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PubMed2001

[Technique and advance of comprehensive two-dimensional gas chromatography].

Many analytical problems require more resolution than the conventional single column chromatographic technique can provide. In such cases the separation power can be enhanced by using more than one separation technique or mechanism. The sample is then dispersed in different time dimensions. The resolution obtained depends strongly on the difference between these dimensions. The highest resolution is gained when there is no correlation between the separations, the dimensions being orthogonal to each other. Comprehensive two-dimensional gas chromatography (GC x GC) provides a true orthogonal separation system in which a modulator serially couples two columns containing dissimilar stationary phases. It focuses and subsequently reinjects components eluting from the first column into the second one. The system generates a peak capacity that is approximately equal to the product of the peak capacities of the two individual separation systems. In this paper, technique and instrumental considerations of GC x GC are discussed. The three designs of contemporary GC x GC systems are presented and compared. A number of typical applications on complex samples such as petroleum products and environmental pollutants are also cited. Finally, the future perspectives of GC x GC are simply discussed.

Chromatography, Gas↗

PubMed2006

An integrated numerical and physical modeling system for an enhanced in situ bioremediation process.

Groundwater contamination due to releases of petroleum products is a major environmental concern in many urban districts and industrial zones. Over the past years, a few studies were undertaken to address in situ bioremediation processes coupled with contaminant transport in two- or three-dimensional domains. However, they were concentrated on natural attenuation processes for petroleum contaminants or enhanced in situ bioremediation processes in laboratory columns. In this study, an integrated numerical and physical modeling system is developed for simulating an enhanced in situ biodegradation (EISB) process coupled with three-dimensional multiphase multicomponent flow and transport simulation in a multi-dimensional pilot-scale physical model. The designed pilot-scale physical model is effective in tackling natural attenuation and EISB processes for site remediation. The simulation results demonstrate that the developed system is effective in modeling the EISB process, and can thus be used for investigating the effects of various uncertainties.

Biodegradation, Environmental↗

PubMedDate not supplied

[Effect of water pollution by oil and oil products on barrier functions of bacterial cell cytoplasmic membranes].

The effects of oil, diesel fuel, and kerosene on the electroorientational spectra and osmo-optical characteristics of bacterial cells were studied. Electroorientational spectra were found to be affected over the entire frequency range studied; changes in low-frequency (< 100 kHz) electroorientation were related to alterations in the cell surface, and those in high-frequency electroorientation, to the impairment of the barrier function of the plasma membrane. The membranotropic activity of petroleum products was also demonstrated by the osmo-optical method. Of nine bacterial species studied, Pseudomonas fluorescens VKM B-894, P. oleovorans VKM B-1522, and P. stutzeri VKM B-903 were most susceptible to the membranotropic action of kerosene; P. putida VKM B-1292 was the most resistant. Other bacterial strains studied were moderately sensitive.

Cell Membrane Permeability↗

PubMed1980

Food and energy choices for India: a programming model with partial endogenous energy requirements.

This paper presents a mathematical model for all matter-energy processing subsystems at the level of the society, specifically India. It explores India's choices in the food and energy sectors over the coming decades. Alternative land intensive, irrigation energy intensive, and fertilizer intensive techniques of food production are identified using a nonlinear programming model. The land saved is devoted to growing firewood. The optimum combination of railway (steam, diesel, and electric traction) and road (automobiles, diesel trucks, and diesel and gasoline buses) transport is determined. For the oil sector, two alternative sources of supply of crude oil and petroleum products are included, namely, domestic production and imports. The optimum choice is determined through a linear programming model. While the model is basically a static one, designed to determine the optimal choice for the target year of 2000-2001, certain intertemporal detail is incorporated for electricity generation. The model minimizes the costs of meeting the needs for food, transport in terms of passenger kilometers and goods per ton per kilometer, energy needs for domestic cooking and lighting, and the energy needs of the rest of the economy.

Conservation of Energy Resources↗

PubMed2001

Polycyclic aromatic hydrocarbon 13C/12C ratio measurement in petroleum and marine sediments application to standard reference materials and a sediment suspected of contamination from the Erika oil spill.

This paper describes a simple and rapid sample preparation procedure allowing to measure the stable carbon isotopic composition of polycyclic aromatic hydrocarbons (PAHs) in petroleum and in sediments. The aromatic fraction is first purified and isolated on alumina and silica micro-columns. A high-performance liquid chromatography fractionation allows one then to isolate each aromatic family in order to limit coelutions between PAHs. Moreover, this purification step reduces the importance of the unresolved complex mixture which otherwise contribute to the GC-isotope ratio MS background signal. The application of this analytical procedure has allowed one to determined PAH isotopic composition in a reference material crude oil (SRM 1582) and a marine sediment (SRM 1944) with good reproducibility as uncertainties between three independent assays performed were lower than 0.5 per thousand. This analytical procedure has then been successfully applied to confirm the contamination of a sediment by the petroleum product spilled by the Erika tanker after its wreck on 12 December 1999 close to the Atlantic Coast of France.

