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PubMed1986

Predicting carcinogenicity of petroleum distillation fractions using a modified Salmonella mutagenicity assay.

The Ames Salmonella/microsomal activation mutagenesis assay has been modified to improve sensitivity and reproducibility to complex mixtures derived from the refining and processing of petroleum. Oil samples were dissolved in cyclohexane and subsequently extracted with dimethyl sulfoxide to produce aqueous compatible solutions which readily interact with tester bacteria. Also, the liver homogenate (S-9) and NADP cofactor concentrations were increased and hamster rather than rat liver S-9 was used. The initial slope of the dose response curve relating mutagenicity (revertants per plate) to the dose of extract added was used as an index of mutagenic activity; this slope was obtained through a computerized curve fitting procedure. The modified assay was used to rank 18 oil samples for mutagenic activity; this ranking correlates highly (r = 0.92) with potency rankings of the same samples previously determined from dermal carcinogenicity bioassays. Sensitivity and reproducibility of the assay are sufficient to permit routine use for detecting potential carcinogenic activity of individual refinery streams and blends which contain components boiling above 500 degrees F.

Animals↗
PubMed1995

Chromosome aberrations in blood lymphocytes from petroleum refinery workers.

To evaluate the possible cytogenetic consequences of exposure of human populations to petrochemicals, the frequency of chromosomal aberrations was studied in blood lymphocytes obtained from 233 persons working at different locations in a large oil refinery (184 exposed and 49 worksite controls) and from 47 individuals who served as community controls. Chromosomal aberrations occurred with frequencies (mean +/- SEM) between 0.023 +/- 0.013 and 0.037 +/- 0.011 breaks per cell (1.56 +/- 0.87% to 2.66 +/- 0.54% aberrant cells) in the exposed groups. These values, with the exception of those observed in two workshops (crude oil unloading as well as petroleum tanker washing and lubrication), were significant compared to the presumably spontaneous (control) levels (0.015 +/- 0.004 to 0.021 +/- 0.007 breaks per cell and 1.17 +/- 0.29% to 1.46 +/- 0.40% aberrant cells). Cigarette-smoking was not associated with increased chromosomal aberrations in the exposed and in the control groups.

Cell Division↗
PubMed1981

Effects of petroleum on adrenocortical activity and on hepatic naphthalene-metabolizing activity in mallard ducks.

Unstressed mallard ducks (anas platyrhychos), given uncontaminated food and maintained on a short photoperiod, show two daily maxima in plasma corticosterone concentration ([B]) on occurring early in the light phase and a second just before the onset of darkness. After one week of exposure to food containing 3% (v/w) South Louisiana crude oil, plasma [B] were significantly lowered throughout the day. Similar abrupt declines in plasma [B] also occurred during the first 10 days of exposure to food containing 1% and 0.5% crude oil. Although the plasma [B] in birds consuming food contaminated with 0.5% crude oil increased between 10 and 50 days of exposure, the concentration after 50 days was still lower than normal. During the same interval, normal plasma [B] were restored in birds consuming food containing 1% and 3% crude oil. Significant increases occurred in the naphthalene-metabolizing properties of hepatic microsomes prepared from birds acutely exposed to all levels of petroleum-contaminated food and elevated levels were sustained throughout the first 50 days of exposure. Birds given food containing 3% crude oil for more than 50 days, however, showed steady declines in hepatic naphthalene-metabolizing activity. After 500 days, the activity was similar to that found in contemporaneous controls. During the same interval the plasma [B] increased until the levels were higher than normal after 500 days of exposure; at this time, an inverse relationship, similar to that seen during the first week of exposure to contaminated food, was once more established between plasma [B] and the concomitant hepatic naphthalene-metabolizing activity.

Animals↗
PubMed1982

Petroleum refinery wastewater induction of the hepatic mixed-function oxidase system in Pacific staghorn sculpin.

