupational↗

A comparative study of manganese and lead levels in human umbilical cords and maternal blood from two urban centers exposed to different gasoline additives.

Manganese (Mn) and lead (Pb) are two neurotoxic chemicals and experimental evidence suggests that they can cross the placental barrier. Tetraethyl lead was still in use as an antiknock agent in Paris during the sampling period of the study, while it has been replaced by methylcyclopentadienyl manganese tricarbonyl (MMT) in Canada since 1977. By 1990, MMT was in 100% of gasoline in Canada. In a study of 160 pairs of mothers-neonates in Montreal and 206 pairs in Paris, we compared levels of Mn and Pb in the umbilical cord and in maternal blood. Neonates and mothers had significantly higher Pb levels in Paris where lead additives were still used in gasoline. Geometric mean maternal blood Pb levels were 5.4 microg/dl compared to 2.1 microg/dl in Montreal and cord blood Pb levels were 3.2 microg/dl in Parisian mothers compared to 1.7 microg/dl in Montreal. The prevalence of Paris Pb values superior to the 95th percentile of the Montreal distribution was highly elevated in all media studied. The prevalence of high Mn levels in umbilical cord blood was also significantly higher in Montreal. Surveillance programs are important to limit Pb overexposure and associated neurological effects in neonates where tetraethyl Pb is still in use as a gasoline additive. Since Mn is an essential element and dietary Mn intake may differ between Montreal and Paris, the difference observed with regard to high Mn values between Montreal and Paris cannot, at this time, be attributed to MMT in Montreal's gasoline. Further studies are needed to infer an association between Mn emissions from MMT and prenatal exposure to Mn.

Adult↗

Effect on exhaust emissions by the use of methylcyclopentadienyl manganese tricarbonyl (MMT) fuel additive and other lead replacement gasolines.

This paper examines the potential effects on car exhaust emissions of a range of alternative lead replacement gasolines in the context of south European countries such as Greece. The main objective of this study was to assess the effects on emissions from non-catalyst passenger vehicles by the substitution of leaded ('super') gasoline with Euro95 unleaded enriched with the additive MMT or other alternative to leaded gasoline fuels. Regulated emissions, two non-regulated pollutants and vehicle performance were measured on two catalyst-equipped and two conventional, non-catalyst vehicles. It was found that there was no measurable effect on regulated emissions (CO, HC and NO(x)) and on fuel consumption by the introduction of the lead replacement fuels for both catalyst and non-catalyst cars. In the case of the non-catalyst car, the shift from leaded to unleaded gasoline was associated with an increase in benzene and formaldehyde emissions, a trend probably attributable to the increased aromatics content of the lead replacement fuels.

Air Pollution↗

Genotoxicity of particulate emissions from gasoline-powered engines evaluated by short-term bioassays.

Atmospheric pollutants, especially airborne particulates, contain a large number of genotoxic substances capable of inducing human health effects via inhalation. One important source of air pollutants are exhaust particles from automobile traffic. This concerns mainly diesel exhaust for which genotoxic properties are evident. With respect to particle emissions produced by gasoline-powered cars little information on a genotoxic potential is available. In this study 3 particulate emission extracts from different gasoline-powered cars driven with leaded or unleaded gasoline were investigated for cytotoxic and genotoxic activities by means of short-term bioassays using mammalian cell culture systems. All tested extracts were found to induce a broad spectrum of cytotoxic and genotoxic effects suggesting that gasoline exhausts are under high suspicion of contributing to health effects in human populations via air pollution.

Administration, Inhalation↗

Sorption and permeability of gasoline hydrocarbons in organobentonite porous media.

