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PubMed1998

Modeling the chemistry of complex petroleum mixtures.

Determining the complete molecular composition of petroleum and its refined products is not feasible with current analytical techniques because of the astronomical number of molecular components. Modeling the composition and behavior of such complex mixtures in refinery processes has accordingly evolved along a simplifying concept called lumping. Lumping reduces the complexity of the problem to a manageable form by grouping the entire set of molecular components into a handful of lumps. This traditional approach does not have a molecular basis and therefore excludes important aspects of process chemistry and molecular property fundamentals from the model's formulation. A new approach called structure-oriented lumping has been developed to model the composition and chemistry of complex mixtures at a molecular level. The central concept is to represent an individual molecular or a set of closely related isomers as a mathematical construct of certain specific and repeating structural groups. A complex mixture such as petroleum can then be represented as thousands of distinct molecular components, each having a mathematical identity. This enables the automated construction of large complex reaction networks with tens of thousands of specific reactions for simulating the chemistry of complex mixtures. Further, the method provides a convenient framework for incorporating molecular physical property correlations, existing group contribution methods, molecular thermodynamic properties, and the structure--activity relationships of chemical kinetics in the development of models.

Drug Interactions↗
PubMed2003

Chromium-microorganism interactions in soils: remediation implications.

Discharge of Cr waste from many industrial applications such as leather tanning, textile production, electroplating, metallurgy, and petroleum refinery has led to large-scale contamination of land and water. Generally, Cr exists in two stable states: Cr(III) and Cr(VI). Cr(III) is not very soluble and is immobilized by precipitation as hydroxides. Cr(VI) is toxic, soluble, and easily transported to water resources. Cr(VI) undergoes rapid reduction to Cr(III), in the presence of organic sources or other reducing compounds as electron donors, to become precipitated as hydroxides. Cr(VI)-reducing microorganisms are ubiquitous in soil and water. A wide range of microorganisms, including bacteria, yeasts; and algae, with exceptional ability to reduce Cr(VI) to Cr(III) anaerobically and/or aerobically, have been isolated from Cr-contaminated and noncontaminated soils and water. Bioremediation approaches using the Cr(VI)-reducing ability of introduced (in bioreactors) or indigenous (augmented by supplements with organic amendments) microorganisms has been more successful for remediation of Cr-contaminated water than soils. Apart from enzymatic reduction, nonenzymatic reduction of Cr(VI) can also be common and widespread in the environment. For instance, biotic-abiotic coupling reactions involving the microbially formed products, H2S (the end product of sulfate reduction), Fe(II) [formed by Fe(III) reduction], and sulfite (formed during oxidation of elemental sulfur), can mediate the dissimilatory reduction of Cr(VI). Despite the dominant occurrence of enzymatic and nonenzymatic reduction of Cr(VI), natural attenuation of Cr(VI) is not taking place at a long-term contaminated site in South Australia, even 225 years after the last disposal of tannery waste. Evidence suggests that excess moisture conditions leading to saturation or flooded conditions promote the complete removal of Cr(VI) in soil samples from this contaminated site; but Cr(VI) reappears, probably because of oxidation of the Cr(III) by Mn oxides, with a subsequent shift to drying conditions in the soil. In such environments with low natural attenuation capacity resulting from reversible oxidation of Cr(III), bioeremediation of Cr(VI) can be a challenging task.

Bacteria, Anaerobic↗
PubMed2003

An analysis of the risk of B-lymphocyte malignancies in industrial cohorts.