Induction of hepatic microsomal cytochrome P450 and aldrin epoxidase was observed in the estuarine sculpin (Leptocottus armatus), following in vivo exposure to Class B petroleum refinery effluent from two West Coast refineries. The data demonstrate the presence and inducibility of the mixed-function oxidase system in Leptocottus armatus. Differences in the extent of mixed-function oxidase induction between the two effluents may be related to differences in wastewater chemistry.

Animals↗
PubMed1991

Automated measurement of lysosomal structure alterations in oocytes of mussels exposed to petroleum hydrocarbons.

The present study examines the structure of the lysosomal system of mature oocytes in mussels, Mytilus galloprovincialis, after a 21 day exposure to the water accommodated fraction (WAF) of two crude oils (types Ural and Maya) and of a commercial lubricant oil. The automated image analysis indicates that lysosomes, showing cytochemically demonstrable beta-glucuronidase activity, are smaller and much more numerous in oocytes of mussels treated with a 40% dose of Ural- and Lubricant-WAF when compared to controls. It is suggested that the structure of the lysosomal system of oocytes is different from that of somatic cells (i.e., digestive cells) and that budding or "fission" into smaller bodies occurs in oocyte lysosomes under certain petroleum hydrocarbon-exposure conditions. These changes in the lysosomal compartment appear to be associated to the process of gamete release or spawning.

Animals↗
PubMed1978

Petroleum hydrocarbon resistance in the marine worm Neanthes arenaceodentata (polychaeta: annelida), induced by chronic exposure to No. 2 fuel oil.

1. Three successive generations of the marine polychaetous annelid Neanthes arenaceodentata taken from a laboratory population, were continuously exposed to one of three sublethal concentrations of No. 2 Fuel Oil water-soluble-fraction (WSFs). During each generation larvae, juvenile, and immature adult polychaetes were challenged with acute (96 hr) doses of No. 2 Fuel Oil or south Louisiana crude oil WSF to test their sensitivity to petroleum hydrocarbons (PHCs). 2. Larvae from all 3 generations, at all exposure concentrations, were no different from control (susceptible) larvae in their sensitivity to the two test oils. F1, F2, and F3 adults exhibited equally increased PHC resistance (X2) compared to control adults. 3. The only evidence of increased resistance beyond that observed in F1 animals was seen in results of bioassays with juvenile worms, wherein PHC resistance increased from slightly below control levels in F1 juveniles to slightly above control tolerance among F3 juveniles. 4. With the exception of F1 worms, removal from chronic exposure 7 or 14 days prior to challenge did not result in termination or reduction of resistance, implicating a genetic mechanism behind PHC resistance in N. arenaceodentata. 5. F3 resistant and unexposed control polychaetes accumulated, metabolized, and excreted a key diaromatic PHC (naphthalene-14C) in quantitatively identical fashion. Mechanisms responsible for resistance appeared unrelated to external permeability and/or excretion rates.

Animals↗
PubMed1978

Effects of petroleum hydrocarbon solvents on alkaline phosphatase of rats.

After administration of benzene, gasoline, IOMEX or petroleum ether, liver alkaline phosphatase showed over 200% increase in activity whereas kidney alkaline phosphatase activity was depressed by 50%. The pattern of separation of isoenzymes of alkaline phosphatase in liver, kidney and serum indicated involvement of one of the isoenzymes. A simple method of detecting the incipent toxicity is described.

Alkaline Phosphatase↗
PubMed1991

Bench scale studies of the soil aeration process for bioremediation of petroleum hydrocarbons.

An alternative to traditional hydrocarbon bioremediation is to pump air through unsaturated soils to create aerobic conditions and induce biodegradation. This study examines the effects of moisture and nutrient augmentation on biodegradation of petroleum hydrocarbons in aerated soils. Findings indicate that forced aeration, coupled with additions of nutrients and moisture, stimulate hydrocarbon-degrading microorganisms and present a feasible approach to bioremediation management.

Bacteria↗
PubMed1994

Bioremediation of petroleum hydrocarbons in soil column lysimeters from Kwajalein island.

