Petrogenic Hydrocarbons Research Articles

Effects of the “Aegean Sea” oil spill on biotransformation enzymes, oxidative stress and DNA-adducts in digestive gland of the mussel ( Mytilus edulus L.)

Possible molecular biomarkers of impact by organic pollution on mussels were applied to samples from five sites along the Galician Coast, Spain, taken 6 months after the oil spill from the tanker “Aegean Sea.” Whole body aliphatic hydrocarbon concentrations were similar at all sites, but specific chemical ratios (resolved/unresolved hydrocarbons; carbon preference index; pristane/phytane) indicated a predominance of degraded petrogenic hydrocarbons nearer the oil spill. Levels of whole body polycyclic aromatic hydrocarbons (sum of 13 PAHs) increased steadily towards the oil spill, and were paralleled by increases in digestive gland levels of total cytochrome P-450, CYP1A-like protein and lipid peroxidation (corr. coeffs. with PAHs of 0.64–0.67). Differences were more marked in CYP1A-like protein than total cytochrome P450, indicating induction of specific P450 isoenzyme(s). No differences between sites were seen for benzo[a]pyrene hydroxylase, glutathione S-transferase, Superoxide dismutase and DT-diaphorase activities. Bulky, hydrophobic DNA-adducts were detected in digestive gland of mussels from industrial and urban sites, but not from the site nearest to the oil spill which had the highest tissue levels of PAHs. Overall the results indicate induction of cytochrome P450(s) and oxidative damage in mussel with oil exposure.

Concentrations and fluxes of organic compounds in the atmosphere of the Swedish west coast

Abstract Measurements of organic compounds in air and deposition have been carried out in parallel on the Swedish west coast. In this investigation the importance of long-range transport for the occurrence of organic compounds in deposition has been studied. Air samples were collected using a high volume sampler (HVS) and the deposition was sampled on a 1 m2 Teflon-coated horizontal surface with runoff for the precipitation to an adsorbent. The samples were analyzed in order to identify and quantify different semivolatile compounds such as PAH and petrogenic hydrocarbons and chlorinated compounds such as PCB, HCH and HCB. Qualitative differences between the content of organic compounds in air and deposition during periods with varying levels of air pollution and different meteorological conditions have been studied and a comparison with other air pollutants, such as soot, has been carried out. The results of the measurements show that deposition of PAH and other hydrocarbons takes place continuously but the greatest amounts are measured in the deposition in connection with episodes together with heavy precipitation. The highest concentrations of PCB and HCH in the air were obtained during a warm dry period in May and the greatest amounts were deposited in a period in May with heavy precipitation.

Mutagenic effect of extracts from particulate matter collected with sediment traps in the archipelago of Stockholm and the open northern Baltic.

The load of various hydrophobic organic compounds (HOCs) on the Baltic Sea aquatic environment is considerable. This investigation samples the water area around Stockholm, of special concern since it is one of the most densely populated urban areas in the Baltic region. Stockholm also houses several power plants, municipal waste incinerators, waste water treatment plants, ports and oil terminals. The runoff from a large lake also passes through the estuarine-like archipelago of Stockholm. Due to the high particulate-water partition coefficients (K[sub p]) of most ecotoxicologically relevant HOCs, particulate matter (PM) becomes very important for occurrence and distribution in the aquatic environment. This PM is the basic food source for important organisms in the benthic, pelagic and littoral parts of the aquatic ecosystem. The load of various HOCs such as petrogenic hydrocarbons (PHCs), various polynuclear aromatic compounds (PACs), and chlorinated hydrocarbons such as polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in association with PM in the aquatic environment of the Stockholm area is well documented. However, the ecotoxicological relevance of organic extracts of PM, including the above identified compounds and various unidentified HOCs, is not fully evaluated. To evaluate the genotoxic potential of extracts of PM, collected with sedimentmore » traps in the Stockholm water area and in the open northern Baltic, we used the Ames test on Salmonella typhimurium strain TA100, with and without a metabolizing system. After extraction and before the mutagenicity tests all PM samples were fractionated on an HPLC-system into three fractions containing aliphatic/monoaromatic-, diaromatic, (containing, e.g., PCDD/Fs and PCBs) and polyaromatic compounds (containing various PACs). The relative mutagenic potential of these fractions at the different sediment trap sampling stations are discussed and evaluated. 13 refs., 1 tab.« less

Hydrocarbons and related photo-oxidation products in Saudi Arabian Gulf coastal waters and hydrocarbons in underlying sediments and bioindicator bivalves

