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Determination of hydrocarbon types in petroleum and coal-derived products by thin-layer chromatography/densitometry.

Different methodologies based on thin-layer chromatography (TLC)/densitometry were used to separate and quantitate hydrocarbon types in middle distillates (gas oil), heavy distillates (lubricant) from petroleum, and coal-derived products. Thus, petroleum products were separated into saturates and aromatics by development, using n-hexane (9 min) followed by dichloromethane (4.5 min), of silica gel plates impregnated with berberine sulfate. Detection of saturates and aromatics was performed by fluorescence scanning using 365 nm as the excitation wavelength. Alternative detection of aromatics can be performed on either silica gel or berberine-impregnated plates by using ultraviolet (UV) densitometry at 250 nm. On the other hand, polar coal-derived products were separated into aromatics, polar compounds, and uneluted components by using silica gel plates and development with toluene (12 min), followed by dichloromethane-methanol (95 + 5, v/v), with detection by UV densitometry at 250 nm. In all cases, external standard calibration was used for quantitation. Results were validated by using standard methods or well-established techniques of the petrochemical industry. The potential usefulness of TLC/densitometry is discussed.

Chromatography, Thin Layer↗

Potential uses of petrochemical products can result in significant benzene exposures: MSDSs must list benzene as an ingredient.

According to 29 CFR1910.1200 (Hazard Communication Standard [HCS]), a material safety data sheet (MSDS) must list a carcinogen as an ingredient if its concentration in a product is 0.1% or more by weight. However, according to the HCS, when the concentration of a carcinogen in a product is less than 0.1% (by weight) it may not be necessary to list it as an ingredient on the MSDS. The standard stipulates that if potential uses of the product can result in exposures to the carcinogen that exceed the Occupational Safety and Health Administration (OSHA) permissible exposure limit or the ACGIH threshold limit value (TLV), then it must be listed. This article focuses on the failure of MSDSs to report benzene as a listed ingredient in products that incorporate petroleum-derived ingredients such as toluene and hexane. In the United States, approximately 238,000 people are occupationally exposed to benzene each year. Only rarely is benzene listed as an ingredient on MSDSs even though it often comprises more than 0.1% of petroleum solvents and, when its concentrations in petroleum-derived products are much less than 0.1%, inhalation exposures to benzene can be much higher that its OSHA PEL of one part per million (ppm) by volume (v/v) andACGIH TLV of/one-half ppm (v/v). As a consequence of benzene's omission from MSDSs as a listed ingredient, employers are frequently unaware of their requirement to implement 29 CFR 1910.1028 (Benzene Standard) and of the need to address employee exposures to benzene in the workplace. This article demonstrates that benzene should be listed as an ingredient on MSDSs, even at concentrations in benzene-containing products that are between one and two orders of magnitude below OSHA's 0.1% threshold. An exposure assessment methodology is presented that is applicable to employees whose conditions of exposure are similar to those in the published study. These workers make up a similar exposure group. The information and methodology presented here are germane to preparation of accurate MSDSs for benzene-containing products, employers who must comply with 29 CFR 1910.1028, and retrospectively estimating exposures to benzene.

Air Pollutants, Occupational↗

[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↗

[Sanitary-toxicological assessment of petroleum slimers undergone biological purification].

Pilot production and production studies using a biological method for treating and neutralizing toxic waste polluted with petroleum products at high concentrations (up to 30%) were conducted. The results have indicated that the use of oil degrading microorganisms is highly promising. Within the first vegetative period as high as 80% of petroleum products withdrew from waste and over 95% of those migrated into the aqueous medium. Purification decreased the content of mobile phases of metals to the values below the maximum allowable concentrations. The waste that is highly toxic for protozoa and the test crop wheat shall be considered to be nontoxic.

Hazardous Substances↗

Optimization of batch and fed-batch bioreactors using simulated annealing.

In order for biobased industrial products to compete economically with petroleum-derived products, significant reduction in their processing cost is necessary. Since most bioprocesses are operated in batch or fed-batch mode, their optimization involves theoretical and computational challenges. Simulated annealing (SA), a stochastic optimization algorithm, is used in this study to solve a number of challenging optimization problems related to the design and operation of bioreactors. Two well-known case studies are considered in which the robustness and efficiency of the SA algorithm is demonstrated. More specifically, in the first case study it is shown that the global optimal solution located by SA achieves significant improved productivity when compared with the results of previous investigations. In the second case study a realistic objective function is considered where the economic performance of a bioprocess is optimized. SA exhibits impeccable performance and robustness and was able to locate the global optimal solution irrespective of the initial point selected.

Algorithms↗

Multiple myeloma and benzene exposure in a multinational cohort of more than 250,000 petroleum workers.