Soil column studies were used to evaluate petroleum hydrocarbon (PHC) remediation in soils from Kwajalein Atoll. Treatments included controls, and combinations of water, air, nutrients, and bioaugmentation with indigenous microbes (W, A, N, and M, respectively). Microbial colony forming units (CFU) decreased in the control columns and in treatments without air. Treatments including W+A+N and W+A+N+ exhibited increased CFU. One third of the PHC was removed by water and another third was removed by W+A+N and W+A+N+M treatments. Bioaugmentation with indigenous PHC degraders did not enhance bioremediation. Potential for bioremediation was demonstrated by air, water, and nutrient amendments.

Air↗
PubMed2002

Determination of petroleum contamination in shellfish using solid phase micro-extraction with gas chromatography-mass spectrometry.

Headspace solid phase micro-extraction (HS-SPME) has been applied as a sampling technique for the determination of petroleum contamination in shellfish using capillary gas chromatography-mass spectrometry (GC-MS). A poly(dimethylsiloxane) fused silica fibre (100 microm thickness) was found to be satisfactory for the extraction of a range of aliphatic hydrocarbons (HCs) from homogenised shellfish tissues. The SPME conditions, including temperature, salt content, extraction time and desorption temperature, were optimised for a range of aliphatic HCs (C9-C20). A methyl silicone column GC (12 m x 0.20 mm, 0.33 microm layer thickness) was used with a temperature programme from 40 to 260 degrees C and the HCs were determined within a mass range of m/ z=50-550 in electron impact mode. Calibration range was from 10 to 5000 ng/g with linear correlation coefficients ( r(2)) of 0.982 for nonane to 0.997 for octadecane. Detection limits for aliphatic HCs, spiked into shellfish (mussel) tissues, varied from 3.6 ng/g (tetradecane) to 51 ng/g (eicosane) and relative standard deviation (% RSD) values ranged from 1.4% (hexadecane) to 24.3%(eicosane).

Animals↗
PubMed2002

Total synchronous fluorescence scan spectra of petroleum products.

Extending the two-dimensional synchronous fluorescence scan to a three-dimensional total synchronous fluorescence scan (TSFS) spectral measurement gives the total synchronous fluorescence characteristics of a multifluorophoric sample at various possible wavelength intervals (Deltalambda), which could help to characterize multifluorophoric systems better. TSFS spectra of petroleum products such as diesel, kerosene, petrol, engine oil etc., available in the Indian market, are reported. Fluorescence in these samples is due to the presence of polycyclic aromatic hydrocarbons (PAHs) of various ring sizes. The TSFS contour plot profiles of the neat samples measured at right-angle geometry is a result of various energy-degrading photophysical processes such as inner filter effect, light attenuation, resonance energy transfer, collisional quenching etc. TSFS plots make it easy to obtain the optimized Deltalambda of an unknown sample of analytical interest. TSFS and the excitation-emission matrix (EEM) techniques are similar, but the contour profiles generated are different. The response of the TSFS contour profiles to dilution is different from that in the EEM contour profiles. Thus, TSFS can provide an alternative way of presenting the fluorescence response of concentrated multifluorophoric samples.

Fuel Oils↗
PubMed2005

Liquid chromatographic properties of aromatic sulfur heterocycles on a Pd(II)-containing stationary phase for petroleum analysis.

