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Mutagenic 1-nitropyrene in wastewater from oil-water separating tanks of gasoline stations and in used crankcase oil.

Wastewater collected from oil-water separating tanks of ten gasoline stations for a year was fractionated into diethyl ether-soluble neutral, acidic, and basic fractions. Mutagenicity of these fractions was measured with Salmonella typhimurium strains TA98 and TA100 in the presence or absence of S9 mix. The neutral fractions showed high mutagenicity in the absence of S9 mix. Each neutral fraction was subjected to high-performance liquid chromatography (HPLC) and fractionated. A 1-nitropyrene(1-NP)-corresponding fraction was collected and analyzed by gas chromatography-mass spectrometry (GC-MS) and HPLC to prove that wastewater contains 1-NP and to quantitate 1-NP in wastewater. GC-MS patterns showed the following molecular and fragment ion peaks of 1-NP: 247, 217, 201, and 189. The amount of 1-NP in 36 samples of wastewater was 4.2-25,600 ng per liter of wastewater, and 1-NP accounted for 0.3-58.5% of the total mutagenicity of the neutral fractions. The other 19 samples of wastewater did not contain any detectable 1-NP. The mutagenicity of wastewater may be due to water from car washing and contamination by used crankcase oil. A Soxhlet extract of crankcase oil used in a gasoline was fractionated into three fractions as above. Mutagenicity was measured with strains TA98, TA100, TA98NR, and TA98/1,8-DNP6 in the absence or presence of S9 mix. The neutral fraction showed the highest mutagenicity with strain TA98 in the absence of S9 mix, and its mutagenicity was decreased in strains TA98NR and TA98/1,8-DNP6. The latter result indicates that the used engine-oil contained 1-NP and dinitropyrenes. Actually, the amounts of 1-NP and 1,6-diNP in used crankcase oil were 138 and 2.0 ng per ml of oil, respectively, and these concentrations accounted for 0.45 and 2.7%, respectively, of the total mutagenicity of the neutral fraction with strain TA98 in the absence of S9 mix. Moreover, the concentrations of 1-NP and 1,6-diNP in used crankcase oil of a diesel engine were 349 and 31 ng per ml of oil, respectively, accounting for 0.9 and 12%, respectively, of the total mutagenicity of the neutral fraction in the same assay system.

Chromatography, High Pressure Liquid↗

Cytotoxic and genotoxic effects of extract of particulate emission from a gasoline-powered engine.

Extract of particulate matter (EPM) from gasoline engine exhaust has been investigated for cytotoxic and genotoxic effects in the concentration range 0.16-10 micrograms/ml by means of short-term bioassays using mammalian cell culture systems. Cytotoxicity is demonstrated by a strong dose-dependent reduction of cloning efficiency after treatment of V79 cells with EPM. Employing the dye exclusion test with erythrosin B, no considerable loss of cell viability was observed. Using the same cell system, EPM revealed a highly increased number of aberrant mitoses, whereby the occurrence of C mitoses and metaphases with chromosome clusters was especially pronounced. This effect led to mitotic arrest as shown by a highly increased mitotic index at 5 and 10 micrograms/ml EPM. The results indicate disturbances of the mitotic spindle in a way similar to the known spindle poison colcemid. As a consequence of spindle disturbances, EPM produced numerical chromosome alterations such as aneuploidy and polyploidy. Cytogenetic analyses using human lymphocyte cultures treated with EPM revealed a slight increase of chromosomal aberrations at 10 micrograms/ml and a dose-dependent induction of sister chromatid exchanges in the range 2.5-10 micrograms/ml. At least, EPM showed a dose-dependent increase in the cell transformation assay using SV 40-infected Syrian hamster kidney cultures. The great variety of cytotoxic and genotoxic effects found with EPM suggests a potential health hazard to human populations exposed to gasoline engine exhaust. The possible contribution to cytotoxic and genotoxic activity by organolead compounds derived from antiknock additives is discussed.

Animals↗

Mass spectral fingerprints of detergents in gasolines using electrospray ionization.

