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).     

Influence of salinity and fish species on PAH uptake from dispersed crude oil

The use of chemical oil dispersants to minimize spill impacts causes a transient increase in hydrocarbon concentrations in water, which increases the risk to aquatic species if toxic components become more bioavailable. The risk of effects depends on the extent to which dispersants enhance the exposure to toxic components, such as polycyclic aromatic hydrocarbons (PAH). Increased salinities can reduce the solubility of PAH and the efficiency of oil dispersants. This study measured changes in the induction of CYP1A enzymes of fish to demonstrate the effect of salinity on PAH availability. Freshwater rainbow trout and euryhaline mummichog were exposed to water accommodated fractions (WAF), and chemically-enhanced water accommodated fractions (CEWAF) at 0 per thousand, 15 per thousand, and 30 per thousand salinity. For both species, PAH exposure decreased as salinity increased whereas dispersant effectiveness decreased only at the highest salinity. Hence, risks to fish of PAH from dispersed oil will be greatest in coastal waters where salinities are low.     

Impact of adsorbed petroleum hydrocarbons on marine organisms

Adsorptions of south Louisiana crude oil from seawater by clays, non-clay minerals and sediments were conducted in the laboratory. Effect of sediment-adsorbed and water dispersed crude oil on adult oysters were investigated in aquaria. Hydrocarbons in oyster tissues and surrounding water were identified by gas chromatography. Field specimens from an area of a new oil spill and an area five months after an oil spill were also analysed. Evidence of secondary chemical effect of aged oil in sediments on oyster mortality is presented. Oil coated asbestos surfaces severely reduced recruitment of sedentary larval organisms.     

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 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.     

Significance of cytochrome P450 system responses and levels of bile fluorescent aromatic compounds in marine wildlife following oil spills

The relationships among cytochrome P450 induction in marine wildlife species, levels of fluorescent aromatic compounds (FAC) in their bile, the chemical composition of the inducing compounds, the significance of the exposure pathway, and any resulting injury, as a consequence of exposure to crude oil following a spill, are reviewed. Fish collected after oil spills often show increases in cytochrome P450 system activity, cytochrome P4501A (CYP1A) and bile fluorescent aromatic compounds (FAC), that are correlated with exposure to polycyclic aromatic hydrocarbons (PAH) in the oil. There is also some evidence for increases in bile FAC and induction of cytochrome P450 in marine birds and mammals after oil spills. However, when observed, increases in these exposure indicators are transitory and generally decrease to background levels within one year after the exposure. Laboratory studies have shown induction of cytochrome P450 systems occurs after exposure of fish to crude oil in water, sediment or food. Most of the PAH found in crude oil (dominantly 2- and 3-ring PAH) are not strong inducers of cytochrome P450. Exposure to the 4-ring chrysenes or the photooxidized products of the PAH may account for the cytochrome P450 responses in fish collected from oil-spill sites. The contribution of non-spill background PAH, particularly combustion-derived (pyrogenic) PAH, to bile FAC and cytochrome P450 system responses can be confounding and needs to be considered when evaluating oil spill effects. The ubiquity of pyrogenic PAH makes it important to fully characterize all sources of PAH, including PAH from natural resources, e.g. retene, in oil spill studies. In addition, such parameters as species, sex, age, ambient temperature and season need to be taken into account. While increases in fish bile FAC and cytochrome P450 system responses, can together, be sensitive general indicators of PAH exposure after an oil spill, there is little unequivocal evidence to suggest a linkage to higher order biological effects, e.g. toxicity, lesions, reproductive failure.     

Preliminary study on biodegradation of phenanthrene by bacteria isolated from mangrove sediments in Hong Kong

Elevated concentrations of polycyclic aromatic hydrocarbons (PAHs) have been found in mangrove sediments due to anthropogenic pollution, and microbial degradation has been suggested as the best way to remove PAHs from contaminated sediments. The degradation of phenanthrene, a model PAH compound by bacteria, either the enriched mixed culture or individual isolate isolated from surface mangrove sediments was examined. The effects of salinity, initial phenanthrene concentrations and the addition of glucose on biodegradation potential were also investigated. Results show that surface sediments collected from four mangrove swamps in Hong Kong had different degree of PAH contamination and had different indigenous phenanthrene-degrading bacterial consortia. The enriched bacteria could use phenanthrene as the sole carbon source for growth and degrade this PAH compound accordingly. A significant positive relationship was found between bacterial growth and percentages of phenanthrene degradation. The phenanthrene biodegradation ability of the enriched mixed bacterial culture was not related to the degree of PAH contamination in surface sediments. The growth and biodegradation percentages of the enriched mixed culture were not higher than that of the individual isolate especially at low salinity (0 and 10 ppt). High salinity (35 ppt) inhibited growth and biodegradation of phenanthrene of a bacterial isolate but less inhibitory effect was found on the mixed culture. The inhibitory effects of salinity could be reduced with the addition of glucose.     