Atlantic Ocean↗

PubMed2002

Effect of nutritional state on Hsp60 levels in the rotifer Brachionus plicatilis following toxicant exposure.

The nutritional state of an organism can affect the results of toxicity testing. Here we exemplified this fact by examining the effect of nutritional deprivation on heat shock protein 60 (hsp60) production in the rotifer Brachionus plicatilis following exposure to two proven inducers of hsp60, a water-accommodated fraction of crude oil (WAF) and a dispersed oil preparation (DO). Both DO and WAF exposures of unfed rotifers resulted in significantly greater hsp60 levels than that of fed DO and WAF exposed rotifers at 8 h: 870 and 3100% of control, respectively. Results clearly demonstrate that a poor nutritional state potentiates stress protein induction upon exposure to water-soluble petroleum products. It is therefore critical to define the organismal nutritional status when reporting toxic responses.

Animals↗

PubMed2003

Composition and structure of agents responsible for development of water repellency in soils following oil contamination.

Soil from the Ellerslie site of experimental oil contamination in Alberta developed water repellency some years after initial remediation. The water-repellent soils were compared to clean soils and contaminated but wettable soils by solid-state nuclear magnetic resonance (NMR). The effects of extraction with CH2Cl2 (for petroleum hydrocarbons), NaOH (for natural organic matter), and 2-propanol/ammonia (IPA/NH3) on wettability were evaluated by the molarity of the ethanol droplet (MED) test. Soil extracts and whole soils, after extraction, were examined using NMR and Fourier transform infrared spectroscopy (FTIR). On the basis of the structure--MED correlations, a model of a thin-layer natural organic matter--petroleum products complex formed under strong drying conditions is proposed to account for the development of water repellency. Studies of two similar soils from accidental oil spills are supportive.

Environmental Pollution↗

PubMed2006

Water-soluble inhibitor on microbiologically influenced corrosion in diesel pipeline.

The effect of water-soluble corrosion inhibitor on the growth of bacteria and its corrosion inhibition efficiency were investigated. Corrosion inhibition efficiency was studied by rotating cage test and flow loop techniques. The nature of biodegradation of corrosion inhibitor was also analyzed by using Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR) and Gas chromatography and mass spectrometer (GC-MS). The bacterial isolates (Serratia marcescens ACE2, Bacillus cereus ACE4) have the capacity to degrade the aromatic and aliphatic hydrocarbon present in the corrosion inhibitor. The degraded products of corrosion inhibitor and bacterial activity determine the electrochemical behaviour of API 5LX steel. The influence of bacterial activity on degradation of corrosion inhibitor and its influence on corrosion of API 5LX have been evaluated by employing weight loss techniques and electrochemical studies. The main finding of this paper is that the water-soluble corrosion inhibitor is consumed by the microbial action, which contributes to the decrease in inhibitor efficiency. The present study also emphasis the importance of evaluation of water-soluble corrosion inhibitor in stagnant model (flow loop test) and discusses the demerits of the water-soluble corrosion inhibitors in petroleum product pipeline.

Anti-Bacterial Agents↗

PubMedDate not supplied

[Space-time water monitoring system at the Iriklinsk hydroelectric power station].

The Microbiosensor B 17677 F test system was applied to make a space-time monitoring of the biotoxicity of water used for production and everyday purposes at the Iriklinsk hydroelectric power station (IHEPS) and to identify the leading causes determining the biotoxicity of tested samples. There were seasonal variations in the biotoxicity with the maximum in spring and with minimum in winter and spring and a relationship of the spring rise in the biotoxicity to water pH changes. There was also an association of the certain values of the biotoxicity of industrial water with the concentration of petroleum products that are major pollutants at the IHEPS. The datum points that characterize the maximum level of technogenic exposure were identified.

Catchment Area, Health↗

PubMedDate not supplied

The confirmation of volatiles by solid-phase microextraction and GC-MS in the investigation of two traffic fatalities.

A simple, sensitive, and reliable method was developed for the confirmation of nonroutine volatiles in the investigation of two traffic fatalities. Solid-phase microextraction (SPME) fibers were used to extract volatile compounds from the headspace of sample vials; components were subsequently analyzed by gas chromatography-mass spectrometry (GC-MS). In the first case, ethanol and methylene chloride were detected in a urine sample by headspace SPME and GC-MS. The second case involved the analysis of volatile petroleum products from submitted specimens by headspace SPME and GC-MS. In both cases, SPME and GC-MS analyses provided crucial evidence in the investigation of the traffic fatalities.