Saudi Arabian coastal waters near sandy beaches, severely contaminated with crude oil released in Kuwait during the 1991 Gulf War, as well as underlying sediments and a few bivalves, were analysed to assess concentrations and composition of petrogenic hydrocarbon mixtures and structurally related oxidation products. Concentrations of dissolved oil residues determined by UV spectrofluorometry (UVF) near oil deposits on beaches did not exceed 3.5 μg l −1; concentrations dropped to approximately 1/10th of this value a few miles offshore. Gravimetric concentrations of unfractionated lipophilic material extracted from large volumes of seawater at the same stations were up to 10 times those determined by UVF. After chromatography on silica gel, individual petroleum hydrocarbons in the low polarity fractions and oxidation products in the polar fractions were characterized by their spectra (GC/MS) and quantitated by Selected Ion Monitoring (SIM) GC/MS. Concentrations of oxidation products (ketones, aldehydes, alcohols) of aromatic hydrocarbons exceeded those of their parent compounds by more than an order of magnitude. Significant concentrations were also found of the presumably pyrogenic triplett sensitizer anthraquinone. Contributions to polar fractions of water extracts by biosynthesized lipids were negligible. UVF determinations appear to underestimate concentrations of dissolved oil residues, because many oxidation products have lower fluorescence quantum yields than the respective parent hydrocarbons. Their ecotoxicological properties are unknown. Concentrations measured in sediments by UVF ranged from 13 to 540 μg g −1 dry wt and 0.5 to 103 μg g −1 as measured by gas chromatography with flame ionization detection (FID GC). Bivalves ranged from 0.8 to 1.5 μg mg −1 extractable organic matter (EOM) by UVF, and 0.1 to 0.3 μg mg −1 EOM by GC analysis. PAHs were identified in sediment and bivalve extracts by GC/MS and quantitated by SIM GC/MS. None of the relatively water soluble alkylbenzene photo-oxidation products found in water samples nor any higher molecular weight quinones could be detected in sediment extracts. However, ion chromatograms strongly suggest the presence of numerous high molecular weight aromatics in that matrix.

Volatile organic compounds in two polluted rivers in Barcelona (Catalonia, Spain)

The distributions of volatile organic compounds (VOC) in two rivers flowing through heavily populated areas, Besós and Llobregat, have been investigated. River waters have been analyzed monthly for a period of 13 months. Marine samples from the coastal area where these rivers discharge as well as from other coastal sites situated away from river influence have also been studied. Petrogenic hydrocarbons, essentially C1–C5 alkylbenzenes and C8–C20 n-alkanes, are the major volatile compounds present in these rivers (estimated annual discharge 260 metric tons). Chlorinated benzenes, C10–C13 alkylbenzenes, some terpenes and tributylphosphates are other main VOC with estimated outputs to seawater of 27, 14, 7 and 2 metric tons per year, respectively. The VOC concentrations in the rivers are generally between two and three orders of magnitude higher than in the marine samples. The discharges of the Besós and Llobregat Rivers result in significant increases of C10–C13 alkylbenzenes, tributylphosphate, hexachlorobutadiene and chlorobenzenes to the nearby coastal area. However, in the case of petrogenic hydrocarbons, the background concentration resulting from marine traffic and related activities developed in the area outnumbers the riverine contributions.

Baseline Studies and Risk Analyses in the Baltic Sea

ABSTRACT In 1986 an oil and gas concession in the Baltic Sea was granted by the Danish Ministry of Energy to a group of oil companies, with Norsk Hydro as operator. A paper describing the goals achieved midway through the program was presented at the 1989 Oil Spill Conference in San Antonio, Texas. This paper presents the final results of the program. The chemical baseline study has shown that the only parameter that exhibits a marked variation is the total hydrocarbon content, where values are seven to eight times higher in the 1989 samples than in the 1987 and 1988 samples. It is suspected that the reason is seasonal variation, since the 1989 samples were collected in June, while the 1987 and 1988 samples were collected in September. Even though the total hydrocarbon content varies significantly between some of the sample suites, only biomarkers related to recent organic material or immature petroleum source rocks are present in the samples. Petrogenic hydrocarbons related to spilled crude oil or exploration activities were not found in the area. The spreading and weathering calculations revealed the zones along the coast where an oil spill was most likely to occur. The transport time for an oil spill to reach the coast was also calculated by the model. In combination with mapping of sensitive resources, the results from the model test runs were used in risk assessments. The information gained in this study was used in the oil spill contingency plan.

