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Assessment of the phototoxicity of weathered Alaska North Slope crude oil to juvenile pink salmon.

Petroleum products are known to have greater toxicity to the translucent embryos and larvae of aquatic organisms in the presence of ultraviolet radiation (UV) compared to toxicity determined in tests performed under standard laboratory lighting with minimal UV. This study assessed the acute phototoxicity of the water accommodated fractions of weathered Alaska North Slope crude oil (ANS) to juvenile pink salmon, which are a heavily pigmented life stage. Fish in the highest ANS treatments exhibited melanosis, less mobility, reduced startle response, erratic swimming, and loss of equilibrium. Gills from fish exposed to ANS had elevated levels of hydroperoxides in oil-only, UV-only, and oil+UV treatments compared to control fish, which was indicative of increased lipid peroxidation in gill tissue. Under the test conditions of moderate salinity, low UV and high short-term oil exposure there were no indications of photoenhanced toxicity as assessed by elevation of mortality, behavioral impairment, or gill lipid peroxidation in oil+UV treatments. The results of this study suggest that pink salmon may be at less risk from photoenhanced toxicity compared to the translucent early-life stages of several other Alaska species.

Alaska↗

Quantification and interpretation of total petroleum hydrocarbons in sediment samples by a GC/MS method and comparison with EPA 418.1 and a rapid field method.

Total petroleum hydrocarbons (TPH) as a lumped parameter can be easily and rapidly measured or monitored. Despite interpretational problems, it has become an accepted regulatory benchmark used widely to evaluate the extent of petroleum product contamination. Three currently used methods (GC/MS, conventional EPA 418.1, and a rapid field method PetroFLAG) were performed to quantify the TPH content in samples collected from a site contaminated by transformer oil. To standardize the method and improve the comparability of TPH data, crucial GC-based quantification issues were examined, e.g., quantification based on internal standards (ISTD) vs external standards (ESTD), single vs multiple ISTD, and various area integration approaches. The interpretation of hydrocarbon chromatographic results was examined in the context of field samples. The performance of the GC/MS method was compared with those of EPA 418.1 and PetroFLAG. As a result, it was observed that the ISTD quantification method was preferred to the ESTD method, multiple ISTD might be better than single ISTD, and three different area integration approaches did not have a significant effect on TPH results. Evaluation of the chromatograms between a reference sample and three unknown samples showed that the extent of contamination varied appreciably with sample depth. It was also found that there existed a good positive correlation between GC/MS and both EPA 418.1 and PetroFLAG, and that EPA 418.1 produced the higher overall estimate while GC/MS and PetroFLAG resulted in lower, more statistically comparable TPH values.

Chemistry Techniques, Analytical↗

Review of behaviour of oil in freezing environments.

The current knowledge of the physical fate and behaviour of crude oil and petroleum products spilled in Arctic situations is reviewed. The fate and final deposition of oil in marine conditions is presented as based on the extant literature. Spreading models were evaluated for oil on ice, under ice, in snow, in brash ice, and between blocks of ice. Models of oil transport under sheet and broken ice were considered, both for sea and river conditions. The ability of ice sheets to trap oil is discussed in relation to oil storage capacity. The effects of oil on a growing ice sheet were examined, both in terms of ice formation and the thermal effects of oil inclusions in ice. The migration of oil through ice was reviewed, focussing primarily on the movement through brine channels. The effects of oil on the surface of ice were considered, with emphasis on the effects of surface pools on ice melt. Similar consideration was given to the effects of oil on snow on the surface of ice. The few quantitative studies of oil in open and dynamic ice conditions are reviewed. Observations of intentional small-scale spills in leads and ice fields are reviewed and compared with observations from real spills. The conditions under which "oil pumping" from leads occurs were quantified. The most common ultimate fate of oil in an ice field is to be released onto the water surface.

Accidents↗

Effect of ethanol on BTEX biodegradation kinetics: aerobic continuous culture experiments.