Accidents, Traffic↗

PubMed1984

Cancer mortality patterns by work category in three Texas oil refineries.

A previous proportionate mortality ratio analysis revealed elevated mortality from brain tumors, stomach cancer, leukemia, and other cancers among OCAW members employed in three Texas oil refineries. In order to evaluate these findings, complete work histories of cases and a matched set of controls who died from other causes of death were obtained from company personnel records. Work histories were summarized by classifying each job title and department entry into one of several broad work categories of refinery unit operations. A worker was considered "exposed" to a work category if he was known to have worked at least 1 day in the category 15 or more years prior to his death. Maximum likelihood estimates of the relative risk for brain tumor, stomach cancer, and leukemia were calculated by work category using a procedure for matched case-control data. No strong associations for brain tumor risk were seen with any work categories. A slight association for leukemia was seen among workers in the Treating category, which included unit operations that reduce the level of aromatic and sulfur constituents of petroleum products and combine them with additives to improve their quality. Stomach cancer risk was elevated among maintenance workers and workers exposed to lubricating oils and paraffin wax processing.

Brain Neoplasms↗

PubMed1981

Benzine-sniffing neuropathy.

Eight children and adolescents with a predominantly motor neuropathy of which the most likely cause was n-hexane are described. n-Hexane is one of the impurities in highest concentration in benzine, a petroleum product freely available at most corner stores in South Africa. It is bought freely by a large number of Black children in Natal and sniffed to produce a state of euphoria. Benzine sniffing by children constitutes a major health hazard in Natal.

Adolescent↗

PubMed2001

Farm-related dermatoses in Iowa male farmers and wives of farmers: a cross-sectional analysis of the Iowa Farm Family Health and Hazard Surveillance Project.

Agricultural workers are exposed to a variety of hazards that increase their risk for dermatitis. Nevertheless, the prevalence, patterns, and risk factors for dermatitis have not been well characterized among farmers in the United States. We assessed the prevalence and risk factors for dermatitis among 382 male farmers and 256 wives of farmers in Iowa using a cross-sectional study design. From 1992 to 1994, we collected data on potential risk factors and dermatitis. The results showed that 9.6% of male farmers and 14.4% of wives of farmers reported dermatitis during the previous 12-month period. In multivariable models, a history of allergy (odds ratio [OR], 8.2; 95% confidence interval [CI], 2.0 to 33.3) was strongly associated with dermatitis among male farmers. Among wives of farmers, some college education (OR, 3.4; 95% CI, 1.1 to 9.9) and exposure to petroleum products (OR, 3.1; 95% CI, 1.3 to 7.0) were associated with dermatitis. These results can be used to form preventive efforts in controlling farmwork-related exposures.

Adult↗

PubMed1976

Oil degradation in soil.

The environmental effects of adding certain selected petroleum products to field soils at widely separated geographical locations under optimum conditions for biodegradation were studied. The locations selected for study of soil biodegradation of six oils (used crankcase oil from cars, used crankcase oil from trucks, an Arabian Heavy crude oil, a Coastal Mix crude oil, a home heating oil no. 2, and a residual fuel oil no. 6) were Marcus Hook, Pennsylvania, Tulsa, Oklahoma, and Corpus Christi, Texas. The investigative process, covering a period of 1 year at each location, was conducted in 14 fields plots (1.7 by 3.0 m) to which the oils were added in a single application at a rate of 11.9 m3/4 X 10(3) m2. One-half of the plots at each location were fertilized, and the incorporation of the oils and fertilizers was accomplished with rototillers to a depth of 10 to 15 cm. Concentrations of all oils decreased significantly at all locations. The average reduction ranged from 48.5 to 90.0% depending upon the type of oil and location. Rates of degradation did not exceed 2.4 m3/4 X 10(3) m2 per month. Compositional changes in the oil with time were investigated using silica gel fractionation, gas chromatography, and ultraviolet absorbance. With the possible exception of the two fuel oils, the compositional changes were generally in the same direction for all of the oils. The silica gel fractionation and gravimetric data on residual oils show that all classes of compounds were degraded, but the more polar type degrade more slowly. Analysis of runoff water, leachate, and soils indicated that at the concentration applied no oil less was observed from these plots via water movement. No significant movement of lead compounds added to the soils in the used crankcase oils was observed. Significant increases in hydrocarbon-utilizing microorganisms were demonstrated in all treated plots using either the pure hydrocarbon, n-hexadecane, or the applied oils as the growth substrate. These increases were usually sustained throughout the year. Significant increases in hydrocarbon-utilizing fungi were not demonstrated by the plating technique used. The concentrations of residual oils or their oxidation products were of sufficient magnitude in the treated plots, 9 months after application, to cause significant inhibition of plant growth. From the data obtained, it was not possible to determine the type of compounds causing this inhibition or their long-term environmental effects.

