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Development of toxicity criteria for petroleum hydrocarbon fractions in the Petroleum Hydrocarbon Criteria Working Group approach for risk-based management of total petroleum hydrocarbons in soil.

The Total Petroleum Hydrocarbon Criteria Working Croup (TPHCWG) was formed in 1993 based on the observation that widely different clean-up requirements were being used by states at sites that were contaminated with hydrocarbon materials such as fuels, lubricating oils, and crude oils. These requirements were usually presented as concentration of total petroleum hydrocarbon (TPH), and ranged from 10 to over 10,000 mg TPH/kg soil. Members of this multi-disciplinary group, consisting of representatives from industry, government and academia, jointly recognized that the numerical standard was not based on a scientific assessment of human health risk and established the following goal for the effort: To develop scientifically defensible information for establishing soil cleanup levels that are protective of human health at hydrocarbon contaminated sites. The approach developed by the TPHCWG for TPH hazard assessment consisted of dividing the petroleum hydrocarbon material into multichemical-containing fractions with similar fate and transport characteristics. These fractions were then assigned fate and transport properties (volatilization factor, soil leaching factor, etc.) and toxicity values (RfDs/RfCs) representative of the fraction. The actual site specific hazard assessment and derivation of cleanup levels is accomplished by analyzing sites to determine which fraction(s) is present and applying the appropriate fate, transport and toxicity factors. The method used by this group to determine TPH Faction specific toxicity criteria is a surrogate approach intended to supplement the indicator approach. Indicators are single, carcinogenic hydrocarbon compounds which are evaluated/regulated individually at either the federal or state level. The TPHCWG surrogate approach utilized all appropriate fraction specific toxicity data (single compound and mixture/product), minus the carcinogenic indicator compounds, to derive the fraction specific RfDs and RfCs. This hazard assessment method for petroleum contaminated sites would be utilized where indicator compounds are not present or are below/remediated to regulatory action levels. Derivation of the RfD/RfC values for the n-hexane containing aliphatic C5-C8 fraction is examined in detail to illustrate the underlying assumptions and use of existing data employed by the TPHCWG to develop fraction specific toxicity criteria. Toxicity RfDs/RfCs for all of the model fate and transport based fractions are also presented.

Animals↗

Biodegradation of crude petroleum and petroleum products by fungi isolated from two oil seeds (melon and soybean).

Crude petroleum oil degrading fungi were isolated from two oil seeds, Cucumeropsis mannii (melon) and Glycine max (soybean) seeds in the presence and absence of petroleum fumes. An assessment of the relative ability of each fungus to degrade crude petroleum, diesel and kerosene on minimum salt solution was done using change in optical density read on spectrophotometer. Twenty-one fungal species (14 genera) were isolated altogether during this experiment. These include eight species of Aspergillus; one species each of Botryodiplodia, Bipolaris, Cladosporium, Cunnighamella, Dreschlera, Fusarium, Helminthosporium, Macrophomina, Mucor, Paeciliomyces, Penicillium, Rhizopus and Talariomyces. It was evident that most of the fungi tested were able to biodegrade the crude petroleum oil, though at different rates. Bipolaris had a low rate of biodegradation of the petroleum oil of all the fungal species isolated Botryodiplodia theobromae had the highest degrading ability on the crude oil, while Aspergillus flavus had the least after 40 days of incubation. Aspergillus flavus had the highest ability to biodegrade diesel while A. niger had the least ability. In kerosene, Macrophomina phaseolina had the highest ability while A. niger had the least ability to biodegrade it. There was fluctuation in the growth pattern of the fungi in the petroleum oil medium. The implication of these are discussed.

Biodegradation, Environmental↗

[Petroleum substances--human health hazards. I. Classification of petroleum substances on the list of dangerous substances and assessment of existing hazards].

