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Toxicological investigation of liquid petroleum gas explosion: human model for propane/ethyl mercaptan exposures.

Four individuals died as the result of a propane explosion. As with many propane explosions, the question was raised as to the adequacy of the product's odorization after the autopsy studies had been conducted. In most cases, this question leads to litigation. Ethyl mercaptan is a widely used odorant for propane and was used in this instance. Three of the four victims had blood available at autopsy for study. Quantitative analyses of the victims' blood, obtained during autopsy, were performed using gas chromatography/mass spectrometry, without subjecting the samples to hydrolysis. These analyses determined the relative amounts of propane and ethyl mercaptan in the blood to be 90, 63, and 175 mL/m3 headspace, and 0.36, 0.34, and 0.77 microgram/L blood, respectively. Since mercaptans have been reported in human blood as products of metabolism, modeling studies were conducted to establish the validity of the autopsy data and to develop an autopsy toxicology protocol for investigating explosion deaths. When subjects were not exposed to an atmosphere containing ethyl mercaptan, dimethylsulfide was the only mercaptan detectable in their blood without severe hydrolysis prior to analysis. Metabolic ethyl mercaptan is sufficiently bound to be undetectable by the methods used without hydrolysis. Human subjects were exposed to a flammable mixture of air and propane odorized with ethyl mercaptan. The analyses of the blood from these subjects produced results which were comparable with those for the explosion victims, establishing that the question of odorant adequacy can be addressed at the autopsy of propane explosion victims. It is extremely important that the pathologist and toxicologist investigating gas explosion deaths recognize the valuable evidence existing in the victim's blood.

Autopsy↗

Gas chromatographic determination of cholesterol in egg products.

A method has been developed for quantification of cholesterol in fresh egg yolks, spray-dried egg yolks, fresh whole eggs, and spray-dried whole eggs. The method uses saponification followed by petroleum ether extraction of cholesterol. Separation of organic and aqueous layers is enhanced by sodium chloride. Petroleum ether extracts are dried under nitrogen and redissolved in chloroform-methanol (2 + 1) for injection into a gas chromatograph. Cholesterol is separated and quantitated on a high temperature capillary column coated with 5% diphenyl and 95% dimethyl polysilicone crosslinked gum. The method was compared with the current AOAC method 17.017-17.022, and results indicated no significant difference (alpha = 0.05). However, the proposed method allowed separation and analysis of 16 samples in 7 h while the current AOAC method allowed separation and analysis of only 4 samples in 9 h.

Animals↗

Carcinogenicity of oil shale tars, some of their components, and commercial products.

Bioassays for carcinogenicity of various primary processing products (crude oils or tars) and commercial products obtained from Estorian oil shale have been carried out since 1951. The products (undiluted or diluted) were painted twice weekly 50 times on the interscapular area of the skin of random-bred or CC57Br mice. The products processed at high temperatures have a higher carcinogenic activity. Blends of products containing over 10% of high temperature crude oil (chamber furnace oil) have about the same carcinogenic activity as the latter. There is no strict correlation between the concentration of benzo(a)pyrene (BP) in oil shale products and their carcinogenic activity. Determination of BP in such products can serve as an approximate estimate of carcinogenic properties. The results of animal experiments with chromatographic fractions of the high temperature shale oil demonstrated the presence of compounds which lengthen the latency period of the carcinogenic effect of BP in the aromatic fraction of this oil as well as other carcinogens and compounds enhancing the activity of carcinogenic compounds. Under industrial conditions, contact of workers with carcinogenic shale oils can be reduced by means of coking the carcinogenic oils, which results in production of solid coke and of distillate which is recycled. Medical vaseline potentiates the carcinogenic action of BP and similar compounds. Dilution of shale oils with oils containing aliphatic hydrocarbons cannot be considered as diminution of the carcinogenic potency of these products.

Animals↗

Elevated blood lead levels among children living in a fishing community, Karachi, Pakistan.