Persistence of spilled crude oil in a tropical intertidal environment

Intertidal sediments at Bahia Sucia, on the southwest coast of Puerto Rico contain discreet subsurface layers of petrogenic hydrocarbons. The uppermost of these layers contains petroleum contaminants in concentrations above 200 mg g −1 and is most probably atributable to the 1977 spill from the tanker Zoe Colocotronis. A deeper layer containing a less concentrated load of petroleum hydrocarbons may correspond to the Argea Prima spill of 1962. Sediments above, between and below these two layers present low concentrations of typically biogenic hydrocarbons. Although petroleum released to the sea in tropical environments generally suffers rapid degradation, petroleum contaminants reaching intertidal sediments may exhibit long-term persistence.

The use of the mussel watch and molecular marker concepts in studies of hydrocarbons in a tropical bay (Todos os Santos. Bahia, Brazil)

Data on aliphatic and aromatic hydrocarbons in different species of edible bivalves collected in the Todos os Santos Bay (Bahia, Brazil) are reported for the first time along the South West Atlantic coast. The species and collection sites were selected for the identification of suitable regional sentinels and for the assessment of different coastal pollutant sources. To this end, the molecular marker concept was applied. A new series of biogenic C20, C25 and C30 highly branched isoprenoid alkenes were present in clean samples. Long-chain alkylbenzenes and specific distributions of isoprenoids, steranes and hopanes reflected local industrial activities. Petrogenic alkanes and aromatic hydrocarbons, ranged respectively between 0.1–42 μg/g wet wt. and 0.1–9.1 μg eq. chrysene/g wet wt., the higher levels being found in the neighborhood of an oil refinery and a plant oil industry.Anomalocardia brasiliana, the dominant and most frequent bivalve of the Brazilian coast, can be an adequate bioindicator, because it accumulates organic pollutants with reasonable sensitivity.

Flavour and hydrocarbon assessment of fish from gas fields in the Southern North Sea

Plaice ( Pleuronectes platessa), dab ( Limanda limanda) and sole ( Solea solea), caught by netting in the vicinity of selected Southern North Sea gas production platforms, were assessed by an expert sensory panel for possible tainting (atypical flavour). Selected samples offish tissue and sediment were analysed for n-alkanes. Any atypical flavours detected were classed as ‘slight’ on the scale used and were found in fish from both platform and reference sites. The incidence of these flavours, but not the mean intensity in affected fish differed between platform sites. When selected fish were assessed specifically for ‘oily’ flavour, only onefish was considered to have a ‘slight’ oily flavour. The levels offlavour detected by the expert panel were close to the detection threshold; it is unlikely they would be detected by the untrained consumer. None of the flavours detected were attributable directly to platform operations. Increased levels of petrogenic hydrocarbons in fish from platform sites were found but these levels were not associated with any impairment offlavour.

Distribution of aliphatic, aromatic and chlorinated hydrocarbons in mussels from the Spanish Atlantic coast (Galicia). An assessment of pollution parameters

Mussel populations collected in a suite of heavily polluted to non-polluted estuarine systems of the NW Spanish Atlantic Coast (Galicia) have been analyzed for alkanes+alkenes (I), monocyclic aromatics and PCBs (II), and polycyclic aromatics (III). Using GC-FID, GC-ECD, GC-MS and UV-fluorescence, molecular marker identifications and correlation trends of chemical composition parameters have been determined for the assessment of pollution. The results have shown that both the resolved and unresolved components of fractions I and II are predominated by petrogenic hydrocarbons. UV-fluorescence is also useful for the measurement of petroleum contributions in fraction II although a standard better than chrysene should be developed for quantitation. The unresolved hydrocarbons of fraction III correspond to a mixture of petrogenic and pyrolytic sources. Finally, the polychlorobiphenyls do not show any correlation with petrogenic or pyrolytic pollutant sources.

Mineralization of polycyclic aromatic hydrocarbons by a bacterium isolated from sediment below an oil field

Microbiological analyses of sediments chronically exposed to petrogenic hydrocarbons resulted in the isolation of a gram-positive, rod-shaped bacterium which mineralized naphthalene (59.5% of the original amount), phenanthrene (50.9%), fluoranthene (89.7%), pyrene (63.0%), 1-nitropyrene (12.3%), 3-methylcholanthrene (1.6%), and 6-nitrochrysene (2.0%) to carbon dioxide when grown for 2 weeks in pure culture with organic nutrients. The bacterium tolerated salt concentrations up to 4% and grew well at 24 to 30 degrees C. The use of this bacterium may be an attractive alternative to existing physicochemical methods for the remediation of polycyclic aromatic hydrocarbons in the environment.

