Spatial distribution and ecotoxicity of petroleum hydrocarbons in sediments from the Galicia continental shelf (NW Spain) after the Prestige oil spill

The distribution of aliphatic and aromatic hydrocarbons was determined in surface sediments collected at 36 stations along the Galicia continental shelf (NW Spain), following the Prestige oil spill. Sampling was performed in December 2002, just after the accident, and in February and September 2003. Concentrations of PAHs (summation operator 13 parent components) were in the range of 0.9-422 microg/kgdw, the highest values being close to coastal urban areas (e.g. Pontevedra and A Coru?a), whereas in the stations of the area most heavily impacted by the spill (off Costa da Morte) concentrations were in the range of 14.8-89.6 microg/kgdw, with a certain predominance of alkylated compounds, which may suggest a mixture of petrogenic and pyrolytic sources. The detailed study of petrogenic molecular markers (e.g. steranes and triterpanes) showed the occurrence of an old (weathered) petrogenic chronic pollution in the shelf sediments but not of the Prestige oil, with the possible exception of few stations in the area of Costa da Morte. This was attributed to the heavy nature of the spilled oil that was barely dispersed in the water column and mainly stranded on the coast or sedimented in the form of oil patches. The addition of increasing amounts of fuel oil to a representative sediment sample showed that the molecular indices were indicative of the presence of the Prestige oil when the amount was above 1g/kg of sediment. The toxicity of selected samples (showing the higher PAH concentrations) was tested using the bivalve embryogenesis bioassay. Embryogenesis success reached high values in all cases (80-88%, with 86% in the control), indicating a lack of toxicity in the sediments and supporting the conclusion that the patchiness of the fuel eventually reaching the seafloor reduced its impact on the benthic communities of the Galician shelf.     

Biomarker responses in pelagic and benthic fish over 1 year following the Hebei Spirit oil spill (Taean, Korea)

After the Hebei Spirit oil spill incident (7th December, 2007) in the west coast of Korea, contamination of biliary PAH metabolite and hepatic biomarkers in a pelagic and a benthic fish was monitored for 1 year. Concentrations of 16 PAHs and alkylated PAHs in fish muscle were highest (22.0 ng/g d.w. for 16 PAHs and 284 ng/g d.w. for alkylated PAHs) at 5 days after the spill and then decreased rapidly to background levels at 11 months after the spill. Fish from the oiled site had elevated biliary PAH metabolite concentrations immediately after the spill; these declined steadily in both species, but were still above reference site concentrations 2 months after the spill. Oiled-site fish showed hepatic CYP 1A induction whose trend closely followed those of biliary PAH metabolite concentrations, implying continuous exposure to PAHs. Brain acetylcholinesterase activity was not related to oil exposure.     

Polycyclic aromatic hydrocarbon (PAHs) and hopanes in stranded tar-balls on the coasts of Peninsular Malaysia: applications of biomarkers for identifying sources of oil pollution

Malaysian coasts are subjected to various threats of petroleum pollution including routine and accidental oil spill from tankers, spillage of crude oils from inland and offshore oil fields, and run-off from land-based human activities. Due to its strategic location, the Straits of Malacca serves as a major shipping lane. This paper expands the utility of biomarker compounds, hopanes, in identifying the source of tar-balls stranded on Malaysian coasts. 20 tar-ball samples collected from the east and west coast were analyzed for hopanes and polycyclic aromatic hydrocarbons (PAHs). Four of the 13 tar-ball samples collected from the west coast of Peninsular Malaysia were identified as the Middle East crude oil (MECO) based on their biomarker signatures, suggesting tanker-derived sources significantly contributing the petroleum pollution in the Straits of Malacca. The tar-balls found on the east coast seem to originate from the offshore oil platforms in the South China Sea. The presence of South East Asian crude oil (SEACO) tar-balls on the west coast carry several plausible explanations. Some of the tar-balls could have been transported via sea currents from the east coast. The tankers carrying SEACO to other countries could have accidentally spilt the oil as well. Furthermore, discharge of tank washings and ballast water from the tankers were suggested based on the abundance in higher molecular weight n-alkanes and the absence of unresolved complex mixture (UCM) in the tar-ball samples. The other possibilities are that the tar-balls may have been originated from the Sumatran oil fields and spillage of domestic oil from oil refineries in Port Dickson and Malacca. The results of PAHs analysis suggest that all the tar-ball samples have undergone various extent of weathering through evaporation, dissolution and photo-oxidation.     