The use of ethanol as an automotive fuel oxygenate represents potential economic and air-quality benefits. However, little is known about how ethanol may affect the natural attenuation of petroleum product releases. Chemostat experiments were conducted with four pure cultures (representing archetypes of the known aerobic toluene degradation pathways) to determine how ethanol affects benzene, toluene, ethylbenzene, and xylene (BTEX) biodegradation kinetics. In all cases, the presence of ethanol decreased the metabolic flux of toluene (measured as the rate of toluene degradation per cell). This negative effect was counteracted by an ethanol-supported increase in biomass, which is conducive to faster degradation rates. When the influent total organic carbon (TOC) of the toluene-ethanol mixture was kept constant, the metabolic flux of toluene was proportional to its relative contribution to the influent TOC. This empirical relationship was used to derive a mathematical model that simulated effluent benzene concentrations as a function of the influent mixed-substrate composition, the dilution rate, and Monod kinetic coefficients. Under carbon-limiting conditions (1 mg/L influent benzene), the data and model simulations showed an increase in benzene removal efficiency when ethanol was fed at low concentrations (ca. 1 mg/L) because its positive effect on cell growth outweighed its negative effect on the metabolic flux of benzene. High ethanol concentrations, however, had a negative effect, causing oxygen limitation and increasing effluent benzene concentrations to higher levels than when benzene was fed alone. The slower BTEX degradation rates expected at sites with high ethanol concentrations (e.g., at gasohol-contaminated sites) could result in longer BTEX plumes and a greater risk of exposure.

Biodegradation, Environmental↗

Optimizing detection limits for the analysis of petroleum hydrocarbons in complex environmental samples.

To evaluate the sources, transport, bioremediation, fate, and effects of spilled petroleum and petroleum products, environmental studies often measure parent and alkylated polycyclic aromatic hydrocarbons (PAH), alkanes, and chemical biomarkers (e.g., triterpanes). Accurate data for low analyte concentrations are required when environmental samples contain hydrocarbons from multiple sources that need to be resolved and quantified. The accuracy and usefulness of the analyses can be improved by lowering the method detection limits (MDLs) for these compounds. Misidentification of hydrocarbon source can result when the MDLs are too high. Modifications to standard analytical methods (i.e., U.S. Environmental Protection Agency Method 8270) can lower MDLs by factors ranging from 10 to 1000. This reduction has important implications for ecological-risk assessments. Modifications having the greatest impact on the MDL include GCMS analysis in the selected-ion-monitoring mode (SIM), increased sample size, column cleanup of the extract, and decreased preinjection volume (volume of final extract prior to injection into instrument). In one study in which a benthic sediment sample was spiked with low levels of topped (heated to remove more volatile PAH that are naturally enriched in crude oil) Alaska North Slope crude, MDLs for individual PAH analytes and biomarkers were determined to be less than 0.5 ng/g (ppb) dry weight and less than 5 ppb dry weightfor individual alkanes. Similar results were obtained when the sediment was spiked with the 16 EPA priority pollutants. In addition, a method has been developed to estimate MDLs for source-specific alkylated PAH analytes and chemical biomarker compounds for which standards are not commercially available or are prohibitively expensive. These improved analytical techniques have been used to identify and quantify low levels of hydrocarbons, derived from both natural and anthropogenic sources, found in the benthic sediments of Prince William Sound, AK.

Environmental Monitoring↗

Antiestrogenicity of clarified slurry oil and two crude oils in a human breast-cancer cell assay.