Polycyclic aromatic sulfur heterocycles (PASHs) can show very poor reactivities in catalytic hydrodesulfurization processes in refineries, especially those in high-boiling fractions and distillation residues. An insight into the structural features of the most recalcitrant PASHs is essential for developing more efficient catalysts and improving refinery processes. The very high complexities of such mixtures necessitate fractionation of the samples into smaller subsets according to defined criteria. A stationary phase containing a palladium(II)-complex was previously shown to be efficient for separating PASHs in lighter petroleum fractions. Here we characterize this ligand exchange chromatographic phase using a large number of sulfur aromatic model compounds that were synthesized for the purpose. In general, compounds containing thiophene rings that are not condensed with other aromatic systems are weakly retained and elute in a first fraction with the polycyclic aromatic hydrocarbons. Thiophene rings condensed with other aromatic rings are more strongly retained and elute in a later fraction with a more polar eluent. If the sulfur is in a non-aromatic ring, the compound is irreversibly retained by the Pd(II) ions. Some steric effects are seen in compounds with alkyl or aryl substituents close to the sulfur atom but in general they do not interfere strongly with the complexation. Thus it seems possible to separate groups of aromatic sulfur compounds according to their complexation properties. For instance, such fractionated samples can be studied much more easily by mass spectrometric techniques.

Chromatography, Liquid↗
PubMed2000

Mathematical algorithm for qualitative and semiquantitative analysis of petroleum hydrocarbons in solid wastes using on-line gas chromatography.

Non-degradated mineral-oils like gasoline, solvent naphtha, diesel fuel, fuel and lubricating oils provide a characteristic fingerprint gas chromatogram. This visual classification, e.g. in solid wastes, is complicated due to the simultaneous presence of several mineral-oils. Therefore, a mathematical algorithm for the separation of gas chromatographic fingerprint of "single mixtures" of aliphatic hydrocarbons is developed. The technique is essential for analysis of time-overlapping "single mixtures" of petroleum hydrocarbons (so-called "complex mixtures") and it relies on the concentration-varying hydrocarbons during evaporation. It is possible to separate the data from the gas chromatogram of a "complex mixture" of hydrocarbons into the chromatograms of the pure "single mixtures" and to give their respective concentrations. A synthetic "complex mixture" of kerosene, diesel fuel and lubricating oil is used to illustrate the method.

Algorithms↗
PubMed2005

Alterations of metabolic enzymes in Australian bass, Macquaria novemaculeata, after exposure to petroleum hydrocarbons.

Australian bass Macquaria novemaculeata were exposed to the water-accommodated fraction of Bass Strait crude oil, dispersed crude oil, or burnt crude oil to assess sublethal effects of oil spill remediation techniques on fish. Fish were exposed to these treatments for 16 days either through the water column or by way of a pre-exposed diet of amphipod Allorchestes compressa. Fish gills, liver, and white muscle were sampled and cytochrome C oxidase (CCO) and lactate dehydrogenase (LDH) activities quantified. In all treatments containing fish exposed by way of the water column, aerobic activity increased in the gills, whereas a decrease of this enzymic activity was observed in the liver and white muscle. Exposures by way of the food pathway indicated similar trends. Anaerobic (LDH) activity increased in the gills, liver, and white muscle after waterborne exposures. Stimulation in anaerobic activity also occurred in the liver and white muscle of fish after exposure to contaminated food. CCO activity in the gills was the most sensitive biomarker when monitoring waterborne exposures to petroleum hydrocarbons. In the gills, the dispersed oil treatment resulted in the most pronounced biological response, suggesting that in the short term the use of dispersants on an oil slick might cause the most perturbations to fish metabolism.

Animals↗
PubMed2001

The effect of different oil spill remediation techniques on petroleum hydrocarbon elimination in Australian bass (Macquaria novemaculeata).

Petroleum hydrocarbons were investigated in juvenile Australian bass, Macquaria novemaculeata, following exposure to the water accommodated fraction (WAF) of Bass Strait crude oil, chemically dispersed crude oil, and burnt crude oil. Each treatment was administered for 16 days either through the water column or through the diet (amphipod, Allorchestes compressa). Polycyclic aromatic hydrocarbon (PAH) elimination was determined by measuring biliary benzo(a)pyrene (B(a)P) and naphthalene-type metabolites. Biliary PAH-type metabolite concentrations varied with the type of oil spill remediation technique, route of exposure (food versus water), and exposure concentration. Fish exposed to chemically dispersed crude oil via the water exhibited the highest PAH-type biliary metabolite concentrations, relative to fish exposed to other treatments. In fish exposed via the diet, the highest concentration of both types of biliary metabolites also appeared in the dispersed oil-exposed individuals. The results suggest that chemically dispersing oil may have the greatest effect on bioavailability of hydrocarbons, both through waterborne and food chain exposures.