Complex products derived from petroleum are widely used as fuels, greases, solvents, and intermediates in many branches of industry. Petroleum exposure-related human health hazards, observed in occupationally exposed people and in the general population, are a serious sanitary problem. Complex and variable composition of individual petroleum products makes the actual assessment of human health hazards difficult. Potential hazards, and resulting classification of individual petroleum substance groups, are discussed in the presented work. This should prove to be helpful to work safety and hygiene services as well as to supervising institutions, mainly the sanitary inspection, in a proper assessment of the hazards, and consequently in taking appropriate preventive actions. In Part I., general issues concerning the hazard assessment and legal aspects of petroleum substances classification are presented. In Part. II., individual groups of petroleum substances are discussed with respect to health hazards, resulting from both physicochemical properties and toxicity, and their classification based on this analysis is suggested.

Abstracting and Indexing↗

[Study of the integral toxicity of aqueous media, polluted by petroleum and petroleum products using bacterial tests].

A biotest kit was used to assess the integral toxicity level of aquatic medium contamination with petroleum and petroleum-based products. The integral toxicity dynamics was also monitored during biodegradation of petroleum and petroleum-based products by an association of petroleum-degrading strains including Acinetobacter sp., Mycobacterium flavescens, and Rhodococcus sp. The following bacterial tests were used: the bioluminescence (BL) test based on Photobacterium leiognathi; electro-orientation (EO), optoosmotic (OO), and growth test; as well as the reducing activity (RA) test based on the Agrobacterium radiobacter culture. No significant increase in the integral toxicity level of aquatic medium was observed when diesel fuel and kerosene contamination had been subjected to biodegradation. Although express biotests (EO, OO, RA, and BL) detected a pronounced increase in the integral toxicity of aquatic medium, long-term growth biotest revealed no statistically significant increase in the toxicity level.

Acinetobacter↗

[Selection of microorganisms capable of degrading petroleum and petroleum products at decreased temperatures].

Of 150 cultures capable of degrading petroleum at +6 degrees C, 40 strains growing in the liquid mineral nutrient medium containing petroleum (2%) as a sole source of carbon were selected. Of them, 13 cultures displaying a petroleum degradation rate exceeding 25% were selected. Abilities of these cultures and their associations to utilize fuel oil and its components--oils and benzene resins--were studied. The culture exhibiting degradation rates of fuel oil, its oils, benzene resins, and petroleum amounting to 17, 26, 10, and 51%, respectively, was selected. This culture can be used for cleanup of petroleum pollution under cold climatic conditions.

Bacteria↗

Application of the Salmonella mutagenicity assay and determination of polycyclic aromatic hydrocarbons in workplaces exposed to petroleum pitch and petroleum coke.

Workplaces of an Italian carbon electrode factory, exposed to petroleum pitch and petroleum coke, were studied using a coupled chemical and biological approach to evaluate occupational mutagenic/carcinogenic hazards. Analytical procedures for the determination of polycyclic aromatic hydrocarbons (PAH) and Salmonella/microsome mutagenicity tests (with TA98 and TA100 strains) were performed on both industrial ingredients (pitch and coke) and airborne particulate matter of the working environment, after fractionating by sequential Soxhlet extractions with four organic solvents of increasing polarity (benzene, chloroform, methanol and acetone). The results showed: (a) the presence of extraordinarily high PAH (carcinogenic and non-carcinogenic) contents in the benzene extracts of petroleum pitch (3.6 wt% of total PAH) and of airborne particulate samples (up to 0.35 wt% of total PAH), in correlation with very high indirect (after metabolic activation) mutagenic responses of benzene extracts with strain TA98; (b) very high indirect mutagenic responses in the other extracts of the airborne particulate samples (especially with strain TA98); (c) the production during the processing at high temperatures of directly acting mutagens (without metabolic activation) which were absent in the starting materials and their release in the air of workplaces. The comparison of chemical analytical and mutagenicity data has proved to be an interesting approach for better defining the relative health hazards due to occupational exposure to potentially mutagenic/carcinogenic petroleum products.

Air Pollutants↗

Crude petroleum-oil biodegradation efficiency of Bacillus subtilis and Pseudomonas aeruginosa strains isolated from a petroleum-oil contaminated soil from North-East India.