Exposure to crude oil and certain petroleum products can be a serious health hazard. Clarified slurry oil (CSO) is a complex mixture of hydrocarbons derived from the processing of crude oil, and is a known systemic and developmental toxicant, mutagen, and carcinogen. In the present study, CSO and two crude oils, Belridge heavy crude oil (BHCO) and Lost Hills light crude oil (LHLCO), were examined for their estrogenic and antiestrogenic properties in a human breast-cancer cell (MCF-7) assay. The MCF-7 focus assay is based on postconfluent cell growth and tissue restructuring, measured as the postconfluent development of multicellular nodules or foci. The mutagenicity indices of BHCO and LHLCO also were determined in a modified Ames Salmonella assay. Oil samples were prepared in dimethyl sulfoxide, resulting in extraction of virtually all of the aromatic compounds including the sulfur- and nitrogen-substituted three- to seven-ring polycyclic aromatic compounds comprising 62.2% of the CSO, 9% of the BHCO, and 2% of the LHLCO by total weight. None of the three samples was estrogenic in the MCF-7 focus assay. In contrast, all of the samples were antiestrogenic; that is, they inhibited the development of foci induced by 1 nM 17beta-estradiol (E2). The potencies of the oil samples for both antiestrogenicity and mutagenicity were correlated with the percent of polycyclic aromatic compounds they contained. Two potential mechanisms for the observed antiestrogenicity were examined. Radiometric analysis of the catabolism of [3H]E2 in MCF-7 cell cultures demonstrated that all three samples increased catabolism of E2. Results from a whole-cell estrogen-receptor (ER) binding assay suggested that metabolites of compounds in the oil samples might have competed with [3H]E2 for ER in the MCF-7 cultures. Thus the antiestrogenicity of the oil samples may occur through at least two mechanisms, increased catabolism of E2 and antagonistic binding to ER.

Binding, Competitive↗

Parental occupation and other factors and cancer risk in children: II. Occupational factors.

A population-based case-control study was conducted on 593 cancer cases in children from 0 to 14 years of age diagnosed in Moscow from 1986 to 1988. The study included 1181 healthy controls matched by age, gender and residence. Parental exposures prior to conception, including exposures to petroleum products, organic solvents, unspecified chemicals, soldering aerosols, ionizing radiation, electromagnetic fields (EMF), visual display units (VDU) and high temperature in the work environment, were significantly more frequent among the cases than among the controls (p < 0.05). Leukemia risk was associated with paternal exposure to ionizing radiation [odds ratio (OR) 6.7; 95% confidence interval (CI) 2.8-15.8], EMF (OR 4.6; 95% CI 1.8-11.9), VDU (OR 2.4; 95% CI 1.0-5.8) and unspecified chemicals (OR 2.0; 95% CI 1.02-4.1). Leukemia risk was also higher when mothers were exposed to solvents (OR 3.1; 95% CI 1.5-6.3), unspecified chemicals (OR 2.0; 95% CI 1.0-4.3), ionizing radiation (OR 10.3; 95% CI 1.3-83.4) and EMF (OR 5.2; 95% CI 1.6-16.8). Increased risk of non-Hodgkin's lymphoma was shown to be related to maternal exposure to oil products (OR 3.3; 95% CI 1.01-10.7) and unspecified chemicals (OR 3.3; 95% CI 1.01-10.7). Exposure to VDU was found to be associated with increased risk of neuroblastoma (6/1; OR 13.8; 95% CI 1.9-100.0).

Adult↗

Occupation, exposure to chemicals and risk of gliomas and meningiomas in Sweden.

BACKGROUND: Occupational exposures may be related to the development of brain cancer. The objective was to estimate occupational-specific risk of gliomas and meningiomas among Swedish men and women gainfully employed in 1970 over the period 1971-1989, and the influence of occupational exposure to chemical substances. METHODS: A dataset linking cancer diagnoses from the Swedish national cancer register to occupational and demographical data obtained in the 1970 census was used to fit log-linear Poisson models, in order to obtain relative risks adjusted by age, period, geographical area and town size. Exposure to 13 chemicals was assessed using a Swedish job-exposure matrix. RESULTS: The main findings of this study among men were the increased risk of glioma with occupational exposure to arsenic, mercury, and petroleum products and of meningioma with lead. Women in occupational sectors with a higher socio-economic status showed an increased incidence of both, gliomas and meningiomas. CONCLUSIONS: Occupational exposure to some chemicals appeared to be related with an increased risk of glioma and meningioma in men. Exposures involved in glioma and meningioma development seemed to be different.

