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Biodegradation of gasoline and BTEX in a microaerophilic biobarrier.

Continuous bioremediation of gasoline-contaminated water in a packed-bed biobarrier system under oxygen-limited conditions is discussed. This study was part of an extensive effort to develop an alternative technology for the in situ bioremediation of hydrocarbons where there is a limited supply of oxygen. Protruded stainless steel pieces and granulated peat moss were used as packing material to support microbial growth in two biobarriers. The inoculum was an enrichment culture of an indigenous microbial population from a soil sample. The biobarriers' inlet gasoline concentrations and the linear liquid velocities were similar to those commonly found at in situ conditions. Gasoline removal efficiencies ranged from 94% to 99.9% in the stainless steel-packed biobarrier, and from 86.6% to 99.6% in the peat moss-packed biobarrier. Effluent gasoline concentrations below 0.03 mg/l were obtained at gasoline loading rates less than 27.5 mg/l.d in the stainless steel-packed biobarrier. The remaining fraction of gasoline in the effluent consisted mainly of three aliphatic compounds and not the aromatic compounds. Both biobarrier packings supported near complete removal of the most soluble aromatic hydrocarbons of gasoline (BTEX) under all the conditions examined. The consumption of sulfate and the presence of sulfate-reducing microorganisms suggested the presence of anaerobic metabolism during the degradation of gasoline. Up to 92% gasoline was removed during the first 3 cm of the biobarriers' length.

Anaerobiosis↗

Health effects of gasoline refueling vapors and measured exposures at service stations.

Liquid gasoline is a complex mixture of at least 150 hydrocarbons with about 60-70% alkanes (paraffins), 25-30% aromatics, and 6-9% alkenes. In order to evaluate the potential for health effects from inhaling gasoline vapors, it is essential to understand the major differences in the composition of vapors versus liquid gasoline. The small chain, low carbon-numbered components are more volatile and thus in higher percentages in the vapor phase than the larger and heavier molecules. It is noteworthy that the concentrations of aromatics (the more toxic of the gasoline components), are depleted to about 2% in the vapor phase, with the light paraffins (the less toxic) enriched to about 90%. Actual measurements of vapor exposure at service stations confirm that the vapor composition is primarily to low weight alkanes although benzene is also emitted and represents the chemical of greatest concern. A perceived health concern from inhaling gasoline vapors is the potential for carcinogenicity based on the induction of kidney tumors in male rats and liver tumors in female mice exposed to wholly-vaporized gasoline. However, the results of the animal studies are of questionable relevance for human risk assessment due to the unique mechanism operative only in the male rat and since the exposure was to wholly-vaporized gasoline rather than the gasoline vapor mixture to which humans are exposed. Recent research supports the hypothesis that branched-chain-alkanes bind to a globulin specific to make rats, alpha 2-u-globulin. The protein complex can not be degraded in the usual manner so that protein accumulation occurs in renal cells, leading to cytotoxicity, death, proliferation, and with prolonged exposure, kidney cancer. The results of epidemiology studies fail to link an increase in cancer to exposure to gasoline vapors.

Air Pollutants↗

A comparison on the emission of polycyclic aromatic hydrocarbons and their corresponding carcinogenic potencies from a vehicle engine using leaded and lead-free gasoline.

Our objective in this study was to assess the effect of using two kinds of lead-free gasoline [including 92-lead-free gasoline (92-LFG) and 95-lead-free gasoline (95-LFG), rated according to their octane levels] to replace the use of premium leaded gasoline (PLG) on the emissions of polycyclic aromatic hydrocarbons (PAHs) and their corresponding benzo[a]pyrene equivalent (BaP(eq)) amounts from the gasoline-powered engine. The results show that the three gasoline fuels originally contained similar total PAHs and total BaP(eq) contents; however, we found significant differences in the engine exhausts in both contents. The above results suggest that PAHs originally contained in the gasoline fuel did not affect the PAH emissions in the engine exhausts. The emission factors of both total PAHs and total BaP(eq) obtained from the three gasoline fuels shared the same trend: 95-LFG > PLG > 92-LFG. The above result suggests that when PLG was replaced by 95-LFG, the emissions would increase in both total PAHs and total BaP(eq), but when replaced by 92-LFG would lead to the decreased emissions of both contents. By taking emission factors and their corresponding annual gasoline consumption rates into account, we found that both total PAH and total BaP(eq) emissions increased from 1994 to 1999. However, the annual increasing rates in total BaP(eq) emissions were slightly higher than the corresponding increasing rates in total PAHs.

