Experimental production of carcinoma in rhesus monkeys.
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Four duplicate samples of cocoa-containing materials, a practice sample, and standards were submitted to the collaborators for theobromine and caffeine analysis by HPLC. In the method the samples are defatted with petroleum ether, and dried. The fat-free residue is then extracted with water and an aliquot is injected into the chromatograph. Compounds are quantitated by comparison with internal or external standards, either by peak height or peak area. Results for all the analyses showed that few of the values were more than 2 standard deviations from the mean. The method has been adopted as official first action.
Methyl chloroform (1,1,1-trichloroethane) was identified as a major component in two fabric-protector spray products. Mutagenic effects were determined at several dosage levels for the two products and some of the identified components. Levels of organics in the air of sealed desiccators, used as exposure chambers in modified Salmonella reversion assays, were measured by a gas chromatographic technique. Both fabric protectors and two samples of trichloroethane were mutagenic in strain TA 1535 and one of each was mutagenic in strain TA 100. Other constituents, such as petroleum distillate and p-dioxane, were nonmutagenic at the tested exposure levels.
Hydrophobic cotton fibers, obtained by acylation of cellulose with fatty acid using microwaves radiations, have a high selective affinity for vegetable or mineral oil, fuel, and petroleum, in aqueous medium. Their sorption capacity (SC) (weight of liquid picked up by a given weight of sorbent) is about 20 g/g, after draining. They are reusable after simple squeezing, and their SC reaches a constant value, ca. 12 g/g. Moreover, this product is stable in water, whereas raw cotton can develop molds, after oil sorption. Besides, it is also biodegradable.
Strain BAS50, isolated from a petroleum reservoir at a depth of 1,500 m and identified as Bacillus licheniformis, grew and produced a lipopeptide surfactant when cultured on a variety of substrates at salinities of up to 13% NaCl. Surfactant production occurred both aerobically and anaerobically and was optimal at 5% NaCl and temperatures between 35 and 45 degrees C. The biosurfactant, termed lichenysin A, was purified and chemically characterized. A tentative structure and composition for the surfactant are described. Lichenysin A is a mixture of lipopeptides, with the major components ranging in size from 1,006 to 1,034 Da. The lipid moiety contains a mixture of 14 linear and branched beta-hydroxy fatty acids ranging in size from C12 to C17. There are seven amino acids per molecule. The peptide moiety is composed of the following amino acids: glutamic acid as the N-terminal amino acid, asparagine, valine, leucine, and isoleucine as the C-terminal amino acid, at a ratio of 1.1:1.1:1.0:2.8:1.0, respectively. Purified lichenysin A decreases the surface tension of water from 72 mN/m to 28 mN/m and achieves the critical micelle concentration with as little as 12 mg/liter, characterizing the product as a powerful surface-active agent that compares favorably to others surfactants. The antibacterial activity of lichenysin A has been demonstrated.
A most probable number (MPN) method was used to enumerate dissimilatory ammonium-producing, nitrate-reducing bacteria (DAP-NRB) in oil field waters and to determine whether they were stimulated by nitrate addition used to control hydrogen sulfide production. An ammonium production medium with 5 carbon and energy sources (acetate, glucose, glycerol, pyruvate, and succinate) and nitrate was used in a 3-tube MPN procedure to enumerate DAP-NRB. These bacteria were detected in 12 of 18 oil field water samples, but they were seldom detected in wellhead samples. Three oil field water samples were amended with nitrate in serum bottles and the numbers of different NRB were determined over a 38-day incubation time. This amendment stimulated increases in the numbers of heterotrophic NRB and autotrophic nitrate-reducing, sulfide-oxidizing bacteria, but DAP-NRB remained a minor portion of these communities. Overall, DAP-NRB were present in many of the oil field waters that were examined but their numbers were low. It appears that DAP-NRB would play a minor role in the consumption of nitrate injected into oil field waters for the control of hydrogen sulfide production.
