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Methyl tertiary-butyl ether antibodies among gasoline service station attendants.

Occupational exposure to petroleum products (gasoline) and elevated blood levels of MTBE have been demonstrated among gasoline station attendants. While MTBE and its metabolites have been considered environmentally inert, immunologically these materials could be reactive. This study was conducted to assess the immunological reactivity of humans to MTBE. Blood samples from 24 gasoline station attendants and 12 healthy controls were examined for levels of IgG, IgM, IgA, and IgE against MTBE by ELISA. In the gasoline-exposed group 7 out of 24 exhibited optical densities or antibody levels of 3-15-fold (OD 0.6-2.68) of the levels detected in controls (OD < 0.2). The detected antibodies both against MTBE-BSA or MTBE-HSA were of IgG and IgM but not IgA or IgE isotypes. These antibodies at much lower levels (OD of 0.45) were detected in only 1 of the 12 healthy control groups. The specificity of these antibodies was evidenced by absorption of MTBE antibodies in different sera using the same haptenic group bound to a different carrier. These results indicate that immune reactions to MTBE do occur through hapten carrier reactions which, in some individuals, end with specific IgG and IgM production.

Antibodies↗

Identification and catabolic activity of well-derived gasoline-degrading bacteria from a contaminated aquifer.

Approximately 300 gasoline-degrading bacteria were isolated from well water and core material from a shallow coastal aquifer contaminated with unleaded gasoline. Identification of 244 isolates revealed four genera: Pseudomonas, Alcaligenes, Nocardia, and Micrococcus, with pseudomonads making up 86.9% of bacteria identified. A total of 297 isolates was sorted into 111 catabolic groups on the basis of aerobic growth responses on 15 gasoline hydrocarbons. Each test hydrocarbon was degraded by at least one isolate. Toluene, p-xylene, ethylbenzene, and 1,2,4-trimethylbenzene were most frequently utilized as growth substrates, whereas cyclic and branched alkanes were least utilized. Most isolates were able to grow on 2 or 3 different hydrocarbons, and nearly 75% utilized toluene as a sole source of carbon and energy. Isolates were remarkably specific for hydrocarbon usage, often catabolizing only one of several closely related compounds. A subset of 220 isolates was sorted into 51 groups by polyacrylamide gel electrophoresis. Pseudomonas aeruginosa was partitioned into 16 protein-banding groups (i.e., subspecies) whose catabolic activities were largely restricted to substituted aromatics. Different members of subspecies groups defined by protein-banding pattern analysis often exhibited different growth responses on the same hydrocarbon, implying marked strain diversity. The catabolic activities of well-derived, gasoline-degrading bacteria associated with this contaminated aquifer are consonant with in situ adaptation at the site.

Bacteria, Aerobic↗

Microbial desulfurization of gasoline in a Mycobacterium goodii X7B immobilized-cell system.

Mycobacterium goodii X7B, which had been primarily isolated as a bacterial strain capable of desulfurizing dibenzothiophene to produce 2-hydroxybiphenyl via the 4S pathway, was also found to desulfurize benzothiophene. The desulfurization product was identified as o-hydroxystyrene by gas chromatography (GC)-mass spectrometry analysis. This strain appeared to have the ability to remove organic sulfur from a broad range of sulfur species in gasoline. When Dushanzi straight-run gasoline (DSRG227) containing various organic sulfur compounds was treated with immobilized cells of strain X7B for 24 h, the total sulfur content significantly decreased, from 227 to 71 ppm at 40 degrees C. GC flame ionization detection and GC atomic emission detection analysis were used to qualitatively evaluate the effects of M. goodii X7B treatment on the contents of gasoline. In addition, when immobilized cells were incubated at 40 degrees C with DSRG275, the sulfur content decreased from 275 to 54 ppm in two consecutive reactions. With this excellent efficiency, strain X7B is considered a good potential candidate for industrial applications for the biodesulfurization of gasoline.

Biodegradation, Environmental↗

Dangerous and cancer-causing properties of products and chemicals in the oil refining and petrochemical industry: Part I. Carcinogenicity of motor fuels: gasoline.