Air Pollutants↗

[Inhalation of gasoline and damage to health in workers at gas stations].

The aim of this study was to made assessment of chronic health effects in 37 workers exposed to gasoline, and its constituents at gasoline stations between 1985 and 1996. By the study we have involved thirty-seven persons who had been exposed to gasoline for more than five years were examined. The evaluation included a medical/occupational history, hematological and biochemical examination, a physical exam, standardized psychological tests, and ultrasound examination of kidneys and liver. The groups were identical in other common parameters including age, gender (all men), and level of education (P < 0.05). The data were compared to two control groups: 61 gasoline unexposed controls and 25 workers at gasoline stations exposed to organic lead for only nine months. Peripheral smear revealed basophilic punctuated eritrocytes and reticulocytosis. We found in chronic exposed gasoline workers haematological disorders: mild leukocytosis (7 of 37), lymphocytosis (20 of 37), mild lymhocytopenia (3 of 37), decrease of red blood cells count (11 of 37). Results indicated that they have suffered from liver disorders: lipoid degeneration of liver (14 of 37), chronic functional damages of liver (3 of 37), cirrhosis (1 of 37). Ultrasound examination indicated chronic kidney damages (8 of 37). These results significantly differed from those of controls (P < 0.05). In 13 out of 37 workers at gasoline stations exposed to gasoline for more than 5 years the symptom of depression and decreased reaction time and motor abilities were identified. The summary of diseases of workers exposed to organic lead and gasoline are discussed.

Adult↗

[Investigation and application of gasoline sample identity technique].

Chemometrics method was used to solve the problem of automatic selecting model for the detailed hydrocarbon analysis (DHA) of gasoline samples by gas chromatography/ flame ionization detection (GC/FID). The 29 peaks in GC/FID DHA chromatogram and their amounts were selected as the discriminating parameters to establish the five pattern models for different gasoline samples, such as fluid catalytic cracking (FCC) gasoline, coking gasoline, straight run gasoline, reformed gasoline, and alkylation gasoline. The principle component analysis (PCA) and Soft Independent Modeling of Class Analogies (SIMCA) were used to classify the gasoline samples and to identify the unknown samples according to the above pattern models. One hundred gasoline samples, derived from known resources, were employed to validate the reliability of the sample identity technique. With the help of the pattern identity method referred here, the automation of GC/FID DHA method becomes possible.

Chromatography, Gas↗

Effect of the gasoline additives on PAH emission.

PAH emission from the powered engines fueled by a 95 leadfree gasoline (95-LFG), a 92 leadfree gasoline (92-LFG) and a Premium leaded gasoline (PLG) with two gasoline additives (SA and SB) were collected using a PAH sampling system with a particulate interception device. Twenty one PAHs were analyzed primarily by an GC/MS, while eight metal elements were determined mainly by an ICP-AES. This investigation showed that the gasoline additives contain more amounts of carcinogenic PAHs than gasolines do. Blending these additives do raise the PAH content in the gasolines, simultaneously, will emit more amount of PAHs from the tailpipe of engine exhaust. It is suggested that before a gasoline additive is commercialized, an assessment on its PAH emission should be evaluated to make sure that the additive will not emit more PAHs and cause adverse effect on public health.

Carcinogens↗

Determination of the effect of exposure to gasoline components on a high density polyethylene geomembrane using the comprehensive test system.