The toxicity and efficacy of a bacteria-based commercial bioremediation agent (CBA) was assessed through bioassays with juvenile inland silverside minnows, Menidia beryllina, and flask studies of oil degradation. Addition of the CBA to weathered Alaska, USA North Slope crude oil (ANS-521) prior to testing increased toxicity of the water-soluble fraction (WSF) of the oil in both chronic (growth) and acute (mortality) toxicity tests. Time-course toxicity assessment of the water-soluble fraction of the CBA/oil combination indicated increases in effect after 7 to 14 d of mixing that coincided with elevated concentrations of both alkanes and aromatics in the WSF. Under controlled laboratory conditions, the CBA significantly enhanced degradation of the oil compared with a treatment with nutrients alone. The alkane fraction was degraded by nearly 100% over a 42-d period while the aromatic fraction was decreased by 70%. While toxicity testing is not currently required to list bioremediation agents on the product schedule of the National Oil and Hazardous Substances Pollution Contingency Plan, the potential interaction between bioremediation agents and oil should be further investigated and listing requirements reassessed as necessary. Recommendations for future investigations of this issue include characterization of temporal trends in toxicity of CBA and oil mixtures, use of multiple test methods (battery testing) when evaluating toxicity, comparative evaluations of indigenous versus product-derived microorganisms in efficacy studies, and the use of a comparable oil between studies to facilitate comparison of efficacy and toxicity data for different products.
The distribution of methan producing bacteria was studied in oil bearing strata of the Apsheron Peninsula and was shown to depend on ecological conditions: the total mineralization of stratal water, the content of hydrogen sulfide, sulfates, the pH, the extent of penetration of surface waters. The bacteria was found in 11 among 14 stratal water samples taken from the studied oil deposits. The flooding of oil collectors with surface waters was shown to be one of the factors responsible for the distribution of methane producing bacteria in the stratal waters of oil deposits. Methane producing cenoses were found in stratal water whose mineralization varied from 17 to 84.8 g per litre and the content of hydrogen sulfide varied from 0 to 585 mg per litre. Most of the samples contained also sulfate reducing bacteria which grew in a medium with lactate, as well as fermenting microorganisms which grew in the presence of peptone and glucose and supplied methane producing bacteria with their substrates, viz. H2, CO2 and acetate. Preliminary experiments in which methane was produced from oil via a two-stage process suggest that flooding favours the formation of oil oxidation products in the strata and these products serve as substrates for the growth of microbial cenoses producing methane.
Surface water Selenium (Se) concentrations are above regulatory standards at several active and inactive phosphate mine sites in the US Western Phosphate Resource Area. The focus of the present study was to examine the impacts of the microbial communities on the oxidation state of Se in overburden waste from the Smoky Canyon phosphate mine in Idaho, USA. Microbial populations were found that reduce soluble selenate (SeO (4) (2-) ) to insoluble elemental Se. Microcosm experiments were conducted for molecular genetic analysis of this microbial community by rRNA gene profiling. An acetone pretreatment step was developed to remove interfering pre-petroleum hydrocarbons from the samples prior to extraction. PCR was used to amplify 16S and 18S rRNA genes present in the microbial community DNA. The amplified products were subjected to denaturing gradient gel electrophoresis (DGGE). Isolates and excised DGGE bands were amplified and sequenced for identification to determine the relative importance of culturable isolates to the total microbial population. Analysis of samples from different sites at the mine showed how Se contamination and previous remediation treatments changed the microbial populations across the site. Members of the family Enterobacteriaceae were dominant among the selenate reducing isolates from the site containing high Se levels. In particular, Serratia fonticola was isolated repeatedly from contaminated Smoky Canyon Mine site samples. Packed column studies were performed with seleniferous waste rock fractions from Smoky Canyon Mine. Column amendments consisted of combinations of iron, compost, and whey. Eh, pH, and extractable Se measurements were taken. Tests with infiltrated water showed columns containing an organic amendment combined with iron metal were the most resistant to Se leaching. Iron-based compounds from the corroding metal are thought to strongly bind the Se reduced by microbial activity, thereby stabilizing the Se in an insoluble form. We conclude that long-term stabilization of selenium at contaminated mine sites may require reductive microbial processes combined with abiotic immobilization by iron, either natural or engineered, to stabilize the Se and retard re-oxidation and release. Iron-selenide or iron-selenite compounds are more stable and resistant to leaching, especially when removed from active weathering.
