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Identification of the methylhopanes in sediments and petroleum.

Three C31 methylhopanes have been prepared by partial synthesis from appropriate diplopterol precursors. 2 alpha-Methyldiplopterol (prepared from 22-hydroxyhopan-3-one), 2 beta-methyldiplopterol (isolated from Methylobacterium organophilum), and a mixture of diplopterol and 3 beta-methyldiplopterol (isolated from Methylococcus capsulatus) were each converted to the corresponding 17 alpha(H), 21 beta(H)-hopane. Comparison of these standards, using gas chromatography--mass spectrometry with multiple reaction monitoring, with the hopanoids from a variety of bitumens showed that all three C31 hydrocarbons may occur in sediments and that they are members of C28 and C30-C36 pseudohomologous series. 2 alpha-Methyl-17 alpha(H), 21 beta(H)-hopane, and 3 beta-methyl-17 alpha(H), 21 beta(H)-hopane are most commonly encountered in mature bitumens. 2 beta-Methyl-17 alpha(H), 21 beta(H)-hopane occurs in some immature bitumens, is much less abundant in others of intermediate maturity, and appears to be absent from mature samples. This, and the similarity of the distribution patterns of homohopane and methylhomohopane isomers, indicates that the common sedimentary methylhopanes are probably derived from biogenic precursors via diagenetic processes analogous to those which give rise to hopanes. In the case of the 2 alpha-methyl series, common to petroleum and mature sediments, derivation from the 2 beta-methyl hopanoids found in certain bacteria implies a maturity-related change in the configuration at C-2.

Bacteria↗

An overview of exposure to, and effects of, petroleum oil and organochlorine pollution in grey seals (Halichoerus grypus).

Most incidences involving oil pollution of grey seals (Halichoerus grypus) seem to have occurred at the breeding sites. Because of the high concentration of animals at this time, even small oil spills will pollute many animals. As a result of chronic low-level pollution from coastal ship traffic and discharges from offshore petroleum activity in the North Sea, approximately 50% of the grey seal pups at the largest breeding colony in Norway are polluted each year by oil. In this case, as well as in other similar cases of spills at breeding colonies, oil has produced little visible disturbance to the seals behaviour and there has been little mortality. The effects and mortality may, however, be more serious following a spill of crude oil, where animals may be affected by inhalation of toxic volatile compounds. High body burdens of PCBs and DDTs seem to have caused skull-bone lesions and occlusions of the uteri in grey seals in the Baltic Sea. Exposure to these persistent compounds has also been suspected to be the cause of reduction in the population of Baltic grey seals. There are indications that thyroid hormone and vitamin A status of grey seal pups are affected by the low exposure concentrations experienced at the Norwegian coast (approximately 1/20 of the concentration detected in grey seal pups from the Baltic Sea). This gives serious cause for concern about the effects that chronic low-level exposure to persistent organochlorine pollutants may have on individuals and on populations of grey seals.

Animals↗

Acute toxicity of petroleum- and shale-derived distillate fuel, marine: light microscopic, hematologic, and serum chemistry studies.

Rats were gavaged with 60, 48, 38, 30, or 24 ml/kg of either petroleum (P) or shale (S)-derived distillate fuel, marine (DFM). Surviving rats were killed 14 days after dosing. There was a slight difference in toxicity of the two fuels but neither fuel was very toxic. The LD50/14 was 43 ml/kg for P-DFM and 50 ml/kg for S-DFM. Lesions in rats that died indicated hepatic and renal toxicity. In another study, rats were gavaged with 24 ml/kg of either P- or S-DFM and killed at 1, 2, or 3 days after dosing. Prominent clinicopathologic findings included loss of body weight, hematologic evidence of dehydration, transient leukopenia, and serum chemistry and histopathologic alterations indicative of mild hepatic and renal toxicity.

Animals↗

Comparison of large unilamellar vesicles prepared by a petroleum ether vaporization method with multilamellar vesicles: ESR, diffusion and entrapment analyses.