The comprehensive testing system (CTS) for geomembranes was used to test the compatibility of high-density polyethylene (HDPE) geomembrane landfill liner material with chemicals typically found in motor vehicle fuel. The CTS is a testing apparatus specifically designed to test the effects of simultaneously applying mechanical load, fluid head, and chemical exposure on the geomembrane. A combination of these factors is present on the geomembrane material in service, and the CTS provides a laboratory reproduction of actual field conditions. The article provides a description of gasoline based upon the desirable qualities of gasoline and provides background on testing of rubbers used in gasoline-powered engine parts. The test's chemicals were gasoline, motor oil, benzene, ethylbenzene, toluene, xylenes, and iso-octane (2,2,4 trimethyl pentane). This work found that gasoline had an effect on the geomembrane greater than the effect of any of the pure chemicals except ethylbenzene. Benzene, and the other aromatic compounds (ethylbenzene, toluene, and xylenes) are typically the primary regulatory concerns at fuel contaminated sites. The fact that gasoline had a greater effect on the performance of the HDPE geomembrane indicated that chemicals are present in gasoline which can decrease the performance of the containment structures used to hold gasoline, while not having a significant health risk. The clear implication is that risk assessments conducted on facilities must not only include the health risks of chemicals placed in a facility, but must also consider the effect of the chemical on a containment structure. The fact that low-health-risk chemicals may have a great impact on the effectiveness of containment structures leads to a possible synergistic mechanism where the low-health-risk chemicals enable a pathway for greater-health-risk chemicals to enter the environment.

Gasoline↗

DNA binding of polycyclic aromatic hydrocarbons in a human bronchial epithelial cell line treated with diesel and gasoline particulate extracts and benzo[a]pyrene.

Particulate matter of vehicle exhaust is known to contain carcinogenic compounds such as polycyclic aromatic hydrocarbons (PAH) and is suggested to increase lung cancer risk in humans. This study examines the differences in diesel and gasoline-derived PAH binding to DNA in a human bronchial epithelial cell line (BEAS-2B). Particulate matter (PM) of gasoline exhaust was collected from passenger cars on filters and semi-volatile compounds on polyurethane foam (PUF). The soluble organic fraction (SOF) extracted from the particles was used to expose the cells and to perform PAH analysis. Gasoline extracts, benzo[a]pyrene (B[a]P) and reference materials (SRM 1650 and 1587) were used to study dose-dependent adduct formation in BEAS-2B cells. The levels of DNA adducts were in good accord with the 10 DNA adduct-forming PAH concentrations analyzed in the extracts. Gasoline extracts, SRM 1650, SRM 1587 and B[a]P formed DNA adducts dose-dependently in BEAS-2B cells. The time-dependent DNA adduct formation of 5.0 micro M B[a]P was lower than that of 2.5 micro M B[a]P. The results of this study indicate that reformulated and standard diesel fuels formed about 11- and 31-fold more adducts than gasoline, respectively, when PAH-DNA adduct levels were calculated on an emission basis (adducts/mg PM/km), whereas on a particulate basis (adducts/mg PM) no difference between the diesel and gasoline extracts was observed. We conclude that the genotoxicity of diesel fuel is based on higher particulate emission rates compared to gasoline emission and although the concentration of PAH compounds was higher in diesel particulate extracts, DNA binding by the gasoline particulate-bound PAH compounds was more pronounced than that by the diesel particulate-bound PAH compounds.

Air Pollutants↗

Response of microorganisms to an accidental gasoline spillage in an arctic freshwater ecosystem.

The response of microorganisms to an accidental spillage of 55,000 gallons of leaded gasoline into an Arctic freshwater lake was studied. Shifts in microbial populations were detected after the spillage, reflecting the migration pattern of the gasoline, enrichment for hydrocarbon utilizers, and selection for leaded-gasoline-tolerant microorganisms. Ratios of gasoline-tolerant/utilizing heterotrophs to "total" heterotrophs were found to be a sensitive indicator of the degree of hydrocarbon contamination. Respiration rates were elevated in the highly contaminated area, but did not reflect differences between moderately and lightly contaminated areas. Hydrocarbon biodegradation potential experiments showed that indigenous microorganisms could extensively convert hydrocarbons to CO(2). In situ measurement of gasoline degradation showed that, if untreated, sediment samples retained significant amounts of gasoline hydrocarbons including "volatile components" at the time the lake froze for the winter. Nutrient addition and bacterial inoculation resulted in enhanced biodegradative losses, significantly reducing the amount of residual hydrocarbons. Enhanced biodegradation, however, resulted in the appearance of compounds not detected in the gasoline. Since the contaminated lake serves as a drinking water supply, treatment to enhance microbial removal of much of the remaining gasoline still may be advisable.