Biomarker responses in flounder (Platichthys flesus) and mussel (Mytilus edulis) in the Klaipeda-Būtinge area (Baltic Sea)

During the EU project BEEP a battery of biomarkers was applied in flounder (Platichthys flesus) and the blue mussel (Mytilus edulis) collected at three locations off the Lithuanian coast (Baltic Sea) in June and September 2001 and 2002. The elevated biomarker responses in specimens sampled in September 2001 were apparently related to the extensive dredging activities in the Klaipeda port area and subsequent dumping of contaminated sediments. High concentrations of organic pollutants (organochlorines and PBDEs) were also measured in the tissues of both indicator species. In addition, response levels of genotoxicity, cytotoxicity, immunotoxicity as well as concentrations of PAH metabolites in the bile of flounder showed elevations in 2002 after an oil spill in the Būtinge oil terminal in November 2001. In flounder, biomarker measurements 10 months after the spill indicated recovery processes but in mussels a high level of genotoxicity could still be observed 22 months later. The present study illustrates the usefulness of the multi-biomarker approach in the detection of biological effects of pollution in this region of the Baltic Sea.     

Temporal variation of chlorophyll a concentration in the coastal waters affected by the Hebei Spirit oil spill in the West Sea of Korea

Time series changes in chlorophyll a concentration before and after the Hebei Spirit oil spill that occurred in December 2007 were analyzed using NCEP wind and SeaWiFS/MODIS ocean color data. Prevailing southwesterly winds and northeast/southwestward tidal currents pushed the oil towards Korea’s West Sea coast of Taean. After the oil spill, daily chlorophyll a concentration decreased about 45-50% compared to the normal condition before the oil spill, and this decrease continued for about two weeks. Monthly mean chlorophyll a concentration in December 2007 was lower compared to the average value for the same month between 1998 and 2007, but, in October and November 2007 before the spill and in January-February 2008 after the spill, the concentration value was higher than average for the same period between 1998 and 2007.     

Fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp in Hong Kong following an oil spill

The fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp (Yi O) in Hong Kong after an oil spill accident was investigated. The concentrations and profiles of PAHs in surface sediments collected from five quadrats (each of 10 m×10 m) covering different degrees of oil contamination and the most contaminated mangrove leaves were examined in December 2000 (30 days after the accident) and March 2001 (126 days later). The concentrations of total PAHs in surface sediments ranged from 138 to 2135 ng g⁻¹, and PAHs concentrations decreased with time. In the most contaminated sediments, total PAHs dropped from 2135 (30 days) to 1196 ng g⁻¹ (120 days), and the decrease was smaller in less contaminated sediments. The percentage reduction in sediment PAHs over three months (44%) was less significant than that in contaminated leaves (85%), indicating PAH in or on leaves disappeared more rapidly. The PAH profiles were very similar in sediments collected from quadrats Q1 and Q2 with benzo[a]anthracene and pyrene being the most abundant PAH compounds, but were different in the other three quadrats. The proportion of the light molecular weight PAHs to total PAHs increased after three months, especially phenanthrene. Results suggest that physical and photo-chemical weathering (tidal washing and photo-oxidation) of crude oil in surface sediments and on plant leaves were important processes in the first few months after the oil spill. The PAH contamination in Yi O swamp came from both petrogenic and pyrolytic sources. The petrogenic characteristic in the most contaminated sediment was confirmed with high values of phenanthrene to anthracene ratio (>10) and low values of fluoranthene to pyrene ratio (0.3–0.4).     