Bacteria↗

PubMed1991

Mutagenicity study of urine from smoking and non-smoking road tanker drivers.

Urine from 32 road tanker drivers handling petrol, diesel, paraffin and white spirit was tested in the Salmonella/microsome mutagenicity system using tester strains TA98 anbd TA100. Urine samples were collected before and after tanking and were concentrated 250-fold on XAD-2 columns before testing. Controls were 33 office employees from the same plant. No effect on urinary mutagenicity of occupational exposure to petroleum products was found. Significant differences in mutagenic effect were demonstrated between smokers and non-smokers. Methodological experiments demonstrated a dose/response effect of smoking on urinary mutagenicity. A modified test using a preincubation period and an increased concentration of bacteria was more sensitive than the standard Ames test to mutagens from tobacco smoking.

Dose-Response Relationship, Drug↗

PubMed2001

Luminescence spectroscopy as a screening tool for the potential carcinogenicity of asphalt fumes.

A subset of polycyclic aromatic compounds (PACs), which contain 4-6 annulated rings, has been documented as the source of carcinogenicity in animal skin painting studies of petroleum products and asphalt fumes (M. L. Machado, P. W. Beatty, J. C. Fetzer, A. H. Glickman and E. L. McGinnis, Fundam. Appl. Toxicol., 1993, 21, 492; T. A. Roy, S. W. Johnson, G. R. Blackburn and C. R. Mackerer, Fundam. Appl. Toxicol., 1988, 10, 466). Because of the chemical complexity of these materials, it has been difficult to identify the specific compounds within this broad range of PACs responsible for their carcinogenicity. An alternative approach using luminescence spectroscopy was taken in this study to quantify, without identification, a subset of these compounds that appears to cause cancer. The fluorescence response at a specific wavelength pair was obtained for 39 laboratory asphalt fume condensates from animal skin painting studies, yielding a linear correlation coefficient of R2 = 0.96 between the fluorescence response in these materials and the carcinogenicity found in animal studies. In the absence of other asphalt fume condensates from animal studies, 17 petroleum oils were also evaluated using this method and compared with the available animal skin painting data. The details of the method include a clean-up step that removes the highly polar compounds and spectral subtraction of two- and three-ring PAC interference, both of which add to the fluorescence response, yet were not found to contribute to a carcinogenic response from skin painting studies. Full scan fluorescence plots also produce a fingerprint which can be used to assess contamination, such as coal tar products or mixtures of materials, that are not defined as asphalt, yet may be present in the working environment.

Air Pollutants↗

PubMed1981

Microextraction and gas chromatographic analysis of selected petroleum hydrocarbons in water and fish tissue.

The most effective water to solvent ratio is determined for the analyses of aromatic hydrocarbons in water using hexane. The recoveries of these hydrocarbons formed in the water soluble fraction of crude oils and petroleum products are measured using a microextraction procedure. Recoveries were in the 30-40% range but are consistent for each compound. Fish muscle samples are fortified with the standards and the recoveries measured with a modified extraction procedure using dichloromethane as the primary extracting solvent. This is dispersed in water using acetone and finally extracted with hexane. Recoveries range from 90-113% with a mean value of 98%.

Animals↗

PubMed2003

Recycling of meat and bone meal animal feed by vacuum pyrolysis.

Due to the recent bovine spongiform encephalopathy (BSE) crisis in the European beef industry, the use of animal-derived products to feed cattle is now severely restricted. Large quantities of waste animal meat and bone meal (MBM), also known as animal flour, have to be safely disposed of or transformed. One disposal option is pyrolysis. Vacuum pyrolysis of an animal flour sample has been performed in a laboratory reactor. The results obtained revealed that vacuum pyrolysis can be an attractive alternative to incineration and cement kilns. The process generated a combustible gas (15.1 wt %), a high calorific value oil (35.1 wt %), a solid residue rich in minerals (39.1 wt %), and an aqueous phase rich in organics (10.7 wt %). The gas and the aqueous phase can be used to provide heat to the vacuum pyrolysis reactor and the MBM drying unit. The oil can be used alone or mixed with petroleum products as a fuel in boilers or gas turbines. Conversion of animal waste by pyrolysis into fuels can contribute to the reduction of greenhouse gases. It is suggested to use the solid residue for agricultural soil enrichment in minerals and as a soil moisturizer.

Abattoirs↗