Thiobacillus denitrificans has been shown to be an effective biocatalyst for the treatment of a variety of sulfide-laden waste streams including sour water, sour gases, and refinery spent-sulfidic caustics. The term 'sour' originated in the petroleum industry to describe a waste contaminated with hydrogen sulfide or salts of sulfide and bisulfide. The microbial treatment of sour waste streams resulting from the production or refining of natural gas and crude oil have been investigated in this laboratory for many years. The application of this technology to the treatment of sour wastes on a commercially useful scale has presented several technical barriers including substrate inhibition (sulfide), product inhibition (sulfate), the need for septic operation, biomass recycle and recovery, mixed waste issues, and the need for large-scale cultivation of the organism for process startup. The removal of these barriers through process improvements are discussed in terms of a case study of the full-scale treatment of sulfide-rich wastewater. The ability of T. denitrificans to deodorize and detoxify an oil-field produced water containing sulfides was evaluated under full-scale field conditions at Amoco Production Co. Salt Creek Field in Midwest, WY. More than 800 m3/d of produced water containing 100 mg/L sulfide and total dissolved solids of 4800 mg/L were successfully biotreated in an earthen pit (3000 m3) over a six-month period. Complete removal of sulfides and elimination of associated odors were observed. The system could be upset by severe hydraulic disturbances; however, the system recovered rapidly when normal influent flow rates were restored.
1,2,3,4,7,7-Hexachloro-2,5-norbornadiene (I), 1,2,3,4,5-endo,7,7-heptachloro-2-norbornene (II), and 1,2,3,4,7,7-hexachloro-5,6-endo-epoxy-2-norbornene (III) have been identified as contaminants in Mississippi River fish by combined gas-liquid chromatography (GLC)-mass spectrometry. The method used to determine residues of these compounds, which are associated with production of the pesticide endrin, is similar to the AOAC multiresidue method for chlorinated pesticides. The residues are extracted from the sample with acetonitrile, transferred to petroleum ether, and chromatographed on a Florisil column. Compounds I and II are eluted from the Florisil with petroleum ether and compound III is eluted with ethyl ether-petroleum ether (6 + 94). The concentrated eluates are analyzed by using electron capture GLC. The method provides adequate recoveries of all 3 chlorinated norbornene derivatives and allows quantitation at or below the 0.05 ppm level in fish with a 20 mg sample equivalent injection.
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This paper presents the results of an experimental investigation into the use of stabilisation/solidification (S/S) to treat synthetic drill cuttings as a pre-treatment to landfilling or for potential re-use as construction products. Two synthetic mixes were used based on average concentrations of specific contaminates present in typical drill cuttings from the North Sea and the Red Sea areas. The two synthetic drill cuttings contained similar chloride content of 2.03% and 2.13% by weight but different hydrocarbon content of 4.20% and 10.95% by weight, respectively; hence the mixes were denoted as low and high oil content mixes, respectively. A number of conventional S/S binders were tested including Portland cement (PC), lime and blast-furnace slag (BFS), in addition to novel binders such as microsilica and magnesium oxide cement. Physical, chemical and microstructural analyses were used to compare the relative performance of the different binder mixes. The unconfined compressive strength (UCS) values were observed to cover a wide range depending on the binder used. Despite the significant difference in the hydrocarbon content in the two synthetic cuttings, the measured UCS values of the mixes with the same binder type and content were similar. The leachability results showed the reduction of the synthetic drill cuttings to a stable non-reactive hazardous waste, compliant with the UK acceptance criteria for non-hazardous landfills: (a) by most of the binders for chloride concentrations, and (b) by the 20% BFS-PC and 30% PC binders for the low oil content mix. The 30% BFS-PC binder successfully reduced the leached oil concentration of the low oil content mix to inert levels. Finally, the microstructural analysis offered valuable information on the morphology and general behaviour of the mixes that were not depicted by the other tests.
