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Synthesis of diethylamine-functionalized soybean oil.

Specialty chemicals based on renewable resources are desirable commodities due to their eco-friendly nature and "green" product characteristics. These chemicals can demonstrate physical and chemical properties comparable to those of conventional petroleum-based products. Suitably functionalized amines in the triacylglycerol structure can function as an antioxidant, as well as an antiwear/antifriction agent. In addition, the amphiphilic nature of seed oils makes them an excellent candidate as base fluid. The reaction of amine and epoxidized seed oils in the presence of a catalyst almost always leads to different intra/intermolecular cross-linked products. In most cases, the triacylglycerol structure is lost due to disruption of the ester linkage. Currently, there is no reported literature describing the aminolysis of vegetable oil without cross-linking. Here the epoxy group of the epoxidized soybean oil has been selectively reacted with amines to give amine-functionalized soybean oil. The optimization procedure involved various amines and catalysts for maximum aminolysis, without cross-linking and disruption of the ester linkage. Diethylamine and ZnCl2 were found to be the best. NMR, IR, and nitrogen analysis were used to characterize the products.

Chlorides↗

Persistence of N-nitrosodiethanolamine contamination in American metal-working lubricants.

The potent carcinogen N-nitrosodiethanolamine (NDELA) was discovered as a contaminant of commercial metal-working lubricants over a decade ago. To determine whether or not improvements in industrial practice suggested in the meantime have eliminated this contamination from United States products, a selection of cutting fluids obtained from the current marketplace was analysed for NDELA content. All six semi-synthetic fluids examined contained NDELA at levels ranging from 0.5 to 4.3 ppm. Three of six petroleum-based lubricants and five of six synthetics also contained significant NDELA (when analysed at a detection limit of 0.03 ppm), at levels of up to 0.16 and 55 ppm, respectively. The mean concentrations were 1.5 ppm for the semi-synthetics, 0.07 ppm for the petroleum-based products, and 11.4 ppm for the synthetic metal-working fluids. While these levels are far below the values of 1-2% by weight (10,000-20,000 ppm) found in some contaminated products 13 years ago, they may nevertheless pose a continuing health risk for the machinists who work with them.

Diethylnitrosamine↗

Acute renal failure after use of diesel fuel as shampoo.

After washing his hair with diesel fuel a 28-year-old patient developed acute renal failure (ARF) and oliguria requiring hemodialysis. The patient recuperated completely. In the absence of other causal factors, we believe that the absorption of the diesel fuel components, either through the respiratory tract or through the skin can be considered to be the cause of the ARF. In spite of the extended everyday use of petroleum distillation products, cases of acute intoxication are infrequent. Even rarer are cases in which these products occasion ARF.

Acute Kidney Injury↗

Petro-state constraints on health policy: guidelines for workable reform in Venezuela.

This article reviews the performance of the Venezuelan health care sector and suggests guidelines for workable health policy under difficult conditions. Two special circumstances constrain policy options. First, Venezuelans share a traditional value, solidarity, which includes a strong desire for equity. Reforms must comply with this norm to succeed. Second, foreign sales of state-controlled oil constitute the bulk of the government budget and the gross domestic product (GDP). Petroleum market fluctuations expose the country to extreme economic cycles. In response, policy making and stakeholders adopt a rentier attitude, focusing on preserving or enlarging entitlements to government oil monies. The side effects of this largesse include poor productivity, a weak private sector, a widespread sense of entitlement without accountability, and a crippled state which controls most of the available resources yet is unable to effectively tax, regulate, steer the economy, or pursue long-term policies. The health care sector shares these problems. As a result, Venezuela's health systems are fragmented, poorly coordinated, excessively centralized, inequitable, and ineffective. Policies to improve public health and public and private medical care must take into account these constraints.

Delivery of Health Care↗

Characterization of the organic matter of sludge: determination of lipids, hydrocarbons and PAHs from road retention/infiltration ponds in France.

This paper presents the results of the organic matter characterization of sludge from two ponds (retention and infiltration) located in France. Special focus was placed on studying hydrocarbons and PAHs. This investigation is part of a global project on road and urban sludge with the aim of identifying a better means for managing these materials. Gas chromatographic and GC/MS analyses indicate that the main component of the organic fraction stems from petroleum-derived products like diesel fuel and motor oil. This finding was confirmed by the presence of biomarkers from the hopane series, as well as by pyrolytic and alkylated PAHs. Results from this study clearly show that the contaminants are mainly generated from anthropogenic petroleum sources. Due to their levels of hydrocarbon contamination, these sludge deposits must be considered as waste and cannot therefore be disposed anywhere, especially within the current context of sustainable development.

Carbon↗

Contact dermatitis and related dermatoses associated with petroleum recovery and use.