Polycyclic aromatic hydrocarbons in coastal sediments of southwest Taiwan: An appraisal of diagnostic ratios in source recognition

Fifty-seven surface sediment samples were collected from the coast of southwest Taiwan and analyzed for polycyclic aromatic hydrocarbons (PAHs). Concentrations of total PAHs (28 PAH compounds) ranged from 15 to 907 ng g⁻¹ dry weight. Diagnostic ratios showed that PAHs in the sediments of the Gaoping estuary were predominantly of petroleum origin, whereas sediments from the Kaohsiung coast contained principally combustion-derived PAHs. Principal component analysis indicated that emissions from automobiles and coal burning were the main sources of combustion-derived PAHs. The relatively high ratios of perylene/penta-aromatic PAH isomers in sediments from the Tainan coast and some off-shore stations on the Kaohsiung coast suggest a significant diagenetic PAH contribution. The study shows that certain diagnostic ratios are useful and sensitive in delineating the distribution of PAHs from specific sources in southwest Taiwan. The phenanthrene/anthracene ratio is a better indicator than the methylphenanthrenes/phenanthrene ratio for tracing petrogenic PAHs, and the benzo(a)anthracene/chrysene and indeno(1,2,3-c,d)pyrene/benzo(g,h,i)perylene ratios are more specific than the benzo(a)pyrene/benzo(e)pyrene and benzo(b)fluoranthcene/benzo(k)fluoranthcene ratios in distinguishing PAHs from various pyrogenic sources.     

Temporal and geographical trends in the genotoxic effects of marine sediments after accidental oil spill on the blood cells of striped beakperch (Oplegnathus fasciatus)

To determine the impact of genetic toxicity caused by the Hebei Spirit oil spill on December 7, 2007, we measured DNA damage in the blood cells of striped beakperch in vitro after exposure to extracts from sediments in the Taean area. The objective of this study was to investigate temporal changes of toxic effects caused by residual PAHs in the sediments up to 18 months after an oil spill. In conclusion, DNA damage had reduced over this 18-month period; that is, the sediments recovered quickly from the oil pollution. In addition, statistically significant correlations between PAHs and DNA damage were observed. Because the comet assay is sensitive to DNA damage induced by genotoxic substances from the polluted sediments, the comet assay can be considered a useful tool as a biomarker in investigating genetic toxicity in environmental monitoring and elucidating the recovery of oil pollution after oil spill as well.     

The 1974 spill of the Bouchard 65 oil barge: petroleum hydrocarbons persist in Winsor Cove salt marsh sediments

Petroleum hydrocarbons persist in salt marsh sediments in Winsor Cove (Buzzards Bay, Massachusetts) impacted from the 1974 spill of No. 2 fuel oil by the barge Bouchard 65. Intertidal sediment cores were collected from 2001 to 2005 and analyzed for total petroleum hydrocarbons (TPHs). TPHs content was greatest (as high as 8.7 mg g(-1) dry weight) in the surface sediments and decreased with distance landward. Select samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) with values as high as 16.7 microg g(-1) for total naphthalenes and phenanthrenes/anthracenes. These remaining PAHs are mainly C(4)-naphthalenes and C(1)-, C(2)-, and C(3)-phenanthrenes/anthracenes revealing preferential loss of almost all of the naphthalenes and the parent compound phenanthrene. Inspection of the data indicates that biodegradation, water-washing and evaporation were major removal processes for many of the petroleum hydrocarbons in the marsh sediments. In addition, historical data and photographs combined with their recent counterparts indicate that erosion has physically removed these contaminants from this site.     

