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Carcinogenic potential of hydrotreated petroleum aromatic extracts.

Five experimental petroleum extracts were produced from luboil distillates derived from Middle East paraffinic crude by solvent extraction and severe hydrotreatment. The polycyclic aromatic content (PCA) of the extracts was determined by dimethyl sulphoxide extraction and ranged from 3.7-9.2% w/w. The five extracts were evaluated for their potential to induce cutaneous and systemic neoplasia in female mice derived from Carworth Farm No 1 strain (CF1). The test substances were applied undiluted (0.2 ml per application) to the shorn dorsal skin twice weekly for up to 78 weeks, with 48 mice in each treatment group and 96 in the untreated control group; two further groups, each of 48 mice, were similarly treated either with a non-hydrotreated commercial aromatic extract (PCA content, 19.7% w/v) or with a low dose of benzo(a)pyrene (12.5 micrograms/ml acetone). The mice were housed individually in polypropylene cages in specified pathogen free conditions. The incidence of cutaneous and systemic tumours was determined from histological analysis of haematoxylin and eosin stained tissue sections. The results were correlated with the PCA content of the extracts and compared with those from female mice exposed to a non-hydrotreated commercial aromatic extract. Four of the hydrotreated extracts were carcinogenic for murine skin; the two products with the lower PCA contents were less carcinogenic than the products with the higher PCA contents and all were less carcinogenic than the commercial extract. One extract with the lowest PCA content was non-carcinogenic. Thus refining by severe hydrotreatment was an effective method of reducing the carcinogenic potential of petroleum aromatic extracts. Although other physicochemical properties may influence the biological activity of oil products, the PCA content determined by dimethyl sulphoxide extraction may be a useful indicator of the potential of oil products to induce cutaneous tumours in experimental animals. There was no evidence that the commercial or hydrotreated extracts increased the incidence of systemic neoplasms when applied twice weekly to the dorsal skin.

Animals↗

Benzene exposure in the United States 1978-1983: an overview.

Due to the interest in reducing the benzene exposure limit from 10 to 1 ppm, the benzene exposure data collected since 1977 were compiled and evaluated. Some 38,000 data points representing either time-weighted air samples or persons exposed were collected from five industries which produce and/or use benzene and two government organizations. Of the reported data, 87% represented exposure levels of 1.0 ppm or less. Petroleum and chemical operations where elevated exposure levels were reported included petrochemical and bulk loading operations. Benzol and by-product plants in the iron and steel industry showed similar elevated results.

Air Pollutants, Occupational↗

A simple graphical method for measuring inherent safety.

Inherently safer design (ISD) concepts have been with us for over two decades since their elaboration by Kletz [Chem. Ind. 9 (1978) 124]. Interest has really taken off globally since the early nineties after several major mishaps occurred during the eighties (Bhopal, Mexico city, Piper-alfa, Philips Petroleum, to name a few). Academic and industrial research personnel have been actively involved into devising inherently safer ways of production. The regulatory bodies have also shown deep interest since ISD makes the production safer and hence their tasks easier. Research funding has also been forthcoming for new developments as well as for demonstration projects.A natural question that arises is as to how to measure ISD characteristics of a process? Several researchers have worked on this [Trans. IChemE, Process Safety Environ. Protect. B 71 (4) (1993) 252; Inherent safety in process plant design, Ph.D. Thesis, VTT Publication Number 384, Helsinki University of Technology, Espoo, Finland, 1999; Proceedings of the Mary Kay O'Connor Process Safety Center Symposium, 2001, p. 509]. Many of the proposed methods are very elegant, yet too involved for easy adoption by the industry which is scared of yet another safety analysis regime. In a recent survey [Trans. IChemE, Process Safety Environ. Prog. B 80 (2002) 115], companies desired a rather simple method to measure ISD. Simplification is also an important characteristic of ISD. It is therefore desirable to have a simple ISD measurement procedure. The ISD measurement procedure proposed in this paper can be used to differentiate between two or more processes for the same end product. The salient steps are: Consider each of the important parameters affecting the safety (e.g., temperature, pressure, toxicity, flammability, etc.) and the range of possible values these parameters can have for all the process routes under consideration for an end product. Plot these values for each step in each process route and compare. No addition of values for disparate hazards (temperature, pressure, inventory, toxicity, flammability, etc.) is being suggested to derive an overall ISD index value since that conceals the effects of different parameters. Further, addition of numbers with different units ( degrees C for temperature, atm/bar for pressure, t for inventory, etc.) is inappropriate in scientific sense. The proposed approach has a major advantage of expanding consideration in future to incorporate economic, regulatory, pollution control and worker health aspects, as well as factors such as the experience one has or 'the comfort level' one feels with each of the processes under consideration. Additionally, it would also guide the designers and decision makers into affecting specific changes in the processes to reduce the unsafe features. We demonstrate our simple approach by using the example of six routes to make methyl methacrylate as documented by Edwards and Lawrence [Trans. IChemE, Process Safety Environ. Protect. B 71 (4) (1993) 252; Quantifying inherent safety of chemical process routes, Ph.D. Thesis, Loughborough University, Loughborough, UK, 1996] and show that the decision could well have been different if addition of disparate hazards had not been done.