Studies in humans and animals have shown that gasoline contains a number of cancer-causing and toxic chemicals such as 1,3-butadiene, benzene, toluene, ethylbenzene, xylenes, isoparaffins, methyltert-butylether, and others. The International Agency for Research on Cancer (IARC) in its Monograph Supplement 7 (1987) concludes that "in the absence of adequate data on humans, it is biologically plausible and prudent to regard agents for which there is sufficient evidence of carcinogenicity in experimental animals as if they present a carcinogenic risk to humans." Epidemiological studies in humans provide important evidence of potential increased risk of leukemia, lymphatic tissue cancers, cancers of the brain, liver, and other organs and tissues. Recently (July, 1990) the American Conference of Governmental Industrial Hygiene (ACGIH) recommended that the TLV-TWA for benzene be reduced from 1 ppm to 0.1 ppm (ACGIH, 1990). The Collegium Ramazzini and others have also recommended that the exposure level for 1,3-Butadiene be reduced from 1,000 ppm to below 0.2 ppm. This recommendation is based on the findings that were presented at the Symposium on Toxicology, Carcinogenesis, and Human Health Aspects of 1,3-Butadiene (Environ. Health Perspec., 1990). Thus, studies on health effects resulting from very low levels of benzene, 1,3-butadiene, and other cancer-causing chemicals--components of gasoline--necessitate that all avoidable exposure to gasoline or gasoline vapors be avoided.

Benzene↗

Ethyl-leaded gasoline: how a classic occupational disease became an international public health disaster.

The author describes the controversy about the use of tetraethyl lead (TEL) as a gasoline additive. Early warnings were ignored by industry, and as leaded gasoline became more profitable, scientists willing to support industry were financed as guardians of the scientific criteria for lead's health impacts. Controversy erupted in 1924 after refinery accidents left workers dying from violent insanity. In efforts to protect their profits, industry executives falsely claimed there was no alternative to leaded gasoline. Fifty years passed before scientific, court, and regulatory challenges had any influence. When independent research finally emerged, the results were damning enough to support an international phase-out of leaded gasoline.

Chemical Industry↗

Acute and chronic progressive encephalopathy due to gasoline sniffing.

Acute encephalopathy caused by gasoline sniffing is well recognized, but has been thought to be completely reversible. We report a patient who developed a progressive encephalopathy characterized by ataxia, tremor and dementia following repeated, deliberate gasoline inhalation. Blood and urine lead levels were consistently elevated and at autopsy, the formalin-fixed brain lead content was between 5200 and 6500 micrograms/100 gm of tissue. This case shows that repeated gasoline sniffing can result in irreversible encephalopathy and that both the acute and chronic encephalopathy probably result from organic lead intoxication and not from the gasoline itself.

Adult↗

Epidemiologic evidence for an association between gasoline and kidney cancer.

A recent animal experiment suggests that gasoline exposure may be a cause of human kidney cancer. This is a literature review to see whether there is any epidemiologic support for these animal findings. Trends and geographic patterns in gasoline consumption and kidney cancer mortality are moderately supportive of a relationship, although this cannot be considered important evidence for a causal relationship. Most other ecological correlations are not supportive of a relationship. Eleven oil refinery populations and one population of petroleum products distribution workers have been studied. These studies taken as a group do not appear to support the notion of a relationship between gasoline exposure and kidney cancer. However, most were not designed or analyzed with this hypothesis in mind. An examination of these data which attempts to consider the ages of the populations studied provides some evidence of a small kidney cancer excess among older workers or among workers exposed for long periods. Because of the importance of gasoline and the potential for exposure by the public further study of exposed populations is needed.

Adolescent↗

Review of the carcinogenic potential of gasoline.

This review examines the animal, human, and mechanistic studies that precede the new studies reported in this volume. Wholly vaporized unleaded gasoline was found to produce a dose-dependent increase in renal carcinoma in male rats and an excess above background incidence of hepatocellular tumors in female mice in the high-dose group. Mechanistic studies suggest that gasoline is not mutagenic and that the probable mechanism for the male rat renal tumors involves a rat-specific protein, alpha 2u-globulin, whose binding with highly branched aliphatic compounds results in renal tubule cell death and, in turn, a proliferative sequence that increases renal tubule tumors. Human evidence generated predominantly from studies of refinery workers does not support a kidney or liver cancer risk in humans. The current epidemiologic database is inadequate to access leukemia risk from low-level benzene exposure from gasoline. Studies of gasoline-exposed workers that incorporate quantitative exposure information are needed.

Animals↗

Fate of gasoline oxygenates in conventional and multilevel wells of a contaminated groundwater table in Düsseldorf, Germany.

In a gasoline-contaminated site in Düsseldorf, Germany a two-year monitoring program was carried out to determine the presence, behavior, and fate of 12 gasoline additives in a total of 96 samples from 14 groundwater wells. The origin of contamination was suspected to be a gasoline spill at a gas station. Target compounds were 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 odor problems: Dicyclopentadiene and trichloroethylene. Purge and trap coupled with gas chromatography-mass spectrometry permitted detection of ng/L concentrations. Ninety of the 96 samples analyzed contained MTBE at levels varying between 0.01 to 645 microg/L. Five contaminated hot spots were identified with levels up to U.S. Environmental Protection Agency (U.S. EPA) drinking water advisory values (20-40 microg/L) and one of them doubling Danish suggested toxicity level of 350 microg/L at a depth of 11 m. No significant natural attenuation was found in MTBE degradation, although samples with high levels of MTBE contained 0.1 to 440 microg/L of TBA. These levels were attributed to its presence in the contamination source more than MTBE degradation. tert-Butyl alcohol was found to be recalcitrant in groundwater. In all cases, BTEX were at low concentrations or not detected, showing less persistence than MTBE. The monitoring of the contamination plume showed that the distribution of the MTBE and TBA in the aquifer formed a similar vertical concentration profile that was influenced by the groundwater flow direction.