Minimal incorporation of Deepwater Horizon oil by estuarine filter feeders

Natural abundance carbon isotope analyses are sensitive tracers for fates and use of oil in aquatic environments. Use of oil carbon in estuarine food webs should lead to isotope values approaching those of oil itself, −27‰ for stable carbon isotopes reflecting oil origins and −1000‰ for carbon-14 reflecting oil age. To test for transfer of oil from the 2010 Deepwater Horizon spill into estuarine food webs, filter-feeding barnacles (Balanus sp.) and marsh mussels (Geukensia demissa) were collected from Louisiana estuaries near the site of the oil spill. Carbon-14 analyses of these animals from open waters and oiled marshes showed that oil use was <1% and near detection limits estimated at 0.3% oil incorporation. Respiration studies showed no evidence for enhanced microbial activity in bay waters. Results are consistent with low dietary impacts of oil for filter feeders and little overall impact on respiration in the productive Louisiana estuarine systems.     

Sediment hydrocarbon contamination at the site of the Baie Verte,Newfoundland, oil spill: Results of a Four Year Study

Sediments samples were taken at 3, 15, 27, and 39 months following a spill of diesel oil at Baie Verte, Newfoundland, to determine the effects of weathering on diesel oil trapped in the sediments and to attempt to develop a suitable method for extraction and analysis.Extraction was carried out using hexane, concentration was effected by a procedure modified from Junk et al. (1974) and analysis was completed within 18.0 min by high performance liquid chromatography (HPLC) using a bonded amino silane-(NH₂) column (5 μm, 5 mm × 25 cm) with hexane as mobile phase. A backflush cycle of 22.0 min using hexane and methl-t-butyl ether (90:10%) was performed to elute any polar compounds from the column.This class analysis by HPLC indicated a decrease in the amount of naphthalene, fluorene, phenanthrene and benzo[a]pyrene equivalents over time and at the conclusion of the study (39 months) no PAHs except for fluorene were found in the sediments from Baie Verte.     

Interaction of Humic Substances and Polycyclic Aromatic Hydrocarbons (PAHs) during the Biodegradation of PAHs

The influence of humic substances (HS) on the biodegradation of naphthalene, phenanthrene, and pyrene was studied. As a source of HS, water samples of a bog lake (Hohlohsee) were used. PAH degradation experiments, both in the presence and absence of HS were carried out. All investigated PAHs were degradable by the used bacterial mixed culture. A correlation between the number of aromatic rings of the PAHs and the influence of HS on biodegradation has been shown. Adding of HS led to a decrease in degradation rate in the case of naphthalene. By way of contrast, the presence of HS gave rise to an increase of degradation rate in the case of phenanthrene. The degradation processes of pyrene revealed a marked alteration in the presence of HS which could be deduced from the biochemical oxygen demand (t(1/2BOD_max) values). With regard to the total turnover of the PAHs, there was no noticeable difference between degradation experiments with and without HS. Analyses of the HS after degradation experiments using liquid chromatography coupled with DOC detection (LC/OCD) verify that there was no formation of stable associations between HS and PAHs or their metabolites. The determination of the toxicity of the degradation media as luminescence inhibition against Vibrio fischeri (Photobacterium phosphoreum) showed no detoxification as a result of the presence of HS.     

Composition, distribution and sources of polycyclic aromatic hydrocarbons in sediments of the Gulf of Trieste, Northern Adriatic Sea

The composition, distribution and the sources of polycyclic aromatic hydrocarbons (PAHs) in the surficial sediments of the Gulf of Trieste were investigated. To document the spatial PAH input, surficial sediment samples from 17 locations throughout the Gulf were analysed. The total PAH load determined in the surficial sediment samples are between 30 and 600 ng g-1, and were the highest in the immediate vicinity of the Port of Trieste. The PAH contents decline rapidly with increasing distance from the shore. The ratios of methylphenanthrenes/phenanthrene and methylpyrene/pyrene are sensitive indicators of the origin of PAH pollution in the Gulf which is mostly pyrolitic. The phenanthrene/anthracene ratio was used to determine the approximate location and distance from the source of PAH pollution, while 1-methy 1-7-isopropylphenanthrene (retene) was used as indicator for forest fires. A sediment depth profile indicates a major increase in the PAH concentrations after the First World War.     

Degradation rates of low molecular weight PAH correlate with sediment TOC in marine subtidal sediments

The degradation rate of low molecular weight (LMW) polycyclic aromatic hydrocarbons (PAH) in subtidal marine sediments was found to correlate with sediment total organic carbon (TOC) in stations sampled two or more times after the North Cape No. 2 fuel oil spill. With 2.5-5 months between samplings, stations with lower sediment TOC had lower fractions of LMW PAH remaining at the time of the second sampling. Apparent first-order degradation rate constants calculated for each station varied by nearly an order of magnitude between stations with a range of TOC from 0.4% to 7.3%. The correlation of degradation rate with sediment TOC can be used to provide improved and site-specific predictions of the initial time-course of LMW PAH concentrations in sediments after oil spills.     