We investigate the use of organobentonites as liners for underground gasoline storage tanks to reduce the risk of subsurface contamination. A series of permeability measurements were conducted on two types of organobentonites: benzyltriethylammonium-bentonite (BTEA-bentonite) and hexadecyltrimethylammonium-bentonite (HDTMA-bentonite). Both water and commercial unleaded gasoline were used as the permeant liquids. Results of these measurements indicate that the intrinsic permeability of the organobentonite decreases by one to two orders of magnitude when the permeant liquid is changed from water to gasoline. Results of batch sorption measurements reveal that benzene sorption to both organobentonites from water is greater than benzene sorption to conventional bentonite. The magnitude of benzene sorption is related to the loading of the organic quaternary ammonium cation on the clay. As the HDTMA cation loading increases from 25% of cation exchange capacity (CEC) to 120% of CEC, benzene sorption increases. However, as the BTEA cation loading increases from 40 to 120% of CEC, benzene sorption decreases. Collectively, these results suggest that organobentonites can be used effectively to reduce hydrocarbon migration rates beneath leaking underground gasoline storage tanks, and that the optimal organic cation loading with respect to pollutant sorption may be less than 50% of cation exchange capacity for some organobentonite-solute combinations.

Adsorption↗

Environmental implications on the oxygenation of gasoline with ethanol in the metropolitan area of Mexico City.

Motor vehicle emission tests were performed on 12 in-use light duty vehicles, made up of the most representative emission control technologies in Mexico City: no catalyst, oxidative catalyst, and three way catalyst. Exhaust regulated (CO, NOx, and hydrocarbons) and toxic (benzene, formaldehyde, acetaldehyde, and 1,3-butadiene) emissions were evaluated for MTBE (5 vol %)- and ethanol (3, 6, and 10 vol %)-gasoline blends. The most significant overall emissions variations derived from the use of 6 vol % ethanol (relative to a 5% MTBE base gasoline) were 16% decrease in CO, 28% reduction in formaldehyde, and 80% increase in acetaldehyde emissions. A 26% reduction in CO emissions from the oldest fleet (< MY 1991, without catalytic converter), which represents about 44% of the in-use light duty vehicles in Mexico city, can be attained when using 6 vol% ethanol-gasoline, without significant variation in hydrocarbons and NOx emissions, when compared with a 5% vol MTBE-gasoline. On the basis of the emissions results, an estimation of the change in the motor vehicle emissions of the metropolitan area of Mexico city was calculated for the year 2010 if ethanol were to be used instead of MTBE, and the outcome was a considerable decrease in all regulated and toxic emissions, despite the growing motor vehicle population.

Air Pollutants↗

Separation of fine particulate matter emitted from gasoline and diesel vehicles using chemical mass balancing techniques.

Samples of fine particulate matter were collected in a roadway tunnel near Houston, TX over a period of 4 days during two separate sampling periods: one sampling period from 1200 to 1400 local time and another sampling period from 1600 to 1800 local time. During the two sampling periods, the tunnel traffic contained roughly equivalent numbers of heavy-duty diesel trucks. However, during the late afternoon sampling period, the tunnel contained twice as many light-duty gasoline-powered vehicles. The effect of this shift in the vehicle fleet affects the overall emission index (grams pollutant emitted per kilogram carbon in fuel) for fine particles and fine particulate elemental carbon. Additionally, this shift in the fraction of diesel vehicles in the tunnel is used to determine if the chemical mass balancing techniques used to track emissions from gasoline-powered and diesel-powered emissions accurately separates these two emission categories. The results show that the chemical mass balancing calculations apportion roughly equal amounts of the particulate matter measured to diesel vehicles between the two periods and attribute almost twice as much particulate matter in the late afternoon sampling period to gasoline vehicles. Both of these results are consistent with the traffic volume of gasoline and diesel vehicles in the tunnel in the two separate periods and validate the ability for chemical mass balancing techniques to separate these two primary sources of fine particles.

Air Pollutants↗

Risk of cancer as a result of community exposure to gasoline vapors.

The Tranguch Gasoline Spill leaked 50,000-900,000 gallons of gasoline from underground storage tanks, potentially exposing an area of Hazle Township and Hazleton, Pennsylvania, to chronic low levels of benzene since at least 1990. A retrospective cohort study of 663 individuals representing 275 households assessed whether affected residents were at increased risk for cancer from 1990-2000 compared with the Pennsylvania populace. Age-adjusted standard incidence ratios (SIRs) were calculated using Pennsylvania rates to determine expected numbers. The age-adjusted SIR for the gasoline-affected area was 4.40 (95% confidence interval: 1.09-10.24) for leukemia. These results suggest an association between living within the area affected by the Tranguch Gasoline Spill and increased risk for leukemia.