Lead is a widespread environmental contaminant worldwide and is associated with adverse outcomes in children, including impaired neurobehavioral development and learning difficulties. A cross-sectional survey of 53 young children was conducted in a fishing village on an island adjacent to Karachi, Pakistan. Whole blood from each individual was tested for lead levels. Also tested were samples of cooked food, house dust, and drinking water from 36 households. Laboratory determinations were made by the Pakistan Council for Scientific and Industrial Research with quality control by the United States Centers for Disease Control and Prevention. Fifty-two subjects (98%) had blood lead levels above 10 microg/dl (mean 21.60 microg/dl), an internationally recognized threshold for potential neurotoxicity. The mean concentration was 3.90 microg/g in cooked food, 4.02 microg/l in drinking water, and 91.30 microg/g in house dust. These findings indicate possible major health concerns and suggest significant environmental contamination in this community as well as the need to identify locally relevant early childhood exposures.

Animals↗

Draught animals and welfare.

In fifty developing countries, which contain half of the total human population of the world, there is a heavy dependence on draught animals as an energy source. These animals are used for agriculture operations in 52% of cultivated areas of the world, as well as for hauling 25 million carts. This situation is likely to continue for at least another fifty years. The work performed annually by these draught animals would require 20 million tons of petroleum, valued at US$6 billion, if it were performed by motorized vehicles. The poor working conditions of these animals often adversely affect their productivity. The application of improved technology and better management (i.e. through better feed and health services, and improved design of agricultural implements and carts) could considerably improve the welfare of these animals. Improved systems would generate sufficient benefits for the economy to justify the required investment. High priority should therefore be given to draught animal power in the economic development agenda.

Agriculture↗

Verification of degradation of n-alkanes in diesel oil by Pseudomonas aeruginosa strain WatG in soil microcosms.

Degradation of n-alkanes in diesel oil by Pseudomonas aeruginosa strain WatG (WatG) was verified in soil microcosms. The total petroleum hydrocarbon (TPH) degradation level in two bioaugmentation samples was 51% and 46% for 1 week in unsterilized and sterilized soil microcosms, respectively. The TPH degradation in the biostimulation was of control level (15%). The TPH degradation in aeration-limited samples was clearly reduced when compared with that in aeration-unlimited ones under both sterilized and unsterilized conditions. Addition of WatG into soil microcosms was accompanied by dirhamnolipid production only in the presence of diesel oil. These findings suggest that degradation of n-alkanes in diesel oil in soil microcosms would be facilitated by bioaugmentation of WatG, with production of dirhamnolipid, and also by participation of biostimulated indigenous soil bacteria.

Alkanes↗

Photoenhanced toxicity of weathered oil to Mysidopsis bahia.

The toxicity of a water-accommodated fraction (WAF) prepared from weathered oil was assessed in a 7-day static renewal test with Mysidopsis bahia. Weathered oil was collected from the 5x monitoring well at the Guadalupe oil field. Solar ultraviolet and visible light intensities were measured in various habitats in the vicinity of the weathered oil sample collection site, and the resultant measurements were used to produce laboratory light treatments that were representative of the on-site quality and intensity of natural solar radiation. Each of five WAF dilutions and a control without WAF was tested under three different simulated solar radiation intensities. During the test, survival and growth of the mysids, irradiance, and total petroleum hydrocarbon (TPH) concentrations in the test treatments were measured. Significant increases (P</=0.05) in mortality occurred among mysids exposed to 0.57 and 1.30 mg TPH/l and the effects were potentiated as irradiance increased. Seven-day LC50 (0.92-0.42 mg TPH/l) and LC20 (0.58-0.15 mg TPH/l) values decreased as the simulated solar irradiance increased. Calculated EC20 and EC50 values for mysid growth indicate that surviving mysids exposed to 0.1-1.0 mg TPH/l would incur significant reductions (P</=0.05) in productivity (biomass). Results of the present study indicate that effects elicited through the interaction of WAF of weathered oil and solar radiation will substantially increase the toxicity of weathered oil. Further, the photomediated effects of petroleum compounds measured as TPH on mysid survival and growth demonstrate a need to consider the interactions of ultraviolet light and contaminant to avoid under estimating toxicity that might occur in the environment.