Chromatography, Ion Exchange↗

[Multi-objectives optimization on life cycle pollutants emission of cassava-based ethanol blended gasoline fuels].

An optimization model on life cycle pollutants emission of cassava-based ethanol blended gasoline fuels, including single and multi-objectives, was carried out in this paper. And, the single and multi-objectives optimization of cassava-based ethanol blended gasoline fuels were done, using the life cycle CO, NOx, PM, HC, SOx, CO2 emissions as objectives. Moreover, sensitivity analysis of design variables was done. The multi-objectives results shown that the blend ratio between cassava-based ethanol and gasoline was 63%. Compare with the initial value, multi-objective optimization of cassava-based ethanol blended gasoline fuels achieved a little more life cycle CO, NOx and PM emissions, about 1%, 15% and 19% respectively, and reduced life cycle HC, SOx and CO2 emissions, 8%, 50%, and 21% respectively.

Air Pollutants↗

[Genotoxicity comparison between gasoline- and methanol-fueled exhaust by TK gene mutation assay].

Methanol fuel is a most promising substitute for gasoline. It is scarcely reported about methanol-fueled exhaust on the health effect, neither about genotoxicity research between methanol- and gasoline-fueled exhaust. In the present study, the two kinds of exhaust were sampled directly from tailpipe at the same type bus, the same state, L5178Y thymidine kinase (TK) gene mutation assay was used to investigate their genotoxicity at the same dose range, and compared with micronucleus and comet assay. The results showed that the genotoxicity of gasoline-fueled exhaust is stronger than that of methanol-fueled exhaust, while the cytotoxicity of methanol-fueled exhaust is stronger than that of gasoline-fueled exhaust at dose range. The study demonstrated that L5178Y TK gene mutation assay is more sensitive than micronucleus and comet assay.

Gasoline↗

Pulmonary function of rats exposed to ethanol and gasoline fumes.

This paper describes the effects of repeated exposure to gasoline and ethanol exhaust fumes on the pulmonary mechanics of rats assessed by whole-body plethysmography. Two groups of 12 male Wistar albino rats each were tested before and after exposure to diluted gasoline or ethanol exhaust gases for 5 weeks, 8 h per day and 5 days per week. An additional group of 12 rats were exposed to clean air under the same experimental conditions. The variations of the functional parameters observed in the three groups before and after exposure were compared. Peak Expiratory Flow and Forced Expiratory Mean Flows in the ranges 0-25%, 25-50% and 50-75% of Forced Vital Capacity were significantly reduced in animals exposed to gasoline exhaust fumes, whereas the group exposed to ethanol exhaust fumes did not differ from the control group. This respiratory impairment is probably due to the presence of SO2 and the quality of the hydrocarbons in gasoline exhaust gases.

Animals↗

Gasoline sniffing and tetraethyl lead poisoning in children.

Two cases of acute organic lead poisoning following gasoline sniffing, with one death, are reported. Signs of lead encephalopathy with elevated blood lead levels and markedly decreased levels of erythrocytic delta-amino levulinic dehydratase (ALAD) were demonstrated. Erythrocytic ALAD activity was used as a screening test for the detection of tetraethyl lead (TEL) poisoning in a group of 43 children who were presumed gasoline sniffers. Their mean ALAD activity was 190 units compared to a mean of 538 units for a control group. A survey of schoolchildren in another isolated community revealed that 59% had decreased ALAD activity, which correlated well with a history of gasoline sniffing. Only 5% of the children had blood lead levels over 40 microgram/dl. The two surveys herein reported suggest that there may be large numbers of children living in isolated communities who are suffering from TEL poisoning as a result of gasoline sniffing. This constitutes a major medical, public health, and social problem heretofore virtually unrecognized.

Adolescent↗

Determination of arsenic in diesel, gasoline and naphtha by graphite furnace atomic absorption spectrometry using microemulsion medium for sample stabilization.