Case reports have suggested an association between benzene exposure and multiple myeloma. Because petroleum workers are exposed to benzene or benzene-containing liquids, studies of these workers provide an opportunity for investigating the relationship between benzene and multiple myeloma. A large number of cohort studies of petroleum workers have been conducted. However, few of them have reported results of multiple myeloma separately. One reason is that multiple myeloma is usually grouped with other lymphopoietic cancers in the analysis. Another reason is that multiple myeloma is relatively rare, and few individual studies are large enough to provide reliable risk estimates. To determine the risk of multiple myeloma in petroleum (refinery, distribution, production, and pipeline) workers, we have identified 22 cohort mortality studies of petroleum workers in the United States, the United Kingdom, Canada, and Australia. Authors of these studies were contacted, and data on the number of observed deaths and age-specific person-years of observation were requested. Data from individual studies were combined in a pooled analysis (meta-analysis). In addition to the pooled analyses, results for individual cohorts, most of which have never been reported before, are also presented. The combined multinational cohort consisted of more than 250,000 petroleum workers, and the observation period covered an interval of 55 years from 1937 to 1991. A total of 205 deaths from multiple myeloma were observed, compared to 220.93 expected, a total derived from respective national mortality rates. The corresponding standardized mortality ratio (SMR) was 0.93 and the 95% confidence interval (95% CI) was 0.81-1.07. Additional analyses were performed by type of facility and industrial process. Stratum-specific SMRs (95% CIs) were 0.92 (0.77-1.09) for refinery workers and 0.93 (0.69-1.23) for distribution workers. When individual cohorts were stratified by length of observation, no pattern was detected. The pooled analysis indicates that petroleum workers are not at an increased risk of multiple myeloma as a result of their exposure to benzene, benzene-containing liquids, or other petroleum products in their work environment. This conclusion is supported by cohort studies of workers in other industries who were exposed to benzene as well as by population-based case-control studies of multiple myeloma and occupational exposures.

Australia↗

[Blastomogenic action of heavy vanadium-rich petroleum and its processing products].

The contributors performed a study of the blastomogenic properties of the heavy high vanadium oil processed at different temperatures. Skin applications of the oil and oil products in hybrid mice induced skin tumours in 27.5 (48.7%), pregastric--6.4 (7.6%), genital--15.4 (21.1%) cases. It was established that high temperatures of oil sublimation increased the benzopyrene contents and the oil products' blastomogenic activity.

Animals↗

Petroleum biodegradation in marine environments.

Petroleum-based products are the major source of energy for industry and daily life. Petroleum is also the raw material for many chemical products such as plastics, paints, and cosmetics. The transport of petroleum across the world is frequent, and the amounts of petroleum stocks in developed countries are enormous. Consequently, the potential for oil spills is significant, and research on the fate of petroleum in a marine environment is important to evaluate the environmental threat of oil spills, and to develop biotechnology to cope with them. Crude oil is constituted from thousands of components which are separated into saturates, aromatics, resins and asphaltenes. Upon discharge into the sea, crude oil is subjected to weathering, the process caused by the combined effects of physical, chemical and biological modification. Saturates, especially those of smaller molecular weight, are readily biodegraded in marine environments. Aromatics with one, two or three aromatic rings are also efficiently biodegraded; however, those with four or more aromatic ring are quite resistant to biodegradation. The asphaltene and resin fractions contain higher molecular weight compounds whose chemical structures have not yet been resolved. The biodegradability of these compounds is not yet known. It is known that the concentrations of available nitrogen and phosphorus in seawater limit the growth and activities of hydrocarbon-degrading microorganisms in a marine environment. In other words, the addition of nitrogen and phosphorus fertilizers to an oil-contaminated marine environment can stimulate the biodegradation of spilled oil. This notion was confirmed in the large-scale operation for bioremediation after the oil spill from the Exxon Valdez in Alaska. Many microorganisms capable of degrading petroleum components have been isolated. However, few of them seem to be important for petroleum biodegradation in natural environments. One group of bacteria belonging to the genus Alcanivorax does become predominant in an oil-contaminated marine environment, especially when nitrogen and phosphorus fertilizers are added to stimulate the growth of endogenous microorganisms.

Biodegradation, Environmental↗

Short-term adverse effects in humans of ingested mineral oils, their additives and possible contaminants--a review.

The toxicological databases for petroleum refinery products such as mineral oils, as well as for their potential contaminants and additives, were reviewed for human cases of poisoning by the oral route. The aim was to determine whether any overlooked adulterant in the oil implicated as the cause of the 1981 outbreak of Toxic Oil Syndrome (TOS) in Spain, may have been responsible for the unusual symptomatology characterizing this disease. The essential features of TOS were peripheral eosinophilia, pulmonary oedema and endothelial damage in the acute phase; myalgia, sensory neuropathy, hepatic injury, skin oedema and sicca in the intermediate phase; and peripheral neuropathy, muscle wasting, scleroderma and hepatopathy in the chronic phase. Of the more than 70 chemical entities and mixtures reviewed here, none had been reported as producing adverse toxic effects upon ingestion resembling the specific set of symptoms and progression that characterized TOS. Because of their viscosity, the most commonly recorded disease process associated with oral ingestion of petroleum refinery products was lipid pneumonia, implicating lung exposure via aspiration. The mineral oil additives and contaminants comprised a highly diverse range of chemical entities, producing a variety of symptoms in instances of poisoning. Specifically, no chemical entity amongst the refinery products, additives or contaminants was described as inducing a syndrome involving vasculitis accompanied by thrombotic events, along with immunological consequences (such as T-lymphocyte activation and cytokine release), as is considered to be the cellular basis of TOS.

Administration, Oral↗