Large unilamellar vesicles, prepared by a petroleum ether vaporization method, were compared to multilamellar vesicles with respect to a number of physical and functional properties. Rotational correlation time approximations, derived from ESR spectra of both hydrophilic (3-doxyl cholestane) and hydrophobic (3-doxyl androstanol) steroid spin probes, indicated similar molecular packing of lipids in bilayers of multilamellar and large unilamellar liposomes. Light scattering measurements demonstrated a reduction in apparent absorbance of large unilamellar vesicles, suggesting loss of multilamellar structure which was confirmed by electron microscopy. Furthermore, large unilamellar vesicles exhibited enhanced passive diffusion rates of small solutes, releasing a greater percentage of their contents within 90 min than multilamellar vesicles, and reflecting the less restricted diffusion of a unilamellar system. The volume trapping capacity of large unilamellar vesicles far exceeded that of multilamellar liposomes, except in the presence of a trapped protein, soy bean trypsin inhibitor, which reduced the volume of the aqueous compartments of large unilamellar vesicles. Finally, measurement of vesicle diameters from electron micrographs of large unilamellar vesicles showed a vesicle size distribution predominantly in the range of 0.1--0.4 micron with a mean diameter of 0.21 micron.

Chromates↗

Effects of petroleum refinery wastewater exposure on gill ATPase and selected blood parameters in the Pacific staghorn sculpin (leptocottus armatus).

1. The effects of in vivo exposure to various concentrations of petroleum refinery wastewater on gill ATPase, plasma protein, plasma osmolarity, and hematocrit were measured in the euryhaline fish, Leptocottus armatus. 2. The extent of the reduction in Na,K-ATPase activity resulting from the exposure to the two refineries wastewaters may be related to wastewater chemical composition. 3. Changes in the blood chemistry parameters did not follow a consistent or easily explainable pattern.

Adenosine Triphosphatases↗

Benzene exposure in a Japanese petroleum refinery.

Time-weighted average (TWA) intensity of exposure of workers to benzene vapor during a shift was monitored by diffusive sampling technique in a Japanese petroleum refinery. The subjects monitored (83 in total) included refinery operators, laboratory personnel and tanker-loading workers. The results showed that the time-weighted average exposures are well below 1 ppm in most cases. The highest exposure was recorded in 1 case involved in bulk loading of tanker ships, in which exposure of over 1 ppm might take place depending on operational conditions. The observation was generally in agreement with levels previously reported.

Benzene↗

Antiinflammatory effect of petroleum ether extract of leaves of Litchi chinensis Gaertn. (Sapindaceae).

Pharmacological studies were conducted with the petroleum ether extract of leaves of the plant Litchi chinensis Gaertn. (Sapindaceae) on experimental animals. The extract was found to possess antiinflammatory, analgesic and antipyretic activity. Acute toxicity studies revealed that the extract, up to a dose of 1 g/kg intraperitoneally, was nontoxic. The extract did not inhibit arachidonic acid-induced paw inflammation thus indicating that it may inhibit the cyclooxygenase pathway of arachidonic acid metabolism. The extract also enhanced peritoneal cell exudate along with macrophage significantly.

Analgesics↗

Seasonal changes in aryl hydrocarbon hydroxylase activity of a marine fish Tautogolabrus adspersus (Walbaum) with and without petroleum exposure.

Organ indices and hepatic aryl hydrocarbon hydroxylase (AHH) were measured periodically from before gonad maturation to post-spawning on cunners (Tautogolabrus adspersus) (a) maintained in captivity, (b) maintained in captivity and treated continuously with 0.3-0.8 ppm crude oil accommodated in seawater and (c) sampled directly from the field population. Total (AHH) activity in field-sampled fish (normalized to 100 g body weight) decreased 166-fold in males and 155-fold in females from maximal values before gonad maturation to minimum values two weeks following spawning. Inducibility of AHH was suppressed during the period of minimum AHH activity but returned about 3 weeks after the end of spawning. Maximal mean AHH induction by exposure to crude oil observed during the study was 5.8-fold in males and 7.5-fold in females. Captive fish had smaller gonads in both sexes and reduced liver size in females relative to fish caught immediately before sampling. Petroleum exposure further inhibited the normal increase in gonad size in both sexes relative to an unexposed fish in addition to the inhibition due to captivity alone. Captive fish did not feed well and decreased in condition index; the oil exposed group was more affected than the control captive group.