The author reviews the skin's structural and functional protections, and causal factors and clinical patterns of occupational skin disease. He then examines the literature concerning petroleum industry operations and petroleum-derived product use as they relate to skin disease. The chapter concludes with commentary on prevention and treatment of related skin disease.

Dermatitis, Contact↗

Microbial production of primary metabolites.

Microbial production of primary metabolites contributes significantly to the quality of life. Through fermentation, microorganisms growing on inexpensive carbon sources can produce valuable products such as amino acids, nucleotides, organic acids, and vitamins which can be added to food to enhance its flavor or increase its nutritive values. The contribution of microorganisms will go well beyond the food industry with the renewed interest in solvent fermentations. Microorganisms have the potential to provide many petroleum-derived products as well as the ethanol necessary for liquid fuel. The role of primary metabolites and the microbes which produce them will certainly increase in importance.

Amino Acids↗

Operational problems related to the preparation of the seawater soluble fraction of crude oil.

Owing to the importance of dissolution and weathering processes following oil spills, this work focused on the operational (quantitative) aspects related to the dissolution of petroleum-derived products, as well as the influence of solar light on both dissolution and the photoproduction of hydrogen peroxide. Four Brazilian crude oil samples were used to study the transfer process of organic compounds from the crude oil film to the aqueous phase (natural seawater) over a period of up to 45 days. Dissolved organic carbon (DOC), measured by non-dispersive infrared spectroscopy followed by high temperature catalytic combustion, was used to follow the partitioning between the two phases. Aqueous DOC values increased as a function of time (up to 15 days) until equilibrium was reached at concentrations ranging from 5 to 45 mg C L(-1). The final DOC concentration as well as the rate of dissolution depends on the nature of the crude oil. When exposed to sunlight, the dissolution was enhanced by up to 67.3%, and inorganic peroxides were generated in the concentration range from 4.5 up to 8.0 micromol L(-1) after 7.3 h irradiation. These results indicate that there is a need for a standard procedure for the production of the WSF in order to generate a more reliable tool to assess the impact of oil spills on the marine environment.

Catalysis↗

Appraisal of existing methodology in aspiration toxicity testing.

New methods or modifications of currently used methods in aspiration toxicology must be capable of accurately assessing the hazard and toxicity potentials of those products which are capable of being aspirated. The methods evaluated in the rat were intratracheal injections,intravenous injections, and modifications of the Gerarde technique. A product containing petroleum distillates and a standard viscosity petroleum distillate sample were administered to Osborne-Mendel rats, rabbits, and guinea pigs in ml/kg doses. The utility of the methods was determined by comparing lung weight increases, lung-body weight ratios, gross pathological lung changes, and mortality. The modified Gerarde technique showed the best potential for predicting aspiration hazard and toxicity based on the severity of the reactions which, using a radiolabeled oil, was shown to be a function of the amount of product which enters and reacts with the lungs. The influence of preventing the swallowing reflex to assure aspiration of the oil was assessed in the rat. The results show that less than 10% of the dose is aspirated when the swallowing reflex occurs. Methods of sacrifice were investigated for an effect on rat lung weight. No tested method except stunning with cervical dislocation produced an effect. Tests were conducted on rats and rabbits to determine differences in lung reactivity to the influence of inhalation anesthetics, pentothal sodium, or no anesthesia in response to petroleum distillate administration and to determine which test species is the better animal model. The resuls indicate that the rat is the better test model because of degree of lung reaction, size, and economy, and that inhalation anesthesia with ether is preferable over the other choices.

Animals↗

Effect of a metal alloy fuel catalyst on bacterial growth.

Many microorganisms have been demonstrated to utilize petroleum fuel products to fulfill their nutritional requirement for carbon. As a result, the ability of these microbes to degrade fuel has both a deleterious affect as well as beneficial applications. This study focused on the undesired ability of bacteria to grow on fuel and the potential for some metal alloys to inhibit this biodegradation. The objective of this study was to review the pattern of growth of two reference strains of petroleum-degrading bacteria, Pseudomonas oleovorans and Rhodococcus rhodocrous, in a specific hydrocarbon environment in the presence of a commercially available alloy. The alloy formulated and supplied by Advanced Power Systems International Inc. (APSI) is sold for fuel reformulation and other purposes. The components of the alloy used in the study were antimony, tin, lead, and mercury formulated as pellets. Surface characterization also showed the presence of tin oxide and lead amalgam phases. Hydrocarbon used for the study was primarily 87-octane gasoline. The growth of the bacteria in the water and mineral-supplemented gasoline mixture over 6-8 weeks was monitored by the viable plate count method. While an initial increase in bacteria occurred in the first week, overall bacterial growth was found to be suppressed in the presence of the alloy. Results also indicate that the alloy surface characteristics that convey the catalytic activity may also contribute to the observed antibacterial activity.

Catalysis↗

New therapy for hydrocarbon pneumonitis--nasal prongs continuous positive airway pressure (NPCPAP).