Journal Article↗

Subsoil TPH and other petroleum fractions-contamination levels in an oil storage and distribution station in north-central Mexico.

Many oil industry related sites have become contaminated due to the activities characteristic of this industry, such as oil exploration and production, refining, and petro-chemistry. In Mexico, reported hydrocarbon spills for the year 2000 amounted to 185203, equivalent to 6252 tons (PEMEX, 2000). The first step for the remediation of these polluted sites is to assess the size and intensity of the oil contamination affecting the subsoil and groundwater, followed by a health risk assessment to establish clean up levels. The aim of this work was to characterize the soil and water in a north-central Mexico Oil Storage and Distribution Station (ODSS), in terms of TPHs, gasoline and diesel fractions, BTEX, PAHs, MTBE, and some metals. Besides, measurements of the explosivity index along the ODSS were made and we describe and discuss the risk health assessment analysis performed at the ODSS, as well as the recommendations arising from it. Considering soils with TPH concentrations higher than 2000 mg kg(-1), the contaminated areas corresponding to the railway zone is about 12776.5 m2, to the south of the storage tanks is about 6558 m2, and to the south of the filling tanks is about 783 m2. Total area to be treated is about 20107 m2 (volume of 20107 m3), considering 1m depth.

Environmental Exposure↗

Determination of polybrominated biphenyl residues in dairy products.

A method for the determination of polybrominated biphenyls (PBBs) in dairy products is described. Fat is extracted from the products by the official AOAC method. The PBB residues are separated from the fatty material by gel permeation chromatography prior to gas-liquid chromatographic (GLC) quantitation. An additional cleanup using petroleum ether elution through a miniature Florisil column is necessary for thin layer chromatographic (TLC) confirmation. Recoveries of PBBs from samples fortified at levels from 0.1 to 0.5 ppm ranged from 94 to 104% with an average of 99%. GLC sensitivity permits the estimation of PBB residue levels as low as 0.007 ppm. Routine TLC confirmation is limited by sensitivity to greater than or equal to 0.2 ppm.

Biphenyl Compounds↗

A scheme for describing injury events.

OBJECTIVE: To develop a data collection system that provides a more comprehensive picture of the components of the preinjury and injury phases of injury events than is usually available in medical records. METHOD: Based on a scheme originally designed for study of occupational injuries among off-shore petroleum drilling workers, eight data areas were designated and lists of categories were developed to permit applicability to a general injury surveillance program. Medical records for 1600 injured patients treated at the Medical Center Hospital of Vermont were reviewed to determine current frequency of recording such information. RESULTS: A scheme for injury surveillance was designed that included location of the event, general and specific activities at time of injury, work relationship, nature of the event, animal or person contact, products or materials being used and those causing injury, and energy type and mechanism. CONCLUSION: An acceptable scheme has been developed that can be used for general surveillance, or modified to focus in greater detail on specific environments, products, or event types.

Abstracting and Indexing↗

Screening studies of yeasts capable of utilizing petroleum fractions.

In these studies, 23 yeast cultures belonging to 10 genera of ascosporogenous, ballistosporogenous, and asporogenous yeasts, were screened with respect to their abilities of hydrocarbon utilization in synthetic media. Thus, kerosene, n-hexadecane, and wax distillate were compared as sole carbon sources in 2% final concentration. Kerosene exhibited marked inhibition on the growth of the majority of the strains, whereas active growth was observed with Debaryomyces vanrijii and many species of the genus Candida in media with n-hexadecane or wax distillate as sole source of carbon. In addition, some cultures belonging to the genera Sporobolomyces, Hansenula, Cryptococcus, and Trigonopsis could utilize some of these substrates, but to a lesser extent. Highest yield of cells and protein was obtained with Candida lipolytica NRRL 1094 in n-hexadecane medium, supplied with 0.03% yeast extract and trace element solutions. The results are discussed with respect to the possibilities of using new yeast genera, with special reference to the genus Debaryomyces, in microbiol protein production.