Animals↗

Respiration of mitochondria from the gonads of the sea urchin, Strongylocentrotus droebachiensis: the effects of petroleum fractions on oxygen consumption.

The respiration of mitochondria from gonads of Strongylocentrotus droebachiensis has been studied in the presence of 2-oxoglutarate, glutamate and succinate. The rate of oxygen consumption increased with temperature between 4 and 20 degrees C. Removal of gametes from ripe gonads was necessary to obtain good respiring mitochondria. Equilibration of respiration media with various petroleum fractions reduced the rate of oxygen consumption and the coupling of O2 consumption to ADP utilization. Lighter fractions (leaded gasolines, unleaded gasoline and related fractions) were more deleterious than medium fractions (kerosene and fuel oil). Heavy fraction (bunker C, vacuum bottoms and crude oil) were least deleterious. Tetraethyl lead contributed to the toxicity of the leaded fractions.

Acclimatization↗

An evaluation of the environmental implications of petroleum refinery emissions by multielemental neutron activation analysis of rumen fluid ash of buffaloes.

In order to study environmental pollution in and around a petroleum refinery complex, a multielemental instrumental neutron activation analysis (INAA) method was used to assay concentrations of As, Ba, Br, Cl, Co, Cr, Cs, Cu, Fe, Hg, La, Mn, Mo, K, Na, P, Sc, Rb, Se, Sr, W and Zn in the rumen fluid ash samples of buffaloes from the vicinity of the refinery. Corresponding samples from a control area 300 km away from the refinery were analysed. Standard Reference Materials, Bovine liver (SRM 1577a), Oyster tissue (SRM 1566a) and Animal bone (CRM H-5) were also analysed for quality control. Samples were irradiated with thermal neutrons at 10(12)-10(13) n cm-2 s-1 and counted by high-resolution gamma spectrometry. Mean elemental concentrations of As, Ba, Br, Cr, Hg and Fe were found to be enhanced, whereas those of Na, K, Cl, Cu, Mn and P were depleted in samples from the vicinity of the refinery complex compared to controls. The environmental implications of anomalous elemental concentrations are discussed.

Animals↗

Isolation and characterization of biosurfactant/bioemulsifier-producing bacteria from petroleum contaminated sites.

Biosurfactant-producing bacteria were isolated from terrestrial and marine samples collected in areas contaminated with crude oil or its byproducts. Isolates were screened for biosurfactant/bioemulsifier production in different carbon sources (glucose, fructose, sucrose and kerosene) using the qualitative drop-collapse test. Glucose produced the highest number of positive results (17 of 185 isolates). All 17 isolates produced emulsions with kerosene and 12 exhibited high emulsion-stabilizing capacity, maintaining 50% of the original emulsion volume for 48 h. Eight of the 17 isolates reduced the growth medium surface tension below 40 mN m(-1) with 5 exhibiting this capacity in cell-free filtrates. Onset of biosurfactant production differed among the isolates, with some initiating synthesis during the exponential growth phase and others after the stationary phase was reached. Increasing temperature from 25 to 35 degrees C accelerated onset of biosurfactant production in only two isolates while pH (6.5-7.6) had no effect in any isolate tested. Isolation from petroleum contaminated sites using the screening protocol presented proved to be a rapid and effective manner to identify bacterial isolates with potential industrial applications.

Bacteria↗

Petroleum hydrocarbons and polycyclic aromatic hydrocarbons in the surficial sediments of Xiamen Harbour and Yuan Dan Lake, China.

Surficial sediments were sampled from nine stations in Xiamen Harbour and two stations in Yuan Dan Lake during April 2002. Sediment samples were extracted by organic solvents, separated by silica gel column chromatography and analyzed by gas chromatography-mass selective detector (GC-MSD). Selected ion monitoring was at M/Z=57 for petroleum hydrocarbons (PHCs) and individual M/Zs for each of the 15 typical polycyclic aromatic hydrocarbons (PAHs) and nine alkylated PAHs. The results showed that concentrations of PHCs and total PAHs in the sediments of Yuan Dan Lake were 1397 microg g(-1) (dry weight, dw) and 1377 ng g(-1) (dw), respectively. The ranges for PHCs and total PAHs in the sediments from Xiamen Harbour were 133-943 microg g(-1) (dw) and 98-309 ng g(-1) (dw), respectively. Shipping activities, industrial wastewater discharges, fuel oil spillage from ships and vehicles were the main sources of PHCs and PAHs in the Harbour. In addition, the widespread use of coal for industrial processes and domestic consumption accounted for the second largest source of PAHs in the sediments, while atmospheric transport and deposition of PAHs are also important.