Shallow sublittoral meiofauna communities and sediment polycyclic aromatic hydrocarbons (PAHs) content on the Galician coast (NW Spain), six months after the Prestige oil spill

The aim of this work was to detect the impact of Prestige oil spill on meiobenthic community structure at higher levels of taxonomic aggregation. In addition, the relationship between sediment individual polycyclic aromatic hydrocarbon (PAH) concentration and meiofauna community structure was investigated. Six months after the Prestige oil spill, meiobenthos community and sediment PAHs content from seven shallow subtidal localities along the Galician coast were studied. Two sites presented differences in community structure, characterized by high densities of nematodes, gastrotrichs and turbellarians, and low densities of copepods. Chrysene and triphenylene were only found at these two disturbed sites and could be responsible for differences of meiobenthos community structure. However, differences in community structure of sites could be linked with sedimentary parameters, and discrimination between the effect of PAHs and sedimentary parameters was impossible due to the lack of baseline studies on meiobenthos and PAHs contents in this area.     

Influence of the oceanographic conditions during spring 2003 on the transport of the Prestige tanker fuel oil to the Galician coast

Hydrographic data collected during the cruise HIDROPRESTIGE were combined with meteorological and dynamic data provided by remote sensors and drifting/moored buoys, to describe the surface circulation of the Northern Iberian basin in March-April 2003. Sea surface winds transported the floating Prestige oil slicks from the sinking area to the continental slope off the Rías Baixas in 1/2 month: the surface current intensity was 2% of the wind intensity and it was rotated clockwise 5 degrees from the wind direction. Mesoscale cyclonic and anticyclonic structures west of 10 degrees W increased the residence time of oil patches in the Northern Iberian basin, as compared with the expected southwards flow of the Iberian current (IC). On the other hand, the Iberian poleward current (IPC) formed a marked surface front with coastal waters, preventing the entry of fuel oil into the rías. PAHs in the surface layer during the cruise were <0.5 microgL(-1), except in the Galicia bank (approximately 1 microg L(-1); where the Prestige tanker was still leaking) and the vicinity of Cape Fisterra (approximately 1.5 microg L(-1); where the convergence front between the IPC and coastal waters vanished).     

Distribution and source recognition of polycyclic aromatic hydrocarbons in the sediments of Hsin-ta Harbour and adjacent coastal areas,Taiwan

Thirty-three sediment samples from Hsin-ta Harbour and neighboring coastal areas were analyzed by GC-MS for polycyclic aromatic hydrocarbons (PAHs). Total concentrations of 30 analyzed parental and alkylated PAHs ( summation operator PAH) varied from 98.1 to 3382 ng/g dry weight. MP/P (methylphenanthrenes/phenanthrene) values larger than 2 coincided with very low P/A (phenanthrene/anthracene) values at inner harbour stations, revealing that a significant portion of low molecular weight PAHs are probably from petrogenic pollution sources, specifically, illegal disposal of used motor oil. The 4,6-dimethyldibenzothiophene/3,6-dimethylphenanthrene (4,6-C(2)D/3,6-C(2)P) ratio is found to be more useful than the MP/P ratio in tracing petrogenic PAHs from the inner harbour area to the adjacent coastal environment. In addition, according to hierarchical cluster analysis, collected sediments cluster in three major groups, Off-shore Group, Near-shore Group and Inner Harbour Group. Three diagnostic ratios, 4,6-C(2)D/3,6-C(2)P, PER/ summation operator PAH (perylene to summation operator PAH) and BaA/CHR (benzo(a)anthracene/chrysene), representing petrogenic, biogenic and pyrogenic origins, are found to be effective in differentiating and characterizing sediments among the groups in this study. Enrichment of pyrogenic and petrogenic PAHs in sediments collected exhibits mixing or dilution, spatially, by biogenic (or natural) PAHs.     