Mass spectral fingerprints of detergents in Austrian, Hungarian, Uruguayan, and Chilean gasolines have been obtained using electrospray ionization mass spectrometry. Polymers or copolymers were observed based on ether motifs (inter-peak spacings of 44, 58 and 72 u) in all samples. Austrian gasoline was found to also contain polymers based on isobutene-amine.

Journal Article↗

Measurement of aqueous Henry's law constants for oxygenates and aromatics found in gasolines by the static headspace method

A simple equilibrium vessel made from a large stopcock was used in conjunction with the static headspace method to measure the aqueous Henry's law constants for methyl tert-butyl ether (MTBE) and other potential oxygenates as well as certain of the aromatics found in gasoline. The present method involves using only one aqueous solution whose concentration is not necessarily known. The only quantity that must be known is the phase ratio. Plotting a series of peak areas of the analyte in the headspace after each equilibrium change against the initial peak area of the analyte found in the headspace leads to a linear relationship whose slope is dependent on the analyte's unitless Henry's law constant and the phase ratio. This new method is found to yield unitless aqueous Henry's law constants in the range from 0.02 to 0.2, which are especially applicable to the oxygenates and aromatics found in gasolines.

Journal Article↗

Carbon monoxide poisonings from small, gasoline-powered, internal combustion engines: just what is a "well-ventilated area"?

This study modeled the time required for a gasoline-powered, 5 horsepower (hp), 4-cycle engine to generate carbon monoxide (CO) concentrations exceeding the National Institute for Occupational Safety and Health 200-ppm ceiling and 1200-ppm immediately dangerous to life and health concentration for various room sizes and ventilation rates. The model permitted the ambiguous term "well-ventilated area" to be defined. The model was compared with field data collected at a site where two workers were poisoned while operating a 5-hp concrete saw in a bathroom having open doors and an operating ventilation system. There is agreement between both the modeled and field-generated data, indicating that hazardous CO concentrations can develop within minutes. Comparison of field and modeling data showed the measured CO generation rate at approximately one-half of the value used in the model, which may be partially because the engine used in the field was not under load during data collection. The generation rate and room size from the actual poisoning was then used in the model. The model determined that ventilation rates of nearly 5000 ft3/min (120 air changes per hour) would be required to prevent the CO concentration from exceeding the 200-ppm ceiling for short periods. Results suggest that small gasoline-powered engines should not be operated inside of buildings or in semienclosed spaces and that manufacturers of such tools should improve their warnings and develop engineering control options for better user protection.

Air Pollution, Indoor↗

Visibility and soiling: a comparison of the effects of leaded and unleaded gasolines.

The emissions from a fleet of late-model cars fueled with commercial, high-aromatic, unleaded gasoline caused nearly twice as much atmospheric light extinction as those from a matched fleet fueled with commercial, low-aromatic, leaded gasoline, when both were driven according to a consumer operating cycle in an idle traffic tunnel. The increased extinction and greater soiling potential result mainly from greater light absorption by the air-suspended particles from the unleaded fleet.

Air Pollution↗

Protozoa in subsurface sediments from sites contaminated with aviation gasoline or jet fuel.

Numbers of protozoa in the subsurface of aviation gasoline and jet fuel spill areas at a Coast Guard base at Traverse City, Mich., were determined. Boreholes were drilled in an uncontaminated location, in contaminated but untreated parts of the fuel plumes, and in the aviation gasoline source area undergoing H(2)O(2) biotreatment. Samples were taken from the unsaturated zone to depths slightly below the floating free product in the saturated zone. Protozoa were found to occur in elevated numbers in the unsaturated zone, where fuel vapors mixed with atmospheric oxygen, and below the layer of floating fuel, where uncontaminated groundwater came into contact with fuel. The same trends were noted in the biotreatment area, except that numbers of protozoa were higher. Numbers of protozoa in some contaminated areas equalled or exceeded those found in surface soil. The abundance of protozoa in the biotreatment area was high enough that it would be expected to significantly reduce the bacterial community that was degrading the fuel. Little reduction in hydraulic conductivity was observed, and no bacterial fouling of the aquifer was observed during biotreatment.

Journal Article↗

Spectral range optimization for the near-infrared quantitative analysis of petrochemical and petroleum products: naphtha and gasoline.