China↗

Effects of nutrient and temperature on degradation of petroleum hydrocarbons in contaminated sub-Antarctic soil.

Mesocosm studies using sub-Antarctic soil artificially contaminated with diesel or crude oil were conducted in Kerguelen Archipelago (49 degrees 21' S, 70 degrees 13' E) in an attempt to evaluate the potential of a bioremediation approach in high latitude environments. All mesocosms were sampled on a regular basis over six months period. Soils responded positively to temperature increase from 4 degrees C to 20 degrees C, and to the addition of a commercial oleophilic fertilizer containing N and P. Both factors increased the hydrocarbon-degrading microbial abundance and total petroleum hydrocarbons (TPH) degradation. In general, alkanes were faster degraded than polyaromatic hydrocarbons (PAHs). After 180 days, total alkane losses of both oils reached 77-95% whereas total PAHs never exceeded 80% with optimal conditions at 10 degrees C and fertilizer added. Detailed analysis of naphthalenes, dibenzothiophenes, phenanthrenes, and pyrenes showed a clear decrease of their degradation rate as a function of the size of the PAH molecules. During the experiment there was only a slight decrease in the toxicity, whereas the concentration of TPH decreased significantly during the same time. The most significant reduction in toxicity occurred at 4 degrees C. Therefore, bioremediation of hydrocarbon-contaminated sub-Antarctic soil appears to be feasible, and various engineering strategies, such as heating or amending the soil can accelerate hydrocarbon degradation. However, the residual toxicity of contaminated soil remained drastically high before the desired cleanup is complete and it can represent a limiting factor in the bioremediation of sub-Antarctic soil.

Aliivibrio fischeri↗

Ion-exchange resins in the isolation of nitrogen compounds from petroleum residues.

In this work, preparative liquid chromatography was used for the separation of the nitrogen compounds in a sample of heavy gas oil from a Brazilian petroleum. Initially it took place a pre-fractionation by neutral aluminium oxide and the compounds were separated in different classes such as: hydrocarbons, resins (compounds of low molecular mass and intermediate polarity) and asphalthenes (polar compounds with high molecular mass). A comparison of the fraction of resins was performed by re-fractionating with modified silica (with potassium hydroxide and hydrochloric acid), or with ion exchange resins (Amberlyst A-27 and A-15), being isolated the basic and neutral compounds, that were analyzed by GC-MS in the scan and selected ion monitoring modes. Quinolines, benzoquinolines, tetrahydroquinolines were found in the basic fraction and carbazoles derivatives were found in the neutral fraction.

Gas Chromatography-Mass Spectrometry↗

Peroxidation in muscle and liver tissues from fish in a contaminated river due to a petroleum refinery industry.

In this study, we aimed to investigate the possible effects of the wastewater water contamination of a petroleum industry on the oxidant/antioxidant status of muscle and liver tissues from fish in the Kizilirmak River, Kirikkale, Turkey. The antioxidant/oxidant parameters were analyzed in the muscle and liver tissues from fish in 10 km of the river above and below the industry. Malondialdehyde (MDA) and susceptibility to oxidation (SO) values were measured in the liver and muscle tissues as indexes of oxidation, and antioxidant potential (AOP), superoxide dismutase (SOD), glutathion peroxidase (GSH-Px), and catalase(CAT) activities were measured as indexes of antioxidant status. There was significant oxidation in the muscle tissue of the fish obtained in the river downstream of the industry compared to those obtained upstream of the industry. Although there were no meaningful differences between the SOD and GSH-Px activities, the AOP value and CAT activities were found to be reduced in the muscle tissues from the fish obtained downstream. In the liver tissues, the SOD and GSH-Px activities were found to be increased in the fish obtained downstream but no differences were observed in the MDA, SO, AOP, and CAT values. Our results suggest that some contaminants from the petrochemical industry cause oxidation in fish muscle tissues by impairing the antioxidant system. However, because no peroxidation was observed in the liver tissue from the downstream fish, it is possible that liver tissues have a stronger antioxidant capacity than muscle.