Among numerous studies of occupational groups with varied chemical exposures (e.g., farmers, petroleum workers, and rubber workers), some have reported excess risk for non-Hodgkin's lymphoma (NHL), multiple myeloma, and other cancers of the B-lymphocyte cell line. While not conclusive, these studies raise questions about the effects of chemical exposures on the lymphocytic versus myeloid cell lines. Almost 70 occupational cohort studies were identified that addressed B-cell cancer risks in 9 major industrial categories, in order to look for common patterns across industries. This effort was substantially limited by the inconsistent nature of lymphohematopoietic (LH) classification schemes across studies and over time, and the relative paucity of B-cell-specific results in studies for any given industry. Taking these limitations into consideration, a descriptive, graphical analysis suggested a pattern of B-cell cancer elevations in the rubber and "general chemical" industries, but no consistent patterns in petroleum production/distribution or petrochemical production. The limited data sources, which lack detail about differences in hazard and exposure for different types of products/chemicals, did not allow a comprehensive look at possible common exposures associated with B-cell cancer elevations across industries. This study suggests that evaluation of possible associations between specific chemical exposures and B-cell malignancies would require additional studies with clear and common definitions of B-cell outcomes. The article concludes by giving an example of a possible common framework for categorizing NHL, the diseases for which most classification issues arise.

Butadienes↗
PubMed1996

Common dermatologic manifestations of cutaneous exposure to petroleum and its derivatives.

Crude petroleum serves as the precursor for thousands of chemicals found in a variety of commercial and industrial products. The authors present a brief background on the composition of petroleum and the production of its derivatives, a description of the common cutaneous manifestations of petroleum derivative exposure, and a review of the treatment options for these diseases.

Chemical Industry↗
PubMed1996

Risk of monoclonal gammopathy of undetermined significance: a case-referent study.

A retrospective study was conducted in 285 cases of monoclonal gammopathy of undetermined significance (MGUS) and in 570 sex- and age-matched hospital controls in order to investigate the possible association between socioeconomic status, residence, alcohol and tobacco habits, occupation, occupational exposure to toxic substances, chronic antigenic stimulation, and risk of MGUS. Significant associations with the risk of MGUS were found for farmers (P < 0.005) and for workers in industry (P < 0.025). Occupational exposure to asbestos, fertilizers, mineral oils and petroleum, paints and related products, pesticides, and radiation was significantly (P < 0.05) associated with an increase in risk of MGUS. Chronic immune-stimulating conditions, when considered as a group, presented a significant (P < 0.025) association with the risk of MGUS, but no specific disease has been found to be significantly associated. These data are in agreement with the previous reports on multiple myeloma, suggesting that these factors may play an important role in the development of monoclonal gammopathies. However, these findings need to be confirmed in prospective larger population-based studies.

Adult↗
PubMed1993

Acute nickel carbonyl poisoning.

Nickel carbonyl [Ni(CO)4], is formed when metallic nickel combines with carbon monoxide. It is used in the refining process of nickel and as a catalyst in petroleum, plastic, and rubber production. Nickel carbonyl is considered to be one of the most toxic chemicals used industrially and the magnitude of its morbidity and mortality has been compared to that of hydrogen cyanide. A 46-year-old man presented to the emergency department 24 hours after accidental occupational exposure to nickel carbonyl. He admitted to dermal contamination and inhaling the vapor from his clothing after his respiratory protection was removed. On presentation the patient was alert and oriented, complained of shortness of breath, chest tightness, and paresthesias. Examination revealed decreased breath sounds bilaterally and arterial blood gas PO2 of 39% with calculated O2 saturation of 75%. After face mask O2 at 60% his PO2 increased to 85%. The patient required 60% O2 with continuous positive airway pressure of 5 for 4 days. Disulfiram (Antabuse) was administered for the first 2 days until sodium diethyldithiocarbamate (dithiocarb) was obtained. Disulfiram was used because it is metabolized to two molecules of dithiocarb and is hypothetically of value. Dithiocarb was obtained and continued over the next several days. The patient's urine nickel level on the day of admission was 172 micrograms/dL (normal < 5 micrograms/dL) and a serum level of 14.6 micrograms/dL (normal .26-.46 micrograms/dL). The patient's condition gradually improved over the next 10 days. Nickel carbonyl exposure produces mild transient initial symptoms which are followed within 24 hours by more severe life-threatening events.(ABSTRACT TRUNCATED AT 250 WORDS)

Acute Disease↗
PubMed1997

Air pollution exposure-DNA adduct dosimetry in humans and rodents: evidence for non-linearity at high doses.