The proper selection of the spectral range in partial least squares (PLS) calibration is critical when highly overlapping spectra from compositionally complex samples are used, such as naphtha and gasoline. In particular, the relevant spectral information related to a given property is frequently localized in a narrow range, and the most selective region may be difficult to locate. We have presented the importance of range optimization in near-infrared (NIR) spectroscopy for the analyses of petrochemical and petroleum products that are generally highly complex in composition. For this purpose, the determination of a detailed compositional analysis (so called PIONA) and the distillation temperature of naphtha were evaluated. In the same fashion, the research octane number (RON) and Reid vapor pressure (RVP) were selected for gasoline. By optimizing the range using moving window (MW) PLS, the overall calibration performance was improved by finding the optimal spectral range for each property. In particular, for a detailed compositional analysis of naphtha, it was effective to search for localized spectral information in a relatively narrow range with fewer factors.

Journal Article↗

Gasoline conservation: a procedure for measuring and reducing the driving of college students.

The study sought to motivate college students to reduce the number of miles they drove each day and thus save gasoline. Students in two psychology classes were divided by class into two groups. The experimental group was offered various combinations of prizes such as cash, a tour of a mental-health facility, car servicing, and a university parking sticker for reducing driving. The value of the prize received was scaled in terms of per cent reduction in driving. The contrast group received no inducements. The condition in which the experimental group's mileage reduction was reinforced was counterbalanced by two baseline conditions. Several special recording procedures were used to reduce and detect the possibility of subjects altering their odometers, the source of the driving data. Experimental subjects reduced their average daily mileage by 20% relative to the initial baseline; the contrast group did not change. During the one-month reinforcement condition, the 12 experimental subjects saved some 170 gallons (worth $102) of gasoline.

Journal Article↗

Environmental effects and exposures to manganese from use of methylcyclopentadienyl manganese tricarbonyl (MMT) in gasoline.

Methylcyclopentadienyl Manganese Tricarbonyl (MMT) has been used since the 1970s in the U.S. as a gasoline octane enhancer Extensive testing of the effects of MMT on regulated gaseous emissions carried out on a wide variety of automobiles showed that use of MMT resulted in significantly lower NOx emissions Tests showed that less than 15% of the manganese from MMT combustion was emitted from the tailpipe, mostly in the PM2.5 fraction as manganese phosphate, with some manganese sulfate and a very small amount of manganese oxide. MMT has been used in Canada in virtually all unleaded gasoline for about 20 years. A probability-based study involving over 900 personal exposure samples in Toronto confirmed exposures to airborne PM2.5 Mn in the general population are quite low (.008 microgram/m3-median). Ambient levels of airborne manganese in Toronto are about the same as those in areas where MMT is not used. Exposures to manganese among the general population in Toronto are well within safe limits determined by the U.S. EPA and other standard setting bodies around the world.

Alkanes↗

Gas chromatographic analysis of aromatic hydrocarbons in gasoline by column switching-back flushing technique and normalization method.

A simple and efficient method based on the technique of capillary column switching-back flushing was developed for the detailed analysis of aromatic hydrocarbons in gasoline. The early eluting components from a pre-column and the components of interest eluting from an analytical column are all directed to a flame ionization detector through a tee piece, which facilitates the quantitation of aromatic hydrocarbons in gasoline by normalization method. Real samples were analyzed and RSD < or = 3%. The operation is simple and easy, and the switching time window is +/- 5 s.

Journal Article↗

[Study on three kinds of gasoline oxygenates-induced DNA damage in mice fibroblasts].

OBJECTIVE: To study DNA damage of three kinds of gasoline oxygenates. METHOD: Single cell gel electrophoresis assay(Comet assay) was used to detect the damage effects of three gasoline oxygenates[methyl tertiary butyl ether(MTBE), ethanol anhydrous(EA) and dimethyl carbonate(DMC)] on DNA in L-929 mice fibroblasts. RESULTS: In certain concentation(37.500-150.000 mg/ml), MTBE could directly cause DNA damage of L-929 mice fibroblasts. There was obvious dose-effect relationship, i.e. when the concentration of MTBE was increased from 9.375 to 150.000 mg/ml, the comet rate also increased from 4% to 85%, and the length of comet tail changed correspondingly. The results of EA and DMC were negative. CONCLUSION: Under the condition of this experiment(150.000 mg/ml), MTBE could directly cause DNA damage while the effect of EA and DMC on DNA damage was not found.