Alaska↗

State of the science on the carcinogenicity of gasoline with particular reference to cohort mortality study results.

As a result of the content of benzene in various streams of refinery products, including gasoline, it is not surprising that over the years studies and case reports have linked gasoline exposure to lymphopoietic cancers (LPC), particularly leukemia and multiple myeloma (MM). Of three recently conducted studies of gasoline-exposed workers, one shows strong associations with leukemia and MM, a second suggests some association with leukemia and did not analyze data for MM, and the third study is not possible to evaluate because of a major problem with study design. Other diseases of particular interest in relation to gasoline exposure are kidney cancer, malignant melanoma, and heart disease. One study suggests an association with kidney cancer, but the second study did not. There appears to be no association between employment in refineries or gasoline exposure and heart disease. However, evaluation of risk of kidney cancer and heart disease is somewhat difficult because investigators did not control for cigarette smoking, even though it is related to these diseases. This is of particular concern when studying gasoline-exposed workers, who because of the explosive nature of gasoline probably smoke less than the general population used for comparison of mortality. Some studies of refinery workers and gasoline-exposed workers in particular show an excess risk of death from malignant melanoma. Whether this latter association is the result of benzene/gasoline exposure, sunlight exposure, or a combination of the two cannot be determined with the data currently available.(ABSTRACT TRUNCATED AT 250 WORDS)

Carcinogens, Environmental↗

[Comparative study on the mutagenicity of the gasoline-fueled vehicle exhaust and methanol-fueled vehicle exhaust].

OBJECTIVE: In order to compare the mutagenicity of the gasoline-fueled vehicle exhaust (gasoline exhaust for short) and the methanol-fueled vehicle exhaust (methanol exhaust for short), provide a scientific basis for replacement gasoline by methanol as fuel in vehicle. METHODS: The Ames assay and A549 cell micronucleus test in vitro were applied to compare the mutagenicity of gasoline-fueled vehicle exhaust and methanol-fueled vehicle exhaust. RESULTS: The results showed that the gasoline-fueled vehicle exhaust expressed evident mutagenicity in Ames assay (TA98 strain) with or without rat liver-derived metabolic activation system (S9). The mutagenicity increased obviously when S9 was used and showed a good dose-response relationship. However, the methanol-fueled vehicle exhaust did not show any mutagenic potential in Ames assay (TA98, TA100 strains) with or without rat liver-derived metabolic activation system (S9). In A549 cells micronucleus test in vitro, between 0.025 - 0.2JL/ml, the rate of A549 cells micronucleus could be induced by the gasoline-fueled vehicle exhaust. For the methanol-fueled vehicle exhaust, there was no significant differences in the rate of A549 cells micronucleus between the tested groups and control. CONCLUSION: The results strongly suggested that the gasoline-fueled vehicle exhaust had potential mutagenicity and the methanol-fueled vehicle exhaust did not show any potential mutagenicity. The results also provided a scientific basis for replacement gasoline by methanol as fuel in vehicle.

Animals↗

[Estrogenic effects of gasoline-fueled vehicle exhausts and methanol-fueled vehicle exhausts].

OBJECTIVE: To investigate the estrogenic effects of gasoline-fueled vehicle exhausts and methanol-fueled vehicle exhausts and provide a scientific basis for replacement of gasoline by methanol as fuel in vehicle. METHODS: The estrogen-like activities of gasoline-fueled vehicle exhausts and methanol-fueled vehicle exhausts were detected using the recombinant yeast estrogen system. RESULTS: The A600 value of gasoline-fueled vehicle exhausts was 0. 081 when the concentration of gasoline-fueled vehicle exhausts was 1000 mL/mL, and there were significantly statistical differences as compared with those of the dimethyl sulfoxide (DMSO) control group (P < 0.05), which indicated that such concentration had poisonous effects on yeast cell; when the concentration of gasoline-fueled vehicle exhausts was 31.25 mL/mL, the estrogen-like activities of gasoline-fueled vehicle exhausts could be detected, and there were significantly statistical differences as compared with those of the DMSO control group (P<0.05). Besides, the estrogen-like activities could not be detected in other groups with various concentrations. The estrogen-like activities of methanol-fueled vehicle exhausts could not be detected, and there were no significantly statistical differences in A600 value (P > 0.05) when each group was compared with the DMSO control group. CONCLUSION: Gasoline-fueled vehicle exhausts have weak estrogenic effects, whereas methanol-fueled vehicle exhausts have no such effects.