Animals↗

Bioremediation of petroleum hydrocarbons in contaminated soils: comparison of biosolids addition, carbon supplementation, and monitored natural attenuation.

Two methods of biostimulation were compared in a laboratory incubation study with monitored natural attenuation (MNA) for total petroleum hydrocarbon (TPH) degradation in diesel-contaminated Tarpley clay soil with low carbon content. One method utilized rapid-release inorganic fertilizers rich in N and P, and the other used sterilized, slow-release biosolids, which added C in addition to N and P. After 8 weeks of incubation, both biostimulation methods degraded approximately 96% of TPH compared to MNA, which degraded 93.8%. However, in the first week of incubation, biosolids-amended soils showed a linear two orders of magnitude increase in microbial population compared to MNA, whereas, in the fertilizer-amended soils, only a one order of magnitude increase was noted. In the following weeks, microbial population in the fertilizer-amended soils dropped appreciably, suggesting a toxic effect owing to fertilizer-induced acidity and/or NH(3) overdosing. Results suggest that biosolids addition is a more effective soil amendment method for biostimulation than the commonly practiced inorganic fertilizer application, because of the abilities of biosolids to supplement carbon. No statistically significant difference was observed between the biostimulation methods and MNA, suggesting that MNA can be a viable remediation strategy in certain soils with high native microbial population.

Bacteria↗

Reflectance properties and physiological responses of Salicornia virginica to heavy metal and petroleum contamination.

Wetland ecosystems of California are located in highly populated areas and subject to high levels of contamination. Monitoring of wetlands to assess degrees of pollution damage requires periodic retrieval of information over large areas, which can be effectively accomplished by rapidly evolving remote sensing technologies. The biophysical principles of remote sensing of vegetation under stress need to be understood in order to correctly interpret the information obtained at the scale of canopies. To determine the potential to remotely characterize and monitor pollution, plants of Salicornia virginica, a major component of wetland communities in California, were treated with two metals and two crude oil types to study their sensitivity to pollutants and how this impacted their reflectance characteristics. Several growth and physiological parameters, as well as shoot reflectance were measured and correlated with symptoms and contamination levels. Significant differences between treatments were found in at least some of the measured parameters in all pollutants. Reflectance was sensitive to early stress levels only for cadmium and the lightweight petroleum. Pollutants that differ in their way of action also had different plant reflectance signatures. The high degree of correlation between reflectance features and stress indicators highlights the potential of using remote sensing to assess the type and degree of pollution damage.

Automation↗

Lysosomal responses as a diagnostic tool for the detection of chronic petroleum pollution at Todos os Santos Bay, Brazil.

Coastal marine environments, especially semienclosed systems such as bays, are under unrelenting stress caused by urban and industrial development. Biomonitoring plays a vital role in strategies to identify, assess, and control stressors. However, due to the magnitude of the challenge there is a demand for new and innovative approaches to provide timely and accessible information to environmental managers and policy makers. The present work aimed to assess hydrocarbon levels in sediments from petroleum-related industrial areas at Todos os Santos Bay (Brazil) and associate them to toxicity-induced responses (neutral red retention (NRR) assay) by the burrowing clam Anomalocardia brasiliana. Surface sediments collected during the dry and rainy seasons were analyzed for aliphatic and aromatic hydrocarbons. At the control site, hydrocarbon levels were low and mainly biogenic. The aliphatic hydrocarbon ("total unresolved complex mixture," alkanes, and isoprenoids) concentrations indicated a chronic situation with very little "fresh" oil contamination at the oil-related sites. The polycyclic aromatic hydrocarbons indicated sites moderately contaminated by chronic oil and some pyrolytic input. The effects of those contaminants were assessed by the lysosomal NRR assay applied to A. brasiliana hemocytes. Sediment toxicity at the oil-related sites was evidenced by the lowered capacity of the lysosomes to retain the neutral red dye compared to results from the control site. This research indicates that the NRR assay is a useful and efficient screening technique able to discriminate polluted from clean sites.

Animals↗