Animals↗
PubMed2005

Monitoring of petroleum hydrocarbon degradative potential of indigenous microorganisms in ozonated soil.

This study was performed to investigate the petroleum hydrocarbon (PH) degradative potential of indigenous microorganisms in ozonated soil to better develop combined pre-ozonation/bioremediation technology. Diesel-contaminated soils were ozonated for 0-900 min. PH and microbial concentrations in the soils decreased with increased ozonation time. The greatest reduction of total PH (TPH, 47.6%) and aromatics (11.3%) was observed in 900-min ozonated soil. The number of total viable heterotrophic bacteria decreased by three orders of magnitude in the soil. Ozonated soils were incubated for 9 weeks for bioremediation. The number of microorganisms in the soils increased during the incubation period, as monitored by culture- and nonculture-based methods. The soils showed additional PH-removal during incubation, supporting the presence of PH-degraders in the soils. The highest removal (25.4%) of TPH was observed during the incubation of 180-min ozonated soil during the incubation while a negligible removal was shown in 900-min ozonated soil. This negligible removal could be explained by the existence of relatively few or undetected PH-degraders in 900-min ozonated soil. After a 9-week incubation of the ozonated soils, 180-min ozonated soil showed the lowest TPH concentration, suggesting that appropriate ozonation and indigenous microorganisms survived ozonation could enhance remediation of PH-contaminated soil. Microbial community composition in 9-week incubated soils revealed a slight difference between 900-min ozonated and unozonated soils, as analyzed by whole cell hybridization. Taken together, this study provided insight into indigenous microbial potential to degrade PH in ozonated soils.

Hydrocarbons↗
PubMed2005

Monitoring of hydrocarbon emissions in a petroleum refinery.

In a petroleum refinery the hydrocarbon emissions which are mostly fugitive in nature are emitted from process, offsites and periodic accidental releases such as: materials storage & handling, process, equipment leaks, solvent evaporation, combustion sources, waste treatment etc. In India, the monitoring of such emissions in a refinery are limited as also the standards are not set for its limit in ambient air. Hence there is an urgent need for generating a database for such emissions. Recently in India, MoEF/CPCB has set some guidelines under CREP rules for monitoring such emissions in a refinery. A detailed monitoring of the hydrocarbon emissions from different sources in a typical 10.5 MMTPA Indian refinery is undertaken during 1999-2001 and the results are presented. It is observed that the storage tank emissions alongwith process leaks form the major contributor towards fugitive hydrocarbon emissions.

Air Pollutants↗
PubMed1983

The carcinogenic effect of a series of petroleum-derived oils on the skin of mice.

Six groups of 30 Swiss mice were treated by application to the skin in the dorsolumbar region two times a week for 12 months of a "white oil" and five samples of petroleum oils derived from the same "crude" (Middle East), which were collected in the same refinery at different stages of "solvent treatment" and which form a homogeneous series with increasing concentrations of polyaromatic hydrocarbons (PAH). The macroscopic and histopathologic examination of the animals (skin and organs) up to 18 months shows the following effects with respect to the 60-mouse control group: --a marked irritating effect for the "aromatic extract," the "distillate," and a "mixture" of intermediary concentration between "distillate" and "raffinate," --a definite tumorigenic effect on the skin (papillomas, kerato-acanthomas, squamous cell carcinomas, and fibrosarcomas) of the "aromatic extract" and the "distillate." The biological answer is in significant association with the PAH concentration of the samples, which is estimated by different analytical methods: viscosity index, percentage of aromatic carbon, "total PAH" according to a gravimetric method, and benzo[a]pyrene concentration.

Animals↗