Animals↗

[The significance of enviromental and biological monitoring in workers employed in service stations after the elimitation of tetraethyl lead from gasoline].

The chemical risk in service stations may be due to toxic compounds present in fuel (particularly benzene and additives) and to the emission of exhausts and fine particulate from vehicles. Owing to the elimination of lead (Pb) from fuel and to the necessity of lowering CO emission, several oxygenated additives have been added to fuel, in particular methyl-tert-butyl-ether (MTBE), whose toxic properties are at present under investigation. The introduction of reformulated gasoline (RFG) and the use of catalytic converters (with possible release of platinum (Pt) in the environment) may have modified the risks for workers employed in service stations. The paper shows data collected from 26 subjects (divided into three specific tasks, namely: fuel dispenser, "self-service" attendant and controller, and cashier) to estimate the actual chemical risk and to compare it with the previous data taken from literature. For this purpose, besides performing the usual medical surveillance, we measured the environmental concentrations of benzene, MTBE and formaldehyde, the urinary levels of benzene metabolites S-phenylmercapturic acid (S-PMA) and t,t-muconic acid (MA) and of unmodified MTBE, and the blood concentrations of Pb and Pt for each subject. Mean values of these compounds were, respectively: 38.81 microg/m3; 174.04 microg/m3; 10.38 microg/m3; 2.36 microg/g creatinine; 96.57 microg/g creatinine; 1.41 microg/L; 7.00 microg/100 mL; 0.0738 ng/ml. The above values were much lower than the corresponding limit values reported by ACGIH and DFG. In particular, after the introduction of vapour recycle systems and the widespread use of "self-service" systems, airborne benzene concentration dropped from 300/400 microg/m3 to lower than 100 microg/m3, without noticeable increasing of exposure to formaldehyde. The disappearing of Pb from gasoline leads to a progressive lowering of its blood levels, while the possible risks due to the very low amounts of Pt released from catalytic converters have still to be defined exactly. Taken all in all, our results seem to indicate that, after the elimination of tetraethyl lead, the chemical risk for workers employed in service stations is now lower than in the past.

Air Pollutants, Occupational↗

The reproductive dysfunction effects of gasoline inhalation in albino rats.

Daily exposure to fuel vapour may pose significant health risk to exposed individuals. Fifteen each of male and female albino rats weighing between 110-230g were divided into test (10) and control (5) groups each. The test animals; were exposed to inhalation gasoline for one hour daily for twenty-one consecutive days. All animals were then bled and the serum levels of the reproductive hormones determined. The results showed significant [P < 0.05] reduction in the serum levels of all the hormones of reproduction in both the male and female test animals. The results suggest that inhalation gasoline exposure significantly [P < 0.05] lowers the levels of reproductive hormones in albino rats and may thus interfere with reproduction.

Journal Article↗

Contribution of polycyclic aromatic hydrocarbons to the carcinogenic impact of gasoline engine exhaust condensate evaluated by implantation into the lungs of rats.

An attempt was made to identify the substances chiefly responsible for the carcinogenicity of gasoline engine exhaust condensate. A carcinogen-specific bioassay was performed by a comparison of the carcinogenic effect of various fractions with that of a total sample of automobile exhaust condensate, tested in two or three different doses. The results were examined by Probit analysis. After implantation into the lungs of OM rats, the condensate emitted from a gasoline-driven automobile and the fraction of polycyclic aromatic compounds consisting of more than 3 rings induced lung carcinomas and sarcomas. The tumor incidence demonstrated a clear-cut dose-response relationship. The fraction of polycyclic aromatic hydrocarbons (PAH) consisting of more than 3 rings accounted for about 81% of the total carcinogenicity of automobile exhaust condensate. This fraction represented only 2.8% by weight of the condensate. The content of benzo[a]pyrene (CAS: 50-32-8; 0.483 mg/g condensate) accounted for 2.4% of the total carcinogenicity of automobile exhaust condensate. Regarding the minor effect of the PAH-free fraction (approximately equal to 87% by wt), no evidence of cocarcinogenic activity was observed, since the total condensate as well as the PAH fraction consisting of more than 3 rings applied proportionally caused about the same tumor incidence.