Adult↗

Parental occupational exposures and risk of childhood cancer: a review.

We reviewed the literature in order to summarize the present knowledge on the association between parental occupational exposures to chemicals and the risk of childhood malignancy. The 32 studies pertaining to this topic were evaluated by considering various study qualities such as sample size, specificity of outcome, confounding, exposure specificity, and control selection. When evaluating the findings from any epidemiologic study, the potential sources of bias have to be considered. The selection of subjects, misclassification of exposure or outcome, and confounding from extraneous factors can contribute to a biased estimate of effect. Studies done to minimize these potential biases will be more valid, and these studies should be given the most weight when parental occupational exposures are evaluated as risk factors for childhood malignancy. We conclude that the preponderance of evidence supports the hypothesis that occupational exposure of parents to chemicals increases the risk of childhood malignancy. The parental occupational exposures implicated in childhood malignancy risk are exposure to chemicals including paints, petroleum products, solvents (especially chlorinated hydrocarbons) and pesticides, and exposure to metals. The available data do not allow the identification of specific etiologic agents within these categories of compounds. Future epidemiologic and toxicologic studies should be designed to pursue these leads.

Chemical Industry↗

Acute high dose exposure to benzene in shipyard workers.

Fifteen degassers were acutely exposed over several days to high concentrations (> 60 ppm) of benzene during removal of residual fuel (degassing) from shipboard fuel tanks. Medical surveillance evaluation mandated by the Occupational Safety and Health Administration's (OSHA) Benzene Standard initially revealed 11 workers (73%) reporting neurotoxic symptoms while degassing. Workers with more than 2 days (16 hours) of acute exposure were significantly more likely to report dizziness and nausea than those with 2 or fewer days of acute exposure. Repeated laboratory analyses performed over a 4-month period after the acute exposure revealed at least one hematologic abnormality consistent with benzene exposure in 9 (60%) of these degassers. One year later, 6 workers (40%) had persistent abnormalities; an additional worker with normal hematologic parameters at the time of our initial evaluation subsequently developed an abnormality consistent with benzene exposure. Numerous large granular lymphocytes were observed on 6 (40%) of the peripheral blood smears. Despite these laboratory findings, there were no significant associations between the presence of hematologic abnormalities and either the number of hours of acute benzene exposure or the duration of employment as a degasser. Volatilization of benzene from the residual fuel was the suspected source of benzene in the headspace of tanks. Confined space exposure to petroleum products may be exposing workers to benzene at levels above the OSHA Short-Term Exposure Limit (STEL). This situation warrants further study.

Adult↗

Nanocap-shaped tin phthalocyanines: synthesis, characterization, and corrosion inhibition activity.

Thermal and microwave reactions between [PcSn(IV)Cl2] (1) and the potassium salts of eight fatty acids (2 a-h) led to cis-[(RCO2)2Sn(IV)Pc] compounds (3 a-h) in yields ranging from 54 to 90 %. Compounds 3 a-h were fully characterized by elemental analysis, spectroscopy (IR, UV/Vis, multinuclear NMR), and seven X-ray diffraction structures, whereby two different allotropes were observed in two cases. The two carboxylates in 3 have a cis anisobidentate binding mode, octacoordination of the tin atoms with square-antiprismatic geometry, and pi-electron-rich nanocap shapes. On account of the latter characteristics, 3 a-h compounds have anticorrosion properties. LPR and Tafel electrochemical methods were used to characterize the behavior of these derivatives in naturally aerated sour brine, which is a common environment in petroleum production and refinery operations. The measurement of the corrosion rate of carbon steel AISI 1018 in the presence of 3 a-h (500 ppm) gave efficiencies of 61-87 % for the inhibitor performance. Of the different derivatives examined, compounds 3 e and 3 h were the most effective corrosion inhibitor prototypes.