The efficiency of Bacillus subtilis DM-04 and Pseudomonas aeruginosa M and NM strains isolated from a petroleum contaminated soil sample from North-East India was compared for the biodegradation of crude petroleum-oil hydrocarbons in soil and shake flask study. These bacterial strains could utilize crude petroleum-oil hydrocarbons as sole source of carbon and energy. Bioaugmentation of TPH contaminated microcosm with P. aeruginosa M and NM consortia and B. subtilis strain showed a significant reduction of TPH levels in treated soil as compared to control soil at the end of experiment (120 d). P. aeruginosa strains were more efficient than B. subtilis strain in reducing the TPH content from the medium. The plate count technique indicated expressive growth and biosurfactant production by exogenously seeded bacteria in crude petroleum-oil rich soil. The results showed that B. subtilis DM-04 and P. aeruginosa M and NM strains could be effective for in situ bioremediation.

Bacillus subtilis↗

Determination of total petroleum hydrocarbons and heavy metals in soils within the vicinity of facilities handling refined petroleum products in Lagos metropolis.

This article discusses the determination of total petroleum hydrocarbons (TPH) and heavy-metal contamination in soils within areas of refined petroleum products handling in Lagos metropolis. Soil samples were collected randomly from two petrol stations, two auto-mechanic workshops, and a National Electric Power Authority (NEPA) station. Control samples were taken from two low-density residential areas. TPH were estimated gravimetrically following standard methods of TPH analysis, while the heavy metals were determined by atomic absorption spectrophotometry. Sites studied had higher levels of TPH and heavy metals compared to the control samples. For TPH, the petrol stations have mean values of 399.83+/-106.19 and 450.83 +/- 90.58 microg/g, respectively; mechanic workshops, 362.60 +/- 185.84 and 428.55 +/- 119.00 microg/g, respectively; while the NEPA station has 356.20 +/- 210.30 microg/g compared to the control mean of 26.63 +/- 4.58. It revealed that the improper handling of refined petroleum products are potential sources of soil contamination in the sampled sites. This is indicated by the statistically significant levels of TPH and heavy metals observed between the control samples and those collected from the petroleum products handling sites. Bioremediation using microorganisms and plants is recommended.

Chemical Industry↗

Determining the temperature of petroleum formation from the kinetic properties of petroleum asphaltenes

Knowledge of the timing and location of petroleum formation is important in assessing the extent of available reserves in hydrocarbon-forming basins. This can be predicted from the thermal history of a basin and the kinetic parameters that characterize the thermal breakdown of kerogen in source rocks. At present, the kinetic parameters of kerogen breakdown are experimentally determined using immature rock samples from basin margins, but questions remain about the accuracy of this approach, especially when significant variability is observed within individual source units. Here we show that the kinetics of hydrocarbon generation from petroleum asphaltenes can be used to determine the temperature conditions of the actual source rock at the time of expulsion of the sampled petroleum. This relationship reflects the structural similarity of asphaltenes to the parent kerogen. We expect that our approach may be used as a comparatively simple alternative method for assessing the petroleum generation characteristics of a given basin, which will allow for better estimates of the available oil resources and the risks associated with their exploration.

Journal Article↗

[Plant biotests of soil and water, polluted with petroleum and petroleum products].

Reactiona of higher plants (mustard, oat, rye, salad, dill and barley) and microalgae (Euglena gracilis) on the contamination of soil and water with petroleum and oil products was studied. The germination of seeds was analyzed. The length of sprouts, dry biomass and length of plant roots, as well as the optical density of micro-algal broth culture were determined. Negative effects of soil and water contamination with petroleum and oil products on plant and microalgal parameters examined was shown. After biological destruction of contaminants by an association of destructor strains (Acinetobacter sp., Mycobacterium flavescens and Rhodoccocus sp.), the toxicity of contaminated mediums decreased. The data suggest that the integral toxicity of soil and water contaminated with petroleum and oil products and toxicity change during biodestruction of these pollutants can be analyzed by using plant test organisms.

Environmental Monitoring↗

[Keratinolytic fungi in an acidic petroleum waste lagoon at a petroleum refinery].