Air Pollution↗

Assessment of health effects in workers at gasoline station.

The aim of this study was to made assessment of health effects in 37 workers exposed to gasoline, and its constituents at gasoline stations between 1985 and 1996. Thirty-seven persons who had been exposed to gasoline for more than five years were examined. The evaluation included a medical / occupational history, haematological and biochemical examination, a physical exam, standardized psychological tests, and ultrasound examination of kidneys and liver. The groups were identical in other common parameters including age, gender (all men), and level of education (P<0. 05). The data were compared to two control groups: 61 healthy non-exposed controls and 25 workers at gasoline stations exposed to organic lead for only nine months. Peripheral smear revealed basophilic stippling and reticulocytosis. We found in chronic exposed gasoline workers haematological disorders: mild leukocytosis (7 of 37), lymphocytosis (20 of 37), mild lymhocytopenia (3 of 37), and decrease of red blood cells count (11 of 37). Results indicated that they have suffered from liver disorders: lipoid degeneration of liver (14 of 37), chronic functional damages of liver (3 of 37), cirrhosis (1 of 37). Ultrasound examination indicated chronic kidney damages (8 of 37). These results significantly differed from those of controls (P< 0.05). In 13 out of 37 workers at gasoline stations exposed to gasoline for more than 5 years the symptom of depression and decreased reaction time and motor abilities were identified. The summary of diseases of workers exposed to organic lead and gasoline are discussed.

Journal Article↗

Comparison of gasolines using gas chromatography-mass spectrometry and target ion response.

Gas chromatography-mass spectrometry was used to compare gasoline samples obtained from different sources based on the difference in amounts of certain components found in the headspace of gasoline using target response data. Many suspected arson cases involve comparing an ignitable liquid extracted from fire debris to a liquid found in a suspect's possession to determine if they could have had a common source. Various component ratios are proposed for determining if an unevaporated gasoline sample could have originated from the same source as an evaporated gasoline extracted from fire debris. Fifty and 75% evaporated gasoline samples were both found to contain similar ratios of certain components when compared with its unevaporated source gasoline. The results of the comparisons in this study demonstrate that for cases involving gasoline that has been evaporated up to 50% and extracted from pine, it is possible to eliminate comparison samples as originating from the same source. The results of the 75% comparisons suggest it may be possible to apply the same type of comparison to cases involving 75% evaporated gasoline.

Journal Article↗

Application of high-performance liquid chromatography with ultraviolet diode array detection and refractive index detection to the determination of class composition and to the analysis of gasoline.

A method of effective application of normal-phase high-performance liquid chromatography (NP-HPLC) with ultraviolet diode array detection (DAD) and refractive index detection (RID) for the determination of class composition of gasoline and its components, i.e. for the determination of content of alkenes, aromatic and saturated hydrocarbons in gasoline meeting modern quality standards, has been developed. An aminopropyl-bonded silica stationary phase was used along with n-hexane or n-heptane as the mobile phase. A DAD signal integrated over the 207-240 nm range was used to determine alkenes. This eliminates the necessity of separating alkenes from saturates, because the latter do not absorb UV radiation above 200 nm. The content of aromatic hydrocarbons is determined by means of a refractive index detector. Calibration was based on hydrocarbon type composition determined by the fluorescent indicator adsorption method, ASTM D1319. The results obtained by the developed method were found to be consistent with those obtained by fluorescent indicator adsorption or by a multidimensional GC method (PIONA) (ASTM D5443). The method can be applied to gasoline meeting recent quality standards, irrespective of refining technology used in the production of gasoline components, including gasoline with various contents of oxygenates. The developed method cannot be used to determine the hydrocarbon type composition of gasoline that contains as a component the so-called pyrocondensate, i.e. the fraction with a boiling point up to 220 degrees C, obtained through thermal pyrolysis of distillation residues of crude oil or coal and, consequently, does not meet the quality standards. The paper includes the procedure for identification of this type of gasoline.