Journal Article↗

A population-based case-control study of cancers of the nasal cavity and paranasal sinuses in Shanghai.

A population-based case-control study of cancer of the nasal cavity and sinuses, involving interviews of 60 incident cases and 414 controls, was conducted in Shanghai. Cigarette smoking was associated with a mild elevation in risk of squamous-cell carcinoma but not cancers of other cell types. Occupational exposures to wood and silica dusts and to petroleum products, and the use of wood and straw as cooking fuel, were linked to moderate increases in risk, while 4-fold or greater increases were associated with a history of chronic nasal diseases, including those occurring 10 or more years prior to cancer diagnosis. Dietary analyses revealed a significant protective effect of consumption of allium vegetables, oranges and tangerines, with a 50% reduced risk of nasal cancer among individuals in the highest intake group of these foods. Consumption of salt-preserved vegetables, meat and fish was associated with a significantly increased risk of nasal cancer in a dose-response fashion, with a 5-fold excess observed for the heaviest intake of these salted foods. These findings suggest that dietary factors may contribute to the development of nasal cancer.

Adult↗

Sources of pollution and sediment contamination in Newark Bay, New Jersey.

A review of historical water quality and sediment quality data and chemical body burdens in biota reveals significant levels of a wide range of chemicals and water quality stressors throughout the Newark Bay, New Jersey estuary. The estuary, which encompasses the Passaic River, Hackensack River, Kill van Kull, and the Arthur Kill, has been heavily impacted by both industrial and urban expansion for more than 200 years. The available information was sufficient to identify the major sources of pollution and the contributions of various metals and organic chemicals to the aquatic environment. Mass loadings for several chemicals and water quality parameters were estimated for publicly owned treatment works (POTWs) and combined sewer overflows (CSOs), industrial waste discharged either directly to the estuary or through POTWs, stormwater runoff, and accidental spills of petroleum products and hazardous chemicals. The recent trend toward regionalized waste treatment systems to provide secondary levels of treatment have provided some reductions of overall contaminant mass loadings. However, CSOs remain a significant source of untreated waste in the estuary. Additionally, the magnitude of the major sources relative to the ability of the estuary to absorb and dilute the various waste streams suggests that much more must be done to reduce chemical inputs at the source.

History, 19th Century↗

European Atlantic: the hottest oil spill hotspot worldwide.

Oil spills caused by maritime transport of petroleum products are still an important source of ocean pollution, especially in main production areas and along major transport routes. We here provide a historical and geographic analysis of the major oil spills (>700 t) since 1960. Spills were recorded from several key marine ecosystems and marine biodiversity hotspots. The past four decades have been characterized by an overall decrease in the number of accidents and tones of oil spilled in the sea, but this trend was less distinct in the European Atlantic area. Recent black tides from the Erika and Prestige vessels provided new evidence for the high risk of accidents with serious ecological impact in this area, which according to our analysis is historically the most important oil spill hotspot worldwide. The English Channel and waters around Galicia in Spain were the areas with most accidents. Maritime transport in European Atlantic waters has been predicted to continue increasing. Together with our own results this suggests that, in addition to measures for increased traffic safety, deployment of emergency capacities in the spill hotspot areas may be crucial for a sustainable conservation of sea resources and ecosystems.