The incidence of keratinolytic fungi in an acidic petroleum waste lagoon (before bioremediation) at a petroleum refinery situated within a highly populated area was examined. High concentrations of petroleum hydrocarbons (aliphatics and PAHs) made the growth of keratinolytic fungi in clay and litter collected from the lagoon impossible. The natural self-purification process considerably decreased the hydrocarbon contamination, increased the pH and caused the abundant growth of Trichophyton ajelloi in organic soil that contained the root-adjacent material from the grass growing in green oases at the lagoon. Ecological and epidemiological aspects of the data were discussed.

Biodegradation, Environmental↗

An attempt to use selected strains of bacteria adapted to high concentrations of petroleum oil to increase the effective removal of petroleum products in excess activated sludge in laboratory conditions.

Forty two strains of bacteria were isolated from excess activated sludge from petroleum wastewater treatment plant. The strains were identified and classified to the following groups: Enterobacteriaceae (7 strains), Anitratum (3 strains), Pseudomonas (13 strains), Micrococcus (12 strains), Comamonas (2 strains), Xanthomonas (2 strains), Achromobacter (1 strain) and Vibrio-Aeromonas (1 strain). One of the isolates was found to be a yeast strain. Following preliminary selection ten strains, showing the best growth in medium with oil fraction as sole carbon source, were chosen for further studies. The selected strains belong to Pseudomonas (6 strains), Xanthomonas (2 strains), Micrococcus (1 strain) and Saccharomyces (1 strain). The strains were adapted to high oil concentration (500-2000 mg/L) and an attempt to use them to intensify removal of petroleum products from excess activated sludge was made. The sludge was inoculated with a mixture of the isolated strains. The experiment was carried out three times, each time with a fresh sample of the excess sludge. The obtained results show that the inoculation of activated sludge with the strains active against oil reduced the petroleum products content by 20% in 14 days. The greatest reduction of oil was observed in sludge with the lowest dry weight, that is with the greatest degree of hydration. The dry weight of the excess sludge did not significantly decrease during the course of the experiment, after having been inoculated with the mixture of strains.

Adaptation, Physiological↗

Utilization of petroleum hydrocarbons by Pseudomonas fluorescens isolated from a petroleum-contaminated soil.

A strain of Pseudomonas fluorescens, isolated from petroleum hydrocarbon-contaminated soil was examined for its ability to utilize a variety of hydrocarbon substrates. Surface tension measurements indicated the production of biosurfactant during the microbial degradation of hydrocarbon. The organism utilized both short and long chain n-alkanes. It emulsified a number of aliphatic and aromatic hydrocarbons.

Biodegradation, Environmental↗

Biochemical effects of petroleum exposure in hornyhead turbot (Pleuronichthys verticalis) exposed to a gradient of sediments collected from a natural petroleum seep in CA, USA.

Concentrations of serum/plasma estradiol, biliary fluorescent aromatic compounds (FACs), levels of hepatic CYP1A expression, and DNA damage were measured in sexually mature hornyhead turbot (Pleuronichthys verticalis) exposed in the laboratory for 7 days to a gradient of sediments collected from a natural petroleum seep in the Santa Barbara Channel. Coal oil point (COP) sediments were homogenized and divided into four treatments containing 0 (sediment from the Orange County Sanitation District's reference location), 33, 66, and 100% (COP) sediments. Sediment concentrations of 20 PAHs ranged from below the detection limit for the 0% COP sediment treatments to 105 microg/g in the 100% treatments with lower molecular weight compounds predominating. Concentrations of biliary FACs were not linear with COP treatment but levels of hepatic DNA damage increased linearly with increasing concentrations of high molecular weight PAHs. Hepatic CYP1A expression was elevated only in the 100% treatments. A reduction of plasma estradiol in male and female fish was observed in all COP exposures. These results demonstrate that acute sediment-only exposure of flatfish to naturally-derived PAHs elicits alterations in biochemical endpoints indicative of PAH bioavailability and adverse effects with different sensitivities.

Animals↗