Respiratory failure and conscious disturbance developed in a 18-month-old girl following ingestion of an unknown quantity of spot remover solution, a petroleum distillate product. Rapid deterioration was noted within 2 hours after ingestion. The patient became stable in condition and dramatically improved through intensive care with respiratory support by using nasal prongs continuous positive airway pressure (NPCPAP). To our knowledge, this may be the first case being successfully managed with this technique.

Female↗

Recent advances in petroleum microbiology.

Recent advances in molecular biology have extended our understanding of the metabolic processes related to microbial transformation of petroleum hydrocarbons. The physiological responses of microorganisms to the presence of hydrocarbons, including cell surface alterations and adaptive mechanisms for uptake and efflux of these substrates, have been characterized. New molecular techniques have enhanced our ability to investigate the dynamics of microbial communities in petroleum-impacted ecosystems. By establishing conditions which maximize rates and extents of microbial growth, hydrocarbon access, and transformation, highly accelerated and bioreactor-based petroleum waste degradation processes have been implemented. Biofilters capable of removing and biodegrading volatile petroleum contaminants in air streams with short substrate-microbe contact times (<60 s) are being used effectively. Microbes are being injected into partially spent petroleum reservoirs to enhance oil recovery. However, these microbial processes have not exhibited consistent and effective performance, primarily because of our inability to control conditions in the subsurface environment. Microbes may be exploited to break stable oilfield emulsions to produce pipeline quality oil. There is interest in replacing physical oil desulfurization processes with biodesulfurization methods through promotion of selective sulfur removal without degradation of associated carbon moieties. However, since microbes require an environment containing some water, a two-phase oil-water system must be established to optimize contact between the microbes and the hydrocarbon, and such an emulsion is not easily created with viscous crude oil. This challenge may be circumvented by application of the technology to more refined gasoline and diesel substrates, where aqueous-hydrocarbon emulsions are more easily generated. Molecular approaches are being used to broaden the substrate specificity and increase the rates and extents of desulfurization. Bacterial processes are being commercialized for removal of H(2)S and sulfoxides from petrochemical waste streams. Microbes also have potential for use in removal of nitrogen from crude oil leading to reduced nitric oxide emissions provided that technical problems similar to those experienced in biodesulfurization can be solved. Enzymes are being exploited to produce added-value products from petroleum substrates, and bacterial biosensors are being used to analyze petroleum-contaminated environments.

Aerobiosis↗

Neurasthenic symptoms in workers occupationally exposed to jet fuel.

Long-term exposure to petroleum distillation products (e.g. jet fuel) has been suggested to cause chronic mental and neurological symptoms. In the present "cross-sectional epidemiological study" the extent of neuropsychiatric ill-health in 30 workers exposed to jet fuel was compared with that in 60 non-exposed matched controls. Standardized medical interviews showed a higher occurrence of neurasthenic symptoms in exposed subjects (P less than 0.001). The result was confirmed by examination of the medical records kept by the factory physician (P less than 0.01). The prevalence of psychiatric symptoms was assessed with a rating scale of 37 items (a modified CPRS). Again, the exposed workers scored higher than the controls (P less than 0.001), particularly regarding the neurasthenic symptoms, i.e. fatigue, anxiety, mood changes, memory difficulties, and various psychosomatic symptoms (P less than 0.01). The results could neither be explained by observer's bias, nor by a greater susceptibility for mental disorders in the exposed subjects. We therefore conclude that occupational exposure to jet fuel vapours around the present threshold limit values may induce a neurasthenic syndrome.

Adult↗

Arhodomonas aquaeolei gen. nov., sp. nov., an aerobic, halophilic bacterium isolated from a subterranean brine.

Arhodomonas aquaeolei gen. nov., sp. nov., isolated from a petroleum reservoir production fluid, is described. The single isolate was an obligately halophilic, aerobic, gram-negative, oval rod-shaped bacterium that was actively motile by means of a single polar flagellum. It was catalase and oxidase positive. The isolate had a specific requirement for NaCl; growth occurred at NaCl concentrations between 6 and 20%, and optimal growth occurred in the presence of 15% NaCl. This species metabolized primarily organic acids and required biotin for growth. The name Arhodomonas is proposed for the new genus, which was placed in the gamma subclass of the Proteobacteria on the basis of the results of a 16S rRNA sequence analysis. Although A. aquaeolei is most closely related to purple sulfur bacteria (the genera Ectothiorhodospira and Chromatium), it is not a phototrophic microorganism, which is consistent with its isolation from a subterranean environment. The major components of its cellular fatty acids were C16:0, C18:1, C19:0, C16:1, and C18:0 acids. The DNA base composition of the type strain is 67 mol% G+C. The type and only strain is strain HA-1 (= ATCC 49307).

Bacterial Typing Techniques↗