Accidents, Occupational↗

Fossil fuel biomarkers in sewage sludges: environmental significance

Fossil fuel biomarkers, or "molecular fossils," are specific organic substances found in coals, petroleums, and sedimentary rocks. They are formed during millions of years of sedimentary burial by geochemical alteration of biological molecules, such as cholesterol, under the effect of biodegradation, temperature, pressure, and mineral catalysis, to produce geochemically mature molecules, for example, aromatic steroids (Fig. 1). Since fossil fuel biomarkers have a very specific molecular structure betraying fossil fuel sources, such markers should be useful in assessing the fossil fuel contamination of various modern media such as soils, plants, waters, and modern sediments. Here the identification of fossil fuel biomarkers of high geothermal maturity in sewage sludges provides evidence of the contamination of sludges by petroleum products. The most likely sources of contamination are contaminated vegetal food, road dust, and soil particles carried by rain water.http://link. springer.de/link/service/journals/00114/bibs/9086010/90860484. htm</HEA

Journal Article↗

Skin analysis following dermal exposure to kerosene in rats: the effects of postmortem exposure and fire.

To evaluate the usefulness of skin analysis for the forensic examination of cases involving postmortem dermal exposure to kerosene and/or fire, an experimental study using rats was performed. Rats received dermal exposure to kerosene before or after death, and the effect of fire was determined by burning an area of exposed skin after death. Kerosene concentrations in skin and blood were determined by gas chromatography-mass spectrometry and microscopic observation was performed for skin samples. No differences were observed in skin kerosene levels between antemortem and postmortem exposure. Kerosene concentrations in mildly burned skin where the stratum corneum (SC) was retained were approximately 84% compared to those in non-burned exposed skin, whereas concentrations in severely burned skin where the SC was almost completely burned off were 28% of non-burned skin. Even in non-exposed control skin 14% of the original kerosene concentrations could be detected, which was considered to be caused by contamination during the experimental protocol combined with kerosene's property of a high affinity for the SC. These results suggest that (1) skin analysis is useful in estimating the type of petroleum product involved in crimes or accidents even for postmortem exposure, (2) whether the SC is retained or not primarily determined the kerosene levels in burned skin, and (3) attention must be paid to evaluate the results obtained from skin samples in the light of the circumstances surrounding the case.

Abdomen↗

Monitoring of fogwater chemistry in the gulf coast urban industrial corridor: Baton Rouge (louisiana).

Seventeen fog events were sampled in Baton Rouge, Louisiana during 2002-2004 as part of characterizing wet deposition by fogwater in the heavily industrialized corridor along the Louisiana Gulf Coast in the United States. These samples were analyzed for chemical characteristics such as pH, conductivity, total organic and inorganic carbon, total metals and the principal ion concentrations. The dominant ionic species in all samples were NH4+, NO3-, Cl- and SO4(2-). The pH of the fogwater sampled had a mean value of 6.7 with two cases of acidic pH of 4.7. Rainwater and fogwater pH were similar in this region. The acidity of fogwater was a result of NO3- but partly offset by high NH4+. The measured gaseous SO2 accounted for a small percentage of the observed sulfate concentration, indicating additional gas-to-particle conversion of SO2 to sulfate in fogwater. The gaseous NOx accounted for most of the dissolved nitrate and nitrite concentration in fogwater. The high chloride concentration was attributable to the degradation of chlorinated organics in the atmosphere. The metal composition was traced directly to soil-derived aerosol precursors in the air. The major metals observed in fogwater were Na, K, Ca, Fe, Al, Mg and Zn. Of these Na, K, Ca and Mg were predominant with mean concentrations > 100 microM. Al, Fe and Zn were present in the samples, at mean concentrations < 100 microM. Small concentrations of Mn (7.8 microM), Cu (2 microM), Pb (0.07 microM) and As (0.32 microM) were also observed in the fogwaters, and these were shown to result from particulates (PM2.5) in the atmosphere. The contribution to both ions and metals from the marine sources in the Louisiana Gulf Coast was minimal. The concentrations of all principal ionic species and metals in fogwater were 1-2 orders of magnitude larger than in rainwater. Several linear alkane organic compounds were observed in the fogwater, representing the contributions from petroleum products at concentrations far exceeding their aqueous solubility. A pesticide (atrazine) was also observed in fogwater, representing the contribution from the agricultural activities nearby.

Adsorption↗