Hazardous Substances↗

Biodistribution of a novel antiestrogen (Analog II) in the mouse and rat.

The biodistribution of a novel antiestrogen Analog II was determined in the mouse and rat. The tritiated product, [3H]-Analog II was prepared by New England Nuclear and was purified by preparative chromatography using silica gel and petroleum ether/methylene chloride (80:20). The fat tissue had the highest uptake due to the hydrophobic nature of Analog II. The second highest uptake was in the mouse uterine tissue which was greater than that observed in the rat. The differences in biodistribution between the mouse and rat may partially explain the differences in biological activity of Analog II previously observed in these two animal species.

Adipose Tissue↗

[Analytical comparison of "paraffin" labeled highly toxic lamp oils with paraffinum perliquidum (DAB 10)].

Coloured and odoriferous lamp oils available as household articles repeatedly lead to ingestion intoxications in children in some cases resulting in a bad course. Labels on containers of lamp oils are misleading, e.g. "pure liquid paraffin" or "without noxious substances", causing considerable misconceptions during therapeutic use by treating doctors. Analyses of four arbitrary chosen lamp oils by GC and GC/MS show that the main components (approx. 98%) are the unbranched saturated hydrocarbons n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane. Tests according to the German Pharmacopoeia 10th ed. prove also that "paraffin"-labelled products are not at all identical with medical/pharmaceutical paraffinum perliquidum or liquidum. Lamp oils are low viscous and high toxic petroleum distillates and should be labelled "toxic to humans".

Fuel Oils↗

Links between geographic location, environmental factors, and microbial community composition in sediments of the Eastern Mediterranean Sea.

The bacterial community composition of marine surface sediments originating from various regions of the Eastern Mediterranean Sea (12 sampling sites) was compared by parallel use of three fingerprinting methods: analysis of 16S rRNA gene fragment heterogeneity by denaturing gradient electrophoresis (DGGE), terminal restriction fragment length polymorphism (T-RFLP), and analysis of phospholipid-linked fatty acid composition (PLFA). Sampling sites were located at variable depths (30-2860 m; water column depth above the sediments) and the sediments differed greatly also in their degree of petroleum contamination (0.4-18 microg g(-1)), organic carbon (0.38-1.5%), and chlorophyll a content (0.01-7.7 microg g(-1)). Despite a high degree of correlation between the three different community fingerprint methods, some major differences were observed. DGGE banding patterns showed a significant separation of sediment communities from the northern, more productive waters of the Thermaikos Gulf and the oligotrophic waters of the Cretan, S. Ionian, and Levantine Sea. T-RFLP analysis clearly separated the communities of deep sediments (>1494 m depth) from their shallow (<617 m) counterparts. PLFA analysis grouped a shallow station from the productive waters of the north with the deep oligotrophic sediments from the Ionian and Levantine Sea, with low concentrations of PLFAs, and hence low microbial biomass, as the common denominator. The degree of petroleum contamination was not significantly correlated to the apparent composition of the microbial communities for any of the three methods, whereas organic carbon content and sediment chlorophyll a were important in this regard.