Weathering of an Arctic oil spill over 20 years: the BIOS experiment revisited. Baffin Island Oil Spill

A small experimental oil spill was conducted on the northern tip of Baffin Island Nunavut, Canada (72 degrees 31' N, 79 degrees 50' W) in August 1981, and the natural weathering of the oil has been followed by periodic visits. This paper reports on the chemical composition of oil collected in August 2001. The vast majority of the initial oil has gone, but small patches remain. Some samples remain essentially unaltered despite their 20 years of exposure to the elements, while others show that biodegradation and photooxidation can play important roles in removing the majority of the components of the oil. Using 17alpha(H)21beta(H)hopane as a conserved marker within the oil, we show that the most biodegraded sample has lost more than 87% of the hydrocarbons initially present, while another has lost a substantial proportion of its initial chrysene and alkylated congeners. Potential explanations for the different weathering patterns seen in samples collected from this small site are briefly discussed.     

Dioxin-like compounds in HPLC-fractionated extracts of marine samples from the east and west coast of Sweden: Bioassay- and instrumentally-derived TCDD equivalents

Lipophilic extracts of sediment, settling particulate matter (SPM) and blue mussel (Mytilus edulis) samples, collected at coastal locations on the east and west coast of Sweden, were HPLC-separated into three fractions containing 1. monoaromatic/aliphatic, 2. diaromatic (e.g. polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDDs/Fs)), and 3. polyaromatic compounds (e.g. polycyclic aromatic hydrocarbons (PAHs)). The fractions were tested for dioxin-like effects using a sensitive bioassay, based on EROD-induction in cultured chicken embryo livers. The concentrations of PCDDs/Fs, PCBs and 15 PAHs in the samples were also determined. The polyaromatic fractions of the sediment samples were more potent as EROD-inducers than the diaromatic fractions. Only a small part of the EROD-induction caused by the polyaromatic fractions could be explained by the analysed PAHs in the samples, indicating presence of non-quantified polyaromatic EROD-inducing compounds in the samples. A greater pollution by EROD-inducing diaromatic and polyaromatic compounds on the east coast site than on the west coast site was seen. The filtration activities and faeces production of the mussels on the east coast experimental site increased the sedimentation of PCDDs/Fs, PCBs and PAHs. The described bioassay proved very useful in the assessment of dioxin-like compounds in both abiotic and biotic samples from the marine environment.     

Cytogenetic and cytotoxic effects in gill cells of the blue mussel Mytilus spp. from different zones of the Baltic Sea

Frequency of micronuclei (MN) and other nuclear abnormalities (nuclear buds, bi-nucleated and fragmented-apoptotic cells) was analysed in gill cells of the blue mussel (Mytilus spp.) from selected coastal sites in the Baltic Sea--Kv?d?fj?rden (Sweden), Klaipeda-Būtinge zone (Lithuania), Gulf of Gdansk (Poland) and Wismar Bay (Germany). Samples were collected from 650 specimens during bi-annual sampling campaigns in 2001 and 2002. The lowest frequency of MN (0.37 MN/1000 cells) was found in blue mussels from the reference site (Kv?d?fj?rden). The highest MN values (up to 6.7 MN/1000 cells) were registered in blue mussels from the Gulf of Gdansk in autumn 2001 and 2002, and at Wismar Bay in spring 2001 (up to 5.06 MN/1000 cells). Gradients of MN incidences were observed when comparing the three studied locations in Wismar Bay, and at the Lithuanian coast before the crude oil spill in the Būtinge oil terminal. Moreover, significant seasonal and inter-location differences in the responses were documented (P<0.0001). Nuclear abnormalities were observed most frequently in blue mussels from the Gulf of Gdansk.     