Accumulation and distribution of hydrocarbons, polychlorobyphenyls, and DDT in tissues of three species of Anatidae from the Ebro Delta (Spain).

Five tissues (breast muscle, liver, kidney, adipose tissue and medulla) of three species of Anatidae (Netta, rufina, Anas crecca andAnas clypeata) from the Ebro Delta have been analyzed for ∑DDT, polychlorobyphenyls (PCBs) and biogenic and petrogenic hydrocarbons, with the aim of obtaining information on the biodynamics of these compounds in wildbirds.

Sediment aliphatic hydrocarbons in the Forth estuary

The sources and distributions of aliphatic hydrocarbons in sediments from the Forth estuary were examined using gas chromatography and computer interfaced gas chromatography/mass spectroscopy. The sediments contained hydrocarbons from petrogenic and land derived biogenic sources. Of the stations examined, the more sandy sediments from Longannet showed the least level of petrogenic pollution. Based on gravimetric data, gas chromatographic, triterpane and sterane fingerprinting, the Grangemouth complex was identified as a major source of some of the petrogenic hydrocarbons found in the sediments.

‘Fingerprinting’ petroleum hydrocarbons in bottom sediment, plankton, and sediment trap collected seston

Water carried particulate matter (seston) collected in sediment traps has been used for fingerprinting petrogenic hydrocarbons (PHC) along an urban influenced transect in the Stockholm archipelago. Gas-chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) have been used for identification and quantification of n-alkanes, the isoprenoids pristane and phytane, pentacyclic triterpanes, the unresolved complex mixture (UCM) and total hydrocarbon content (THC). Preserved seston has been compared with anoxic seston and anoxic bottom surface sediments to establish the effects of degradation processes, and with spring bloom plankton as a reference of biological material. The results show that samples of seston, collected and preserved in sediment traps, are very suitable for carrying out fingerprint analyses of petrogenic hydrocarbons. A gradient of increasing PHC downflux towards the urban area was found and petrogenic contamination of the waters was detected along the whole transect.

The flavour and chemical assessment of dabs ( Limanda limanda) caught in the vicinity of the Beatrice Oil Platform

Dabs ( Limanda limanda) caught in close proximity to the Beatrice Oil Platform have been assessed for the presence of an oil taint and chemically analysed for n-alkane and polynuclear aromatic hydrocarbons. Although contamination from petrogenic hydrocarbons was apparent, none of the fish were found to have a definite taint.

Georges bank monitoring program: hydrocarbons in bottom sediments and hydrocarbons and trace metals in tissues

Hydrocarbons in sediments and hydrocarbons and trace metals in tissues from Georges Bank were analyzed to evaluate potential changes to the henthic environment resulting from exploratory drilling operations. Sediment hydrocarbon concentrations varied with grain size: concentrations up to 2·5μg/g dry weight total aromatic equivalents occurred in the fine-grained sediments of Lydonia Canyon and the ‘Mud Patch’ area south of Martha's Vineyard, whereas concentrations were less than I μg/g dry weight in sediments from the shallow areas of Georges Bank, at a regional control site, and at the site of drilling operations. Increases in total aromatic equivalents from approximately 0·1 μg/g dry weight to 0·4 μg/g dry weight were measured in sediments from a site 0.25 km from the drill rig concurrent with drilling operations. Petrogenic hydrocarbons were detected in both drilling fluid extracts and in sediments collected during drilling operations, suggesting short-term deposition of drilling discharges in near-rig sediments. Drilling discharge residues were not observed in the near-rig sediments one month after drilling operations were terminated. Furthermore, hydrocarbon residues from drilling discharges werenot observed in sediments from stations located at distances greater than 6 km from the drill site either during or subsequent to the drilling operations.

The effects of oil exploration and production in the northern north sea: Part 1–The levels of hydrocarbons in water and sediments in selected areas, 1978–1981

In the light of increasing oil exploration and production in the northern North Sea, the Brent, Beryl and Forties oil fields, representing three different types of operation, and a number of stations between the Forties field and the Firth of Forth, were sampled to determine the levels of total (by fluorescence), alkane (by glass capillary gas chromatography) and aromatic (by gas chromatography-mass spectrometry) hydrocarbons in water and sediments. Close to the Beryl platform, where diesel-washed drill cuttings have been dumped, there was an accumulation of petrogenic hydrocarbons in the sediment, resulting in a build up of certain aryl hydrocarbons, notably the dibenzthiophenes and 3- and 4-ring aromatic compounds. In all the sediment samples analysed for aromatic hydrocarbons, relatively large amounts of 5- and 6-ring compounds were found in areas expected to be free of pollution, as well as from areas around oil platforms and from the Firth of Forth. Their source is likely to be windborne combustion products.