The impact of air pollution exposure on the level of total DNA adducts in human white blood cells (WBCs) was evaluated in two populations in the Czech Republic and compared to the exposure-DNA adduct relationship in other populations in the US and China in human lung cells and rodent lung tissue. The human populations examined were exposed to respirable particles (< 2.5 microm) (PM2.5) in urban, rural, and occupational settings where the particles originated from coal and petroleum fuel combustion, coke production, and other coal-tar aerosols (e.g., used in aluminum production). These particles contain carcinogenic polycyclic aromatic hydrocarbons (PAHs) that are known to form DNA adducts through covalent binding. Personal exposure to PM2.5 and PAHs were measured prior to collection of blood samples for DNA adduct analysis by 32P-postlabeling. Coke oven workers (n = 76), in 10 job categories on the top and side of a coke oven in Ostrava, CZ, were studied and compared to a different population exposed to environmental levels of PAHs from air pollution in Teplice, CZ. Personal exposures to airborne particles ranged from < 1 to more than 15,000 microg/m3 and carcinogenic PAHs exposure ranged from < 5 to > 200,000 ng/m3. At low to moderate environmental exposures to carcinogenic PAHs, DNA adduct levels in the WBCs were significantly correlated with exposure. However, at the higher occupational levels found on the coke oven, the exposure-DNA adduct relationship became non-linear. Under these high exposure conditions, the relative DNA adduct level per unit of exposure (DNA-binding potency) was significantly lower than measured at environmental exposures. This finding is consistent with observations in lung cells from bronchoalveolar lavage of humans exposed to a wide range of PAH. This same high exposure-dose non-linearity was also observed in lung DNA from rats exposed by inhalation to a coal-tar pitch aerosol. DNA adduct levels in all these cases show evidence of a form of non-linearity at high doses that has been described by Lutz (W.K. Lutz, Dose-response relationship and low dose extrapolation in chemical carcinogenesis, Carcinogenesis, 11 (1990) 1243-1247) as a superlinear dose response. This superlinear response may be due to saturation of metabolic activation enzymes, induction of either DNA repair processes or detoxification enzymes, or other mechanisms. Regardless of the mechanism, this decrease in the DNA-binding potency at moderate to high doses of PAH has important implications for dose-response extrapolation in risk assessment.

Air Pollutants↗
PubMed2000

Metabolism of alkylbenzenes, alkanes, and other hydrocarbons in anaerobic bacteria.

Aromatic and aliphatic hydrocarbons are the main constituents of petroleum and its refined products. Whereas degradation of hydrocarbons by oxygen-respiring microorganisms has been known for about a century, utilization of hydrocarbons under anoxic conditions has been investigated only during the past decade. Diverse strains of anaerobic bacteria have been isolated that degrade toluene anaerobically, using nitrate, iron(III), or sulfate as electron acceptors. Also, other alkylbenzenes such as m-xylene or ethylbenzene are utilized by a number of strains. The capacity for anaerobic utilization of alkylbenzenes has been observed in members of the alpha-, beta-, gamma- and delta-subclasses of the Proteobacteria. Furthermore, denitrifying bacteria and sulfate-reducing bacteria with the capacity for anaerobic alkane degradation have been isolated, which are members of the beta- and delta-subclass, respectively. The mechanism of the activation of hydrocarbons as apolar molecules in the absence of oxygen is of particular interest. The biochemistry of anaerobic toluene degradation has been studied in detail. Toluene is activated by addition to fumarate to yield benzylsuccinate, which is then further metabolized via benzoyl-CoA. The toluene-activating enzyme presents a novel type of glycine radical protein. Another principle of anaerobic alkylbenzene activation has been observed in the anaerobic degradation of ethylbenzene. Ethylbenzene in denitrifying bacteria is dehydrogenated to 1-phenylethanol and further to acetophenone; the latter is also metabolized to benzoyl-CoA. Naphthalene is presumably activated under anoxic conditions by a carboxylation reaction. Investigations into the pathway of anaerobic alkane degradation are only at the beginning. The saturated hydrocarbons are most likely activated by addition of a carbon compound rather than by desaturation and hydration, as speculated about in some early studies. An anaerobic oxidation of methane with sulfate as electron acceptor has been documented in aquatic sediments. The process is assumed to involve a reversal of methanogenesis catalyzed by Archaea, and scavenge of an electron-carrying metabolite by sulfate-reducing bacteria. Among unsaturated non-aromatic hydrocarbons, anaerobic bacterial degradation has been demonstrated and investigated with n-alkenes, alkenoic terpenes and the alkyne, acetylene.