Study on the fate of petroleum-derived polycyclic aromatic hydrocarbons (PAHs) and the effect of chemical dispersant using an enclosed ecosystem,mesocosm

Polycyclic Aromatic Hydrocarbons (PAHs) are one of the components found in oil and are of interest because some are toxic. We studied the environmental fate of PAHs and the effects of chemical dispersants using experimental 500 l mesocosm tanks that mimic natural ecosystems. The tanks were filled with seawater spiked with the water-soluble fraction of heavy residual oil. Water samples and settling particles in the tanks were collected periodically and 38 PAH compounds were analyzed by gas chromatography-mass spectrometry (GC-MS). Low molecular weight (LMW) PAHs with less than three benzene rings disappeared rapidly, mostly within 2 days. On the other hand, high molecular weight (HMW) PAHs with more than four benzene rings remained in the water column for a longer time, up to 9 days. Also, significant portions (10-94%) of HMW PAHs settled to the bottom and were caught in the sediment trap. The addition of chemical dispersant accelerated dissolution and biodegradation of PAHs, especially HMW PAHs. The dispersant amplified the amounts of PAHs found in the water column. The amplification was the greater for the more hydrophobic PAHs, with an enrichment factor of up to six times. The increased PAHs resulting from dispersant use overwhelmed the normal degradation and, as a result, higher concentrations of PAHs were observed in water column throughout the experimental period. We conclude that the addition of the dispersant could increase the concentration of water column PAHs and thus increase the exposure and potential toxicity for organisms in the natural environment. By making more hydrocarbon material available to the water column, the application of dispersant reduced the settling of PAHs. For the tank with dispersant, only 6% of chrysene initially introduced was detected in the sediment trap whereas 70% was found in the trap in the tank without dispersant.     

Quantitative analysis of residual fuel oil in sediment samples by absorption spectrophotometry

The ultraviolet spectra of samples of an oil pollutant and crude oil at various concentrations were examined. Strong absorption maxima appear at approximately 228 nm and 256 nm. These permit a quantitative analysis in polluted sediment samples many months after the spill. Results obtained from three visits to an oil polluted beach on the South coast of South Africa are reported.     

Polycyclic aromatic hydrocarbon contamination and recovery characteristics in some organisms after the Nakhodka oil spill

Following the oil spill from the Russian tanker Nakhodka in 1997 in the Sea of Japan, polycyclic aromatic hydrocarbons (PAH) were monitored for three years in some molluscs from the Mikuni-cho shore in Japan. Total PAH concentrations in marine organisms except for spiny top shell, ranged from 5.3 to 32.7 ng/g wet weight, but no trends were evident. Total PAH concentration in spiny top shell (Turbo cornutus) was 44 ng/g w.w. in the first month after the oil spill. However, it rapidly decreased to less than 5.4 ng/g w.w. from the second month. Spiny top shell, which was exposed to dietary Nakhodka heavy fuel oil, concentrated benzo(a)pyrene to 17.1 ng/g w.w. after two weeks of exposure and then rapidly eliminated it during an elimination phase. These results suggest that spiny top shell accumulates PAHs because of their low ability to metabolize PAH, but it can excrete parent PAHs rapidly when removed from the source of contamination. Thus it is suitable as an indicator organism in monitoring oil contamination. It can also be inferred from these field and laboratory investigations that, in three years, organisms from the Mikuni-cho shore seem to have adequately recovered from the Nakhodka oil spill contamination.     

Phase distribution of hydrocarbons in the water column after a pelagic deep ocean oil spill

Spills from wrecks are a potential major source of pollution in the deep ocean. However, not much is known about the fate of a spill at several kilometers depth, beyond the oceans continental shelves. Here, we report the phase distribution of hydrocarbons released from the wrecks of the Prestige tanker, several years after it sank in November 2002 to depths between 3500 and 3800 m. The released oil reached the surface waters above the wrecks without any signs of weathering and leaving an homogenous signature throughout the water column. At depths of several kilometers below the sea surface, the occurrence and spread of the deep sea oil spill could be evaluated better by quantifying and characterizing the dissolved hydrocarbon signature, rather than just the investigation of hydrocarbons in the suspended particulate matter.