Animals↗

Genotoxic effects in workers exposed to low levels of benzene from gasoline.

To study genotoxic effects of exposure to low levels of benzene, single-strand breaks (SSB) in DNA of leukocytes and urinary levels of the oxidative DNA adduct 8-hydroxydeoxyguanosine (8OHdG) were determined in 33 men occupationally exposed to benzene from gasoline and in 33 controls. The average exposure to benzene over a shift was determined by personal air sampling in the breathing zone. The 8-hr time-weighted average exposure to benzene was 0.13 ppm (mean value, range 0.003-0.6 ppm). Exposed workers had a significant increase of SSB (p = 0.04) over the shift compared with controls. Storage time of the samples seemed to affect the results. An analysis of samples with the same storage time showed a nonsignificant increase among the workers compared with controls. Urinary 8OHdG increased over the shift among the exposed workers but not among the controls. The highest values among the exposed workers were seen in late evening, with a slight decrease the next morning. Multiple linear analysis adjusting for smoking habits showed a significant association between the exposure level of benzene during the shift and the increase of 8OHdG in the urine over the shift among exposed workers (p = 0.02). These findings indicate a genotoxic effect in humans of benzene at relatively low exposure levels, that is, about 0.1 ppm (0.3 mg/m3).

Adult↗

Occurrence of crude oil degrading bacteria in gasoline and diesel station soils.

Microbial enumeration and identification were carried out on several oil contaminated soil samples collected from gasoline and diesel stations. Bacteria were the most dominant microbiota and were therefore classified to generic level. Eleven main genera were detected and Corynebacterium was the predominant genus in all the samples. Biochemical characterisation and substrate utilisation showed high percentage of lipolytic ability combined with high inorganic nitrogen utilisers. The ability of these cultures to degrade crude oil was tested individually and in mixed bacterial consortium at different temperatures and pH values. Maximum crude oil biodegradation of 78% was achieved using a bacterial consortium containing five cultures (Micrococcus sp. GS2-22, Corynebacterium sp. GS5-66, Flavobacterium sp. DS5-73, Bacillus sp. DS6-86 and Pseudomonas sp. DS10-129) with 1% crude oil at 30 degrees C and pH 7.5. Such a consortium may be useful for bioaugmentation of oil contaminated environments.

Bacteria↗

Use of MMT in Canadian gasoline: health and environment issues.

BACKGROUND: Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic derivative of manganese (Mn) used in Canadian gasoline since 1976 as an antiknock agent and to improve octane rating. Combustion products of MMT are mainly a mixture of Mn phosphate and Mn sulfate. In 1997, the Canadian federal government adopted a law (C-29) which banned both the interprovincial trade and the importation for commercial purposes of manganese-based substances, including MMT. However, the government reworded this law in July 1998 so that manganese-based fuel additives were not included in the restrictions. MMT is now approved for use in Argentina, Australia, Bulgaria, the United States, France, Russia, and conditionally in New Zealand. Nevertheless, these countries are not using MMT intensively and they are waiting for strong evidence of the absence of effects on human health. Even after several years of use of MMT in Canada, many uncertainties remain. METHODS: Different methods were used in order to assess (1) environmental contamination and human exposure to the parental form of MMT, (2) nitrogen oxides (NO(x)) and carbon monoxide (CO) emissions associated with the use of MMT, and (3) qualitative and quantitative assessments of Mn emissions to the environment. RESULTS: The results provide timely information with regard to the impact of MMT on environmental/ecosystem Mn contamination in abiotic and biotic systems as well as on human exposure. Moreover, results raise major concerns with regard to public health effects related to exposure to Mn. CONCLUSIONS: Obviously, there is still an important lack of adequate toxicological information and further studies are needed to provide successful implementation of evidence-based risk assessment approaches.

Air Pollution↗