A procedure for the determination of As in diesel, gasoline and naphtha at microg L(-1) levels by GFAAS is proposed. Sample stabilization was achieved by the formation of three component solutions prepared by mixing appropriate volumes of the samples propan-1-ol and nitric acid aqueous solution. This mixture resulted in a one-phase medium, which was indefinitely stable. No changes in the analyte signals were observed over several days in spiked samples, proving long-term stabilization ability. The use of conventional (Pd) and permanent (Ir) modification was investigated and the former was preferred. Central composite design multivariate optimization defined the optimum microemulsion composition as well as the temperature program. In this way, calibration using aqueous analytical solutions was possible, since the same sensitivity was observed in the investigated microemulsion media and in 0.2% v/v HNO(3). Coefficients of correlation larger than 0.999 and an As characteristic mass of 22 pg were observed. Recoveries (n=4) obtained from spiked samples were 98+/-4, 99+/-3 and 103+/-5%, and the limits of detection in the original samples were 1.8, 1.2 and 1.5 microg L(-1) for diesel, gasoline and naphtha, respectively. Validation was performed by the analysis of a set of commercial samples by independent comparative procedures. No significant difference (Student's t-test, p<0.05) was observed between comparative and proposed procedure results. The total determination cycle lasted 4 min for diesel and 3 min for gasoline and naphtha, equivalent to a sample throughput of 7 h(-1) for diesel and 10 h(-1) for gasoline and naphtha.

Journal Article↗

Determination of palladium in gasoline by neutron activation analysis and automated column extraction.

Palladium in gasoline was determined by means of neutron activation analysis (NAA) and selective sorbent extraction. Unleaded gasoline consistent with DIN EN 228, RON 95 was irradiated at a thermal neutron flux of phith = 1.68 x 10(13)s(-1)cm(-2) and an epithermal neutron flux of 3.32 x 10(11)s(-1)cm(-2) for t(irr) = 12 h. The irradiated gasoline was digested with nitric acid and palladium was then separated as N,N-diethyl-N'-benzoylthiourea complex by an automated column pre-concentration procedure. The eluate of 50 microL was dried on a filter paper and the 88.03 keV photons resulting from the decay of 109Pd were detected in a low level HPGe spectrometer with an efficiency of 35.5%. Severe interferences with other matrix constituents, especially 82Br could be overcome and the detection limit for palladium was improved to 3.4 ng/L at a confidence level of 90%. Although the analytical procedure applied yielded the lowest detection limit for palladium obtained in gasoline up to now, no indications for the presence of palladium were found.

Journal Article↗

A comparison of ten different methods for the analysis of saturates, olefins, benzene, total aromatics, and oxygenates in finished gasolines.

The Technical Committee 19 of the European Committee for Standardization (CEN/TC19) in the "Lisbon resolution" requested to evaluate replacement methods to the fluorescent indicator absorption (FIA) (American Standardization for Testing and Material D 1319) method for the determination of aromatics and olefins in gasolines. In the same resolution it was requested to review the two existing methods for the determination of benzene content of gasolines, anticipating lower limit values in future European gasoline specifications. As a result of this request, a round robin (RR) was organized in which 8 gasoline samples are analyzed using 10 different methods in 33 laboratories. The methods used in the RR include, apart from the FIA method, one-dimensional gas chromatography (GC) and multidimensional GC, with and without specific detectors and spectroscopic analysis methods. This study describes these methods in short, gives an evaluation of the results of the RR, and draws a conclusion on the outcome.

Journal Article↗

Benzo(a)pyrene in gasoline partially persists in automobile exhaust.

On average 36 percent of the benzo[a]pyrene in an automobile's exhaust gas comes from the benzo[a]pyrene originally in the gasoline. Between 0.1 and 0.2 percent of the benzo[a]pyrene in the gasoline survives the combustion process and is recovered from the exhaust; 5 percent accumulates in the crankcase oil. Some of the benzo[a]pyrene in the gasoline is converted into other polynuclear aromatic hydrocarbons and other more polar compounds. For our experiments we used commercial gasoline containing benzo[a]pyrene at 1.0 part per million to which was added benzo[a]pyrene-8,9-(14)C at 1.1 parts per million as a radioactive tracer.

Benzopyrenes↗

[Analysis of sulfur compounds in residue fluid catalytic cracking gasoline].

Sulfur compounds in residue fluid catalytic cracking (RFCC) gasolines from Refinery of SINOPEC Beijing Yanshan Company and Refinery of Shijiazhuang were analyzed by gas chromatograph connected with flame photometric detector (FPD) and atomic emission detector (AED). Twelve and 26 kinds of sulfur compounds were detected by AED in RFCC gasolines from Yanshan and Shijiazhuang respectively. Only 0 and 19 kinds of sulfur compounds were found by FPD in these two gasolines respectively. The experimental results demonstrated that AED is more sensitive and selective to sulfur compounds than FPD. It also indicated that thiophenes were the major sulfur compounds in the RFCC gasoline. In addition, mercaptan, sulfoether and disulfide species were found.

English Abstract↗