Bacteria↗

Ethanol can contribute to energy and environmental goals.

To study the potential effects of increased biofuel use, we evaluated six representative analyses of fuel ethanol. Studies that reported negative net energy incorrectly ignored coproducts and used some obsolete data. All studies indicated that current corn ethanol technologies are much less petroleum-intensive than gasoline but have greenhouse gas emissions similar to those of gasoline. However, many important environmental effects of biofuel production are poorly understood. New metrics that measure specific resource inputs are developed, but further research into environmental metrics is needed. Nonetheless, it is already clear that large-scale use of ethanol for fuel will almost certainly require cellulosic technology.

Biotechnology↗

Response of microbial populations in arctic tundra soils to crude oil.

Experimental crude oil spillages of 5 and 12 litre/m2 were established on the four major topographically distinguished soils of Arctic coastal polygonized tundra. The response of microbial populations to contaminating oil was found to depend on soil type and depth. Increases in numbers of heterotrophs were initially restricted to the top 2 cm of the soils. Increase in oil-degrading populations were found in oil-treated soils. Increases in microbial populations in subsurface soils paralleled downward migration of the oil. Some of the observed population increases probably resulted from input of plant residues and products from oil biodegradation.

Arctic Regions↗

Riboflavin formation by mould fungi cultivated on hydrocarbon-containing media.

The potentiality of some mould fungi, isolated from petroleum sludge to produce riboflavin when grown on hydrocarbon-containing media was tested. Aspergillus terreus was found to be distinguished by its capacity to produce riboflavin when cultivated on the different culture media tested. It was able to grow more luxuriantly and produce good riboflavin output on solar-containing medium. A solar concentration of 5% v/v favoured high riboflavin productivity. The maximal vitamin B2 yields were achieved after 20 days incubation at 30 degrees C. An initial pH value of 5.5-6.0 was found to be the optimum for growth of A. terreus and for riboflavin production.

Aspergillus↗

Toxicoses related to the petroleum industry.

During 1977, 4,976 oil and gas wells were drilled in Oklahoma to an average depth of 4,892 feet. There were 2,253 successful oil wells and 1092 successful gas wells (26). The Oklahoma Animal Disease Diagnostic Laboratory investigated several cases where livestock in close proximity to drilling sites became ill or die. The case histories emphasize the need for a careful and complete diagnostic work-up. The identification and quantification of petroleum hydrocarbons, toxic chemicals and heavy metals in intestinal contents and tissues are diagnostically significant. The most difficult cases involve chronically ill and poor-doing animals following exposure to oil field wastes. The potential for litigation exists whenever cattle in close proximity to drilling and production sites become ill or die. Many of these cases could be prevented if livestock were prevented access to such sites by fencing or other means. The circumstantial evidence in many cases suggests the need for additional research on the toxicity of petroleum hydrocarbons, drilling muds and other oil dield wastes. Improves diagnostic methods should benefit both the livestock and oil industries.

Animals↗

Identification of conjugated linoleic acid isomers in cheese by gas chromatography, silver ion high performance liquid chromatography and mass spectral reconstructed ion profiles. Comparison of chromatographic elution sequences.