Bacteria, Anaerobic↗
PubMed2002

Assessment of in-situ bioremediation at a refinery waste-contaminated site and an aviation gasoline contaminated site.

A combination of geochemical, microbiological and isotopic methods were used to evaluate in-situ bioremediation of petroleum hydrocarbons at one site contaminated with refinery waste and a second site contaminated with aviation gasoline at Alameda Point, California. At each site, geochemical and microbiological characteristics from four locations in the contaminated zone were compared to those from two uncontaminated background locations. At both sites, the geochemical indicators of in-situ biodegradation included depleted soil gas and groundwater oxygen, elevated groundwater alkalinity, and elevated soil gas carbon dioxide and methane in the contaminated zone relative to the background. Radiocarbon content of methane and carbon dioxide measured in soil gas at both sites indicated that they were derived from hydrocarbon contaminant degradation. Direct microscopy of soil core samples using cell wall stains and activity stains, revealed elevated microbial numbers and enhanced microbial activities in contaminated areas relative to background areas, corroborating geochemical findings. While microbial plate counts and microcosm studies using soil core samples provided laboratory evidence for the presence of some microbial activity and contaminant degradation abilities, they did not correlate well with either contaminant location, geochemical, isotopic, or direct microscopy data.

Alkalies↗
PubMed1987

Evaluation of occupational exposure to mixed dusts and polycyclic aromatic hydrocarbons in silicon carbide plants.

Workers in the silicon carbide industry have experienced occupational health diseases, particularly lung disorders such as silicosis. The silicon carbide production process mainly employs petroleum coke, sawdust, pure crystalline silica and graphite. Since crystalline silica is present in the occupational environment, the airborne dust content of various polymorphs of silica, especially quartz, cristobalite and tridymite, was determined by X-ray diffraction analysis. The analytical method was modified to eliminate graphite, since it overlaps with the main diffraction plane of quartz. Exploratory field surveys were conducted to identify the minerals present in that occupational environment and to evaluate the validity of the analytical method. The surveys provided information on the mineralogical nature of the dust, its respirable content and the concentration of silica polymorphs. Polycyclic aromatic hydrocarbons also were measured, and the effect of their adsorption on graphite was evaluated.

Air Pollutants, Occupational↗
PubMed1997

Anaerobaculum thermoterrenum gen. nov., sp. nov., a novel, thermophilic bacterium which ferments citrate.

A thermophilic anaerobic bacterium designated strain RWcit2T (T = type strain) was isolated from the production water of a petroleum reservoir. The cells of this organism are straight to slightly curved rods that are gram negative and nonmotile. Spore formation has not been demonstrated. Growth occurs at temperatures ranging from 28 to 60 degrees C, with optimum growth occurring at 55 degrees C, and at pH values ranging from 5.5 to 8.6, with optimum growth occurring between pH 7 and 7.6. Growth occurs in media containing 0 to 20 g of NaCl per liter, and optimum growth occurs in the presence of 10 g of NaCl per liter. Strain RWcit2T grows on a range of organic acids, including citrate, pyruvate, malate, fumarate, and tartrate; on protein extracts; and on a limited number of carbohydrates. Sulfur, thiosulfate, and cystine are reduced to hydrogen sulfide. Sulfate, sulfite, and nitrate are not reduced. The DNA base composition is 44 mol% G + C. The 16S ribosomal DNA sequence revealed that strain RWcit2T is a member of the domain Bacteria and forms a branch that is approximately equidistant from Dictyoglomus thermophilium and Thermoanaerobacter spp. (level of similarity, 82%). Strain RWcit2T cannot be placed in any previously described taxon based on its phylogenetic and physiological traits and is named Anaerobaculum thermoterrenum gen. nov., sp. nov.