Adolescent↗

Biocatalytic sulfur removal from fuels: applicability for producing low sulfur gasoline.

Environmental regulations are driving R&D efforts to produce low sulfur fuels, including diesel fuel and gasoline for motor vehicles. Biocatalytic sulfur removal from fuels has potential applicability for producing low sulfur gasoline. Microbial biocatalysts have been identified that can biotransform sulfur compounds found in fuels, including ones that selectively remove sulfur from dibenzothiophene heterocyclic compounds. Most attention is give to the 4S pathway of Rhodococcus, which can remove sulfur from substituted and unsubstituted dibenzothiophenes, including sulfur compounds that hinder chemical catalysis and that resist removal by mild hydrotreatment. Various bioreactor and bioprocess designs are being tested for use with biocatalysts, including recombinant biocatalysts, for use in removing sulfur from fuels and feedstocks within the petroleum refinery stream. With bioprocess improvements that enhance biocatalyst stability, achieve faster kinetics, improve mass transfer limitations, temperature and solvent tolerance, as well as broaden substrate specificity to attack a greater range of heterocyclic compounds, biocatalysis may be a cost-effective approach to achieve the production of low sulfur gasoline. The challenge will be to accomplish these improvements by the time the regulations for low sulfur gasoline and other vehicle fuels go into effect in order to be competitive with emerging nonbiological desulfurization technologies.

Fossil Fuels↗

Effect of methyl tertiary butyl ether concentrations on exhaust emissions from gasoline used in the metropolitan area of Mexico City.

In this work, the primary objective was to assess the impact of oxygenated fuel on the exhaust emissions from an important fraction of vehicles in the Metropolitan Area of Mexico City (MAMC). The results aim to provide information on the actual effect of MTBE on a fleet that represents more than 60% of the in-use vehicles in the MAMC. Ten vehicles were tested with a low-octane base gasoline, and 10 more with a regular-grade unleaded base gasoline. Three MTBE concentrations, 5, 10, and 15 vol %, were tested following the U.S. Federal Test Procedure (FTP). CO, total HC, and NOx from the exhaust gases were quantitatively evaluated and also characterized for FTP speciated organic emissions. From this data, the O3-forming potential of the fuels was calculated. Results show that for the fleet using low-octane gasoline, the addition of 10% MTBE substantially reduced CO emissions, but total HC concentration in the exhaust showed a modest decrease. For the regular gasoline, the 10% MTBE blend seemed to be the best choice, but there was not a significant decrease in emissions. The specific reactivity of each fuel, expressed in grams of O3 per gram of nonmethane organic gases, increased with MTBE concentration in both cases. This result is important to consider, especially for a region like Mexico City, which has high atmospheric O3 concentrations.

Air Pollutants↗

Benzene in gasoline and crude oil: occupational and environmental implications.

A review of studies, published in peer-reviewed journals and articles available as technical reports of various organizations, regarding benzene in gasoline and crude oil was performed. The summarized data will be useful for retrospective exposure assessments in epidemiological studies. It shows that in the past, benzene in gasoline has been quite high, but now, there is a distinct trend in North America and Europe to reduce benzene in gasoline to a level of about 1%. The reduction of benzene in gasoline results not only in the lowering of occupational exposure for workers, but it also has far greater influence in decreasing the environmental benzene exposure for the general public.

Benzene↗

Unusual facial markings and lethal mechanisms in a series of gasoline inhalation deaths.

A review of deaths associated with hydrocarbon toxicity from gasoline sniffing in South Australia throughout a 10 year period from July 1987 to June 2002 revealed 4 cases. The victims were all Aboriginal people from remote inland communities. Each death had occurred while the victim was lying in bed sniffing gasoline from a can held to the face. Once unconsciousness had occurred, the mouth and nose had been pressed firmly against the can by the weight of the head. In each case, the effects of gasoline toxicity had been exacerbated by hypoxia and hypercapnia from rebreathing into the container once a tight seal had been established between the face and the can. The circular impressions left by the can edges on the faces of each of the victims provided an autopsy marker that assisted in clarifying the details of the fatal episodes. Discouraging solitary gasoline sniffing in bed may reduce the death rate in communities where this behavior is practiced.

Administration, Inhalation↗

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.

Fresh Water↗