Commercial cheese products were analyzed for their composition and content of conjugated linoleic acid (CLA) isomers. The total lipids were extracted from cheese using petroleum ether/diethyl ether and methylated using NaOCH3. The fatty acid methyl esters (FAME) were separated by gas chromatography (GC), using a 100-m polar capillary column, into nine minor peaks besides that of the major rumenic acid, 9c,11t-octadecadienoic acid (18:2), and were attributed to 19 CLA isomers. By using silver ion-high performance liquid chromatography (Ag+ -HPLC), CLA isomers were resolved into seven trans,trans (5-9%), three cis/trans (10-13%), and five cis,cis (<1%) peaks, totaling 15, in addition to that of the 9c,11t-18:2 (78-84%). The FAME of total cheese lipids were fractionated by semipreparative Ag+ -HPLC and converted to their 4,4-dimethyloxazoline derivatives after hydrolysis to free fatty acids. The geometrical configuration of the CLA isomers was confirmed by GC-direct deposition-Fourier transform infrared, and their double bond positions were established by GC-electron ionization mass spectrometry. Reconstructed mass spectral ion profiles of the m + 2 allylic ion and the m + 3 ion (where m is the position of the second double bond in the parent conjugated fatty acid) were used to identify the minor CLA isomers in cheese. Cheese contained 7t,9c-18:2 and the previously unreported 11t,13c-18:2 and 12c,14t-18:2, and their trans,trans and cis,cis geometric isomers. Minor amounts of 8,10-, and 10,12-18:2 were also found. The predicted elution orders of the different CLA isomers on long polar capillary GC and Ag+ -HPLC columns are also presented.

Cheese↗

Systemic toxicity following gasoline aspiration.

The major cause of mortality and morbidity associated with the ingestion of aliphatic hydrocarbon products is related to pulmonary aspiration. Despite the high frequency of the ingestions, there is little documentation of nonpulmonary toxic effects of petroleum distillates. Two cases of gasoline aspiration/ingestion that resulted in probable intravascular hemolysis are reported. In one of these cases, the patient also manifested a consumptive coagulopathy, acute renal failure and elevation of transaminase enzymes. With modern intensive pulmonary care, the outlook for patients with petroleum distillate aspiration is good, but any documented extrapulmonary manifestations of this condition may be important in the overall management of these patients.

Child, Preschool↗

Effects of alkylphenols on redox status in first spawning Atlantic cod (Gadus morhua).

Offshore oil production releases large amounts of lipophilic compounds in produced water and into the ocean. The discharge of produced water from the Norwegian petroleum sector has increased from 26 million m3 in 1993 to 120 million m3 in 2001, and it continues to increase. Produced water contains significant amounts of alkylphenols, which have been reported to be estrogenic, causing endocrine disruption in fish. In year 2000, approximately 44 tons of alkylphenols were released on the Norwegian continental shelf in connection with discharge of produced water. Except from being estrogenic, relatively little is known about the effects of alkylphenols when released in the marine environment. Our objective was to study how alkylphenols affect the redox status in first spawning Atlantic cod (Gadus morhua) of both sexes. Model compounds tested included 4-tert-butylphenol (C4), 4-n-pentylphenol (C5), 4-n-hexylphenol (C6) and 4-n-heptylphenol (C7), all found in produced water. First spawning Atlantic cod were force-fed a mixture of these four alkylphenols, ranging between 0.02 and 80 ppm or 5 ppm 17beta-estradiol (E2), for 1 or 4 weeks. Increased hepatic total glutathione concentration in response to alkylphenol exposure was detected in female fish compared to control group after 1-week exposure, an effect not seen after 4 weeks. Furthermore, hepatic total glutathione concentration was sex dependent, where male fish sampled after 4 weeks had higher levels of glutathione than female fish. Increased glutathione reductase catalytic activities in both male and female fish were seen after exposure to 0.02 ppm alkylphenol mixture in 4 weeks. The glutathione S-transferase activity was only affected in male fish exposed to 0.02 ppm alkylphenols, and glucose-6-phosphate dehydrogenase activity increased in female fish exposed to 0.02 ppm alkylphenol mixture for 1 week. The increase of hepatic total glutathione content as well as the effects on glutathione reductase activities suggests that alkylphenol exposure affects the redox status in Atlantic cod.

Animals↗