This article will outline a pragmatic approach directed to incorporating key elements of a scientific review of the literature and derive a proposal for an occupational exposure standard for coal tar, coal tar pitch, creosote, petroleum pitch, bitumen and asphalt, six substances which contain polynuclear aromatic hydrocarbons. Five approaches to the standard setting process are reviewed and their strengths and weaknesses discussed. Unfortunately there does not exist an acceptable epidemiological data set, other than the coke oven emission studies, on which to base a valid and reliable risk assessment model. Based on comparative potency experiments of complex mixtures, consideration of the state-of-the-art sampling and analytical methods, prevention of acute human health effects, and current existing standards for these substances throughout the world, a set of recommended exposure standards are derived for health policy makers.
Hydrothermal systems associated with oceanic spreading centers are now recognized as relatively common phenomena, and the organic chemical alterations occurring there are rapid and efficient. In the marine hydrothermal systems at water depths > 1.5 km, the conditions driving chemical reactions are high temperatures (up to >400 degrees C), confining pressures (>150 bar), and other parameters such as pH, Eh, and mineralogy in an aqueous open flow medium. Continental hydrothermal systems may also be of interest, as, for example, in failed or dormant rifts and regions around piercement volcanoes. Organic matter alteration by reductive reactions to petroleum hydrocarbons occurs in hydrothermal systems over a wide temperature window (approximately 60 to >400 degrees C), under elevated pressure, and in a brief geological time (years to hundreds of years). The products are rapidly moved as bulk phase or in fluids from the regions at higher temperatures to areas at lower temperatures, where the high molecular weight material separates from the bulk. These conditions are conducive to organic chemistry which yields concurrent products by primarily reduction (due to mineral buffering), oxidation (high thermal stress), and synthesis reactions. This chemistry is just beginning to be elucidated by the geochemical community, but there are various industrial applications which provide useful preliminary insight. Therefore, the behavior of organic matter (inclusive of methane to high molecular weight compounds > C40) in warm to supercritical water needs to be characterized to understand the implications of this novel phenomenon in geological and geochemical processes, and the chemistry occurring over the full temperature spectrum of hydrothermal systems is of relevance to origins of life research.
Diesel particulate matter (DPM) has been recognized as carcinogenic due to its respirable sizes and toxic compositions. It is essential to understand its formation mechanisms to effectively reduce DPM emissions. Studies have indicated that resonance stabilize radicals can result in more soot and PAC (polycyclic aromatic compounds) formation in combustion processes. As the largest single polycyclic aromatic constituent in petroleum fuels, 1- and 2-methylnaphthalenes can readily form resonance-stabilized radicals in combustion, and yet the reaction mechanisms are not well understood. In this paper, product formation mechanisms of these compounds are experimentally investigated in a flow reactor. The pyrolysis of 1- and 2-methylnaphthalene was studied from 800 to 1000 degrees C, and the oxidation of 2-methylnaphthalene was studied from 650to 950 degrees C. The PACs were quantified by GC/MS and HPLC, and soot was quantified gravimetrically. Naphthalene is the most abundant product and is formed from methyl loss by H displacement. Isomerization in pyrolytic conditions results in the second most abundant product. The methyl radicals recombine with the reactants to form ethylnaphthalenes and dimethylnaphthalenes. 2-Naphthaldehyde is formed from the oxidation of the naphthylmethyl radicals. 1-Methylnaphthalene is of slightly higher reactivity in comparison to its isomer. The experimental results indicate that the PAC formation from the pyrolysis and oxidation of the two methylnaphthalenes are likely to be governed by similar mechanisms. The lack of carbon dimerization products in significant quantities may be due to their further growth into soot.