Recent contributions of high resolution gas chromatography to the analysis of environmental hydrocarbons

AbstractAnalyses of hydrocarbon fractions from different areas of the marine environment are described to illustrate the possibilities and limitations of high resolution gas chromatography (HRGC) in the analysis of environmental samples. Examples are given of dissolved, particulate, and sedimentary hydrocarbons and organochlorine compounds; the importance of an adequate sampling of the marine environment is stressed. HR chromatographic profiles obtained in two columns of low and high polarity (SE‐52 and PEG 20M) permit the sources and transport pathways of both natural and anthropogenic hydrocarbons to be traced. Analysis of tissues of marine mammals, which metabolize or excrete many of the biogenic and petrogenic hydrocarbons present in other areas of the marine environment, may provide an opportunity to obtain relatively clean profiles of many anthropogenic compounds of interest. The plotting of mass chromatograms from data compiled by COM‐GC‐MS remains the most appropriate method for the conclusive indentification of these compounds.

Detection of aliphatic hydrocarbons derived by recent “bio-conversion” from fossil fuel oil in North Sea waters

The higher boiling point range of saturated aliphatic hydrocarbon fractions extracted from North Sea water have been re-investigated in detail with improved high resolution glass capillary columns suitable for high temperature gas-chromatography. The resulting chromatograms reveal hydrocarbon patterns, most of which have the same common feature: a smooth distribution of the long-chain n-alkanes combined with a lack of the branched alkanes normally expected for fossil fuel oil. Instead, two homologous series of iso- and anteiso-alkanes could be detected. Since this finding is always associated with traces of present or past fossil fuel oil contamination of the upper water column, these environmental n-, iso and anteisoalkanes are considered to be recently ‘bio-converted’ from fossil fuel oil hydrocarbons. They form a third group beside recent biogenic and fossil petrogenic hydrocarbons in the marine environment. Oil pollution records of the marine environment will have to take into account this group of microbial hydrocarbons.

Investigation of the sources of aliphatic hydrocarbons in the musselMytilus edulisfrom north sea oil production platforms by Capillary glc and CGCMS†

Aliphatic hydrocarbons isolated from mussels collected over a 20 month period from three North Sea Forties field oil production platforms have been examined by capillary gas chromatography and gas chromatography‐mass spectrometry. The biological hydrocarbons consist predominantly (300–700 μh g‐1 lipid) of C31 and C33 n‐alkenes with 2, 3 and 4 double bonds probably derived from a dietary intake of Emiliania huxleyi, a microscopic coccolithophorid alga. In some of the mussels C18, C20 and C22 n‐alkanes are present in unusually high abundance compared to their odd carbon number homologues. Possible reasons for this distribution are discussed. The concentrations of fossil fuel hydrocarbons (mainly unresolved complex mixtures) in the mussels ranged from 330 to 5,298 μg g‐1 of lipid. No significant increase in values was detected two months after the start of discharge of treated Forties production water from the Forties D platform. To determine the pollutant hydrocarbon sources, the sterane and terpane distributions of hydrocarbon fractions isolated from the mussels and from a number of fossil fuels, including Forties crude oil, were examined by mass fragmentography. The steranes in the mussels from the Forties C and D platforms contained higher proportions of regular 14α(H), 17α(H) components than Forties oil in which the steranes were mainly 13ß(H), 17α(H) diasteranes. In addition, the terpane distributions of the mussel fractions differed markedly from that of Forties crude oil, particularly in the relative abundance of diterpanes to triterpanes, which was higher in the mussel fractions than in the oil, and in the absence of 17α(H), 18α(H), 21ß(H)‐18, 30‐bisnorhopane, a known component of Forties crude. Furthermore, the ratio of C29 to C30 triterpanes was greater than unity in the mussels but much less than unity in the Forties oil. These data preclude Forties or other similar North Sea crudes as the major source of pollutant aliphatic hydrocarbons in the mussels. The relative concentrations and distributions of steranes and triterpanes suggest that the most likely source of pollutants is a Middle Eastern based oil derived either from rig activities, or from background pollution in the North Sea. The low concentration of ≥ C27 steranes in the more polluted mussels (e.g. Forties B; UCM > 200 ppm dry wt.) suggests that gas oils used on the platforms may be the major source of petrogenic hydrocarbons in these samples.