Alkanes↗

Antioxidant activity of tomato products as studied by model reactions using xanthine oxidase, myeloperoxidase, and copper-induced lipid peroxidation.

The antioxidant content and activity of commercial tomato products differing in variety and processing were studied. Two procedures for extracting hydrophilic and lipophilic antioxidants, namely, two-step 0.1 M phosphate buffer (pH 3.0 and 7.4) extraction and tetrahydrofuran extraction followed by petroleum ether fractionation, were developed. Carotenoids (lycopene, beta-carotene, and lutein) and ascorbic acid were analyzed by HPLC with spectrophotometric and electrochemical detectors, respectively. Total phenolics were determined by using the Folin-Ciocalteu reagent. The antioxidant activity was studied by the following three model systems: (a) the xanthine oxidase (XOD)/xanthine system, which generates superoxide radical and hydrogen peroxide; (b) the myeloperoxidase (MPO)/NaCl/H(2)O(2) system, which produces hypochloric acid; and (c) the linoleic acid/CuSO(4) system, which promotes lipid peroxidation. Results showed that the hydrophilic and lipophilic fractions of all tomato products were able to affect model reactions, whatever reactive oxygen species and catalysts were used to drive oxidation. In the XOD/xanthine system both the hydrophilic and lipophilic fractions displayed an inhibitory activity. The hydrophilic fractions were more effective (I(50) ranging from 680 to 3200 microg, dry weight) than the lipophilic fractions (I(50) ranging from 4000 to 7750 microg, dry weight). In the MPO/NaCl/H(2)O(2) system the hydrophilic fractions inhibited oxidation (I(50) ranging from 2300 to 2900 microg, dry weight), whereas the lipophilic fractions had a lower inhibitory effect at the same concentration. Conversely, in the copper-catalyzed lipid peroxidation only the lipophilic fractions were effective (I(50) ranging from 1030 to 2100 microg, dry weight), whereas the hydrophilic fractions had a pro-oxidant effect in the same concentration range. The extent of inhibition varied according to the tomato sample in the superoxide and hydrogen peroxide generating system and in lipid peroxidation, but was substantially the same in the HClO generating system. Fresh tomato varieties differed considerably in the antioxidant activities of their hydrophilic and lipophilic fractions. Processed tomatoes showed a significantly lower antioxidant activity than fresh tomatoes in their hydrophilic fractions but had a high antioxidant activity in their lipophilic fractions. Because the oxidative reactions produced by the above-mentioned model systems are also involved in the pathogenesis of several chronic diseases, the antioxidant activity of tomato fractions might be related to their in vivo activity. Hence, these measurements may be used for optimizing tomato technologies.

Antioxidants↗

[The determination of diuron and chlortoluron residues in beef and beef products by high performance liquid chromatography].

Amethod for the determination of diuron and chlortoluron in beef and beef products with high performance liquid chromatography is described. The sample was extracted with a mixture of acetonitrile and methanol (50:50, V/V). After filtration, the filtrate was defatted with petroleum ether, then water was added and further extracted with chloroform. The chloroform collected was evaporated in a rotary evaporator(45 degrees C). The residue was dissolved in acetonitrile-methanol(50:50, V/V) mixture, poured into an Al2O3 column and eluted with the same mixture. The eluate was collected for HPLC analysis. The analytical column was Selectosil C18 (5 microns, 250 mm x 4.6 mm i.d.), mobile phase was methanol-water(60:40, V/V) and detection wavelength was UV-245 nm. The minimum amounts of detection were 0.4 ng for diuron and 0.5 ng for chlortoluron. Recoveries were 87.34%-87.64% for diuron and 88.78%-91.94% for chlortoluron.

Animals↗