Chromatography, High Pressure Liquid↗

Penetration of benzene, toluene and xylenes contained in gasolines through human abdominal skin in vitro.

Few studies are available in literature on the risk for humans from skin exposure to gasolines. This work is focused on the in vitro skin penetration of benzene (carcinogenic substance), toluene and xylenes. We examined three commercial gasolines using the Franz diffusion cells and human abdominal full thickness skin. Gasoline composition was determined using a multi-dimensional gas chromatographic (MDGC) technique. Aromatic compounds into the receptor fluid, consisting of saline solution were quantitated by a gas chromatography technique equipped with a flame ionization detector (GC-FID) and coupled with a headspace-solid phase micro extraction system (HS-SPME). Among the three substances, benzene showed the highest average apparent permeability coefficient (K(p)=43.8x10(-5)cmh(-1)) compared to toluene (K(p)=6.48x10(-5)cmh(-1)) and xylenes (K(p)=0.84x10(-5)cmh(-1)). This value could be explained by the lower boiling point and higher water solubility of benzene. Lag times were about 1h for benzene and 2h for toluene and xylenes. Averaged total recoveries in the receptor fluid were 0.43% of dose for benzene, 0.06% for toluene and 0.008% for xylenes. A statistical significative difference (Student's t-test, P<0.05) between the fluxes calculated for the three gasolines are noted only for xylene and for toluene between gasolines #1 (richer in aromatic compounds) and #3. The obtained apparent permeability coefficient are useful for determining the permeability of these aromatics components from gasolines of a different composition. Hands exposure risk, calculated using RfD and RfC as defined by US EPA, is critical for benzene. The risk of skin permeation of gasoline, and, in particular, of benzene, should be better evaluated for those workers who have a large potential for exposure. Adequate personal protective equipment should be used in the high exposure jobs, mainly for hands and forearms.

Abdomen↗

Gasoline sniffing multifocal neuropathy.

The polyneuropathy caused by chronic gasoline inhalation is reported to be a gradually progressive, symmetric, sensorimotor polyneuropathy. We report unleaded gasoline sniffing by a female 14 years of age that precipitated peripheral neuropathy. In contrast with the previously reported presentation of peripheral neuropathy in gasoline inhalation, our patient developed multiple mononeuropathies superimposed on a background of sensorimotor polyneuropathy. The patient illustrates that gasoline sniffing neuropathy may present with acute multiple mononeuropathies resembling mononeuritis multiplex, possibly related to increased peripheral nerve susceptibility to pressure in the setting of neurotoxic components of gasoline. The presence of tetraethyl lead, which is no longer present in modern gasoline mixtures, is apparently not a necessary factor in the development of gasoline sniffer's neuropathy.

Administration, Inhalation↗

Life cycle assessment of gasoline blending options.

A life cycle assessment has been done to compare the potential environmental impacts of various gasoline blends that meet octane and vapor pressure specifications. The main blending components of alkylate, cracked gasoline, and reformate have different octane and vapor pressure values as well as different potential environmental impacts. Because the octane and vapor pressure values are nonlinearly related to impacts, the results of this study show that some blends are better for the environment than others. To determine blending component compositions, simulations of a reformer were done at various operating conditions. The reformate products of these simulations had a wide range of octane values and potential environmental impacts. Results of the study indicate that for low-octane gasoline (95 Research Octane Number), lower reformer temperatures and pressures generally decrease the potential environmental impacts. However, different results are obtained for high-octane gasoline (98 RON), where increasing reformer temperatures and pressures increase the reformate octane values faster than the potential environmental impacts. The higher octane values for reformate allow blends to have less reformate, and therefore high-octane gasoline can have lower potential environmental impacts when the reformer is operated at higher temperatures and pressures. In the blends studied, reformate and cracked gasoline have the highest total impacts, of which photochemical ozone creation is the largest contributor (assuming all impact categories are equally weighted). Alkylate has a much lower total potential environmental impact but does have higher impact values for human toxicity by ingestion, aquatic toxicity, terrestrial toxicity, and acidification. Therefore, depending on environmental priorities, different gasoline blends and operating conditions should be chosen to meet octane and vapor pressure specifications.

Gasoline↗