Bacteria, Anaerobic↗
PubMed2003

Corporate citizenship: Statoil.

Open markets alone do not guarantee equitable and sustainable development. Income disparities are growing both within and between countries to the extent that the marginalization of the poor has become a key challenge of globalization. To meet this challenge, the global community must address the governance gap between global finance/economics and local or national politics in world affairs. This article discusses how globalization is shaping Statoil's approach to corporate citizenship. The Norwegian firm, with 17,000 workers in some 25 countries, is one of the major net sellers of crude oil and supplies Europe with natural gas. Statoil maintains that corporations can contribute to global governance by conducting business in a manner that is ethical, economically viable, environmentally sound, and socially responsible. This contribution can be achieved through development partnerships with national governments, multilateral institutions, and nongovernmental organizations. Norway's Statoil ASA is one of the world's largest net sellers of crude oil and a major supplier of natural gas to Europe. It is the leading Scandinavian retailer of petroleum and other oil products. Statoil employs approximately 17,000 workers and operates in 25 countries.

Journal Article↗
PubMed2000

Naturally occurring radioactive materials (NORM): a matter of wide societal implication.

Naturally occurring radioactive materials are ubiquitous on Earth and their radioactivity may become concentrated as a result of human activities. Numerous industries produce concentrated radioactivity in their by-products: the coal industry, petroleum extraction and processing, water treatment, etc. The present reference system of radiation protection does not provide a complete framework for the coherent management of all types of radioactively contaminated materials. Inconsistencies in waste management policy and practice can be noted across the board, and especially vis-à-vis the management of radioactive waste from the nuclear industry. This article reviews the present societal approach to manage materials that are radioactive but are often not recognised as being such, and place the management of radioactive materials from the nuclear industry in perspective.

Background Radiation↗
PubMed2001

[Fire-eater's pneumonia--a difficult differential diagnosis].

Acute aspiration of petroleum or other hydrocarbon products can cause a distinct type of chemical pneumonitis known as fire-eater's pneumonia. Initial findings on chest X-rays are ambiguous and not uniform in nature. Among the most common belong mottled or patchy, local or diffuse perihilar and basal uni- or bilateral infiltrates, areas of atelectasis, tumor-like lesions and rarely pleural effusions. CT finding often shows formation of smaller or larger pneumatoceles. Those cavities tend to regress spontaneously over weeks or months. Clinical diagnosis is sometimes very difficult, especially in cases, when past history of "fire-eating" is not known to the physician. The authors present clinical manifestation, sequential X-ray and CT findings in one patient with fire-eater's pneumonia. To diagnose the disease, not only paraclinical exploration is needed, but also the patient's past history plays an important role. Without it this puzzling clinical unit can remain undiagnosed.

Adult↗
PubMed1983

[Is benzo(a)pyrene an indicator of carcinogenic pollution?].

High-pressure liquid chromatography was used in the measurement of level of polycyclic aromatic hydrocarbons (PAH) in 60 environmental specimens (water, bottom sediments and soil in fresh- and sea-water basins, solid wastes of fuel combustion). Concentrations of benzo(a)pyrene considered to be an indicator of carcinogenic PAH, varied significantly: 0.05-13.0% of the total hydrocarbon level and 0.8-100.0% of carcinogenic PAH in water; 2.7-8.1 and 4.0-36.8 in bottom sediments, and 0.4-6.0 and 9.9-45.1 in solid wastes of fuel combustion, respectively. Since PAH, other than benzo(a)pyrene, e. g. benzofluoranthenes and dibenzopyrenes, sometimes predominated, it is suggested that benzo(a)pyrene cannot be used as indicator of environmental pollution, unless a full-scale test for other PAH is completed. Benzo(a)pyrene level may be used for monitoring carcinogenic pollution after relevant hygienic and cancer control tests are carried out.

Benzo(a)pyrene↗