A hierarchical approach measures the aerial extent and concentration levels of PAH-contaminated shoreline sediments at historic industrial sites in Prince William Sound, Alaska

A field study was conducted in 2003 to estimate the areal distribution and concentrations of polycyclic aromatic hydrocarbons (PAH) in intertidal sediments at sites of past human and industrial activity (HA sites) in Prince William Sound (PWS), Alaska, the site of the 1989 Exxon Valdez oil spill. More than 50 HA sites, primarily in western PWS, were identified through analysis of historic records and prior field studies, and nine sites were selected for detailed surveys. The areal assessment process consisted of seven steps: (1) identify site from historic records and field surveys; (2) locate visual evidence of surface oil/tar at a site; (3) prepare a site map and lay out a sampling grid over the entire site with 10-m grid spacing; (4) excavate pits to 50 cm depth on the grid; (5) perform a field colorimetric test to estimate total PAH (TPAH) in sediments from the wall of each pit and record the results in the ranges <1 ppm; 1-10 ppm; >10 ppm TPAH; (6) expand grid size if necessary if elevated PAH levels are detected colorimetrically; (7) select 20 samples from each site for same-day shipboard PAH analysis by immunoassay (SDI RaPID PAH) and, based on these results, select sediment samples from each site for full PAH analysis in the laboratory to identify PAH sources. A total of 416 pits were dug at the nine sites. Nine acres of sediments with TPAH >2500 ppb dry wt. were mapped at the nine sites. TPAH concentrations obtained by immunochemical analysis of 181 samples from the nine sites ranged from 20 to 1,320,000 ppb (wet wt.). The contaminants are mixtures of petroleum products (2-3 ring PAH) and combustion products (4-6 ring PAH) unrelated to the 1989 Exxon Valdez oil spill. Mussels and clams collected at these sites have elevated levels of PAH that are compositionally similar to the PAH in the sediments. These findings indicate that at least a portion of the sediment PAH is bioavailable. The PAH sources at these historic industrial sites are chronic. They include relict fuel oil tanks and works located above and within the intertidal zone, with contamination at some locations extending into nearshore sub-tidal sediments. This study shows how a hierarchical approach can be used to quickly and successfully map, quantify, and subsequently, identify sources of PAH in shoreline sediments.     

IT-OSRA: applying ensemble simulations to estimate the oil spill risk associated to operational and accidental oil spills

Oil Spill Risk Assessments (OSRAs) are widely employed to support decision making regarding oil spill risks. This article adapts the ISO-compliant OSRA framework developed by Sepp Neves et al. (J Environ Manag 159:158–168, 2015) to estimate risks in a complex scenario where uncertainties related to the meteo-oceanographic conditions, where and how a spill could happen exist and the risk computation methodology is not yet well established (ensemble oil spill modeling). The improved method was applied to the Algarve coast, Portugal. Over 50,000 simulations were performed in 2 ensemble experiments to estimate the risks due to operational and accidental spill scenarios associated with maritime traffic. The level of risk was found to be important for both types of scenarios, with significant seasonal variations due to the the currents and waves variability. Higher frequency variability in the meteo-oceanographic variables were also found to contribute to the level of risk. The ensemble results show that the distribution of oil concentrations found on the coast is not Gaussian, opening up new fields of research on how to deal with oil spill risks and related uncertainties.     

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.     

The aegean sea oil spill in the Galicia Coast (NW Spain). I. Distribution and fate of the crude oil and combustion products in subtidal sediments.

The spatial distribution and fate of petrogenic and pyrogenic hydrocarbons in coastal sediments following the Aegean Sea oil spill (Galicia, NW Spain) was investigated through a detailed study of chemical markers. Alkanes and acyclic isoprenoid hydrocarbons were degraded within six months of the accident, but triterpane and sterane distributions were still detectable and were useful in monitoring, respectively, the oil source and weathering. Aromatic steranes were also useful source indicators, and oil degradation was clear from the decrease of certain alkyl dibenzothiophene and phenanthrene isomers. The pyrogenic polycyclic aromatic hydrocarbons produced in the tanker wreck were found more persistent than the petrogenic ones. However, the presence of the oil in the sediments was recognized even one year after the accident and was found particularly preserved in the subsurface layers.     

Nature, distribution and origin of polycyclic aromatic hydrocarbons (PAHs) in the sediments of Olbia harbor (Northern Sardinia, Italy)

The nature, origin and distribution of US EPA polycyclic aromatic hydrocarbons (PAHs) in the sediments of Olbia harbor (North Sardinia, Italy) were investigated by gas-chromatography/mass spectrometry (GCMS). PAH concentrations in the sediments (SigmaPAHs) ranged from 0.16 to 0.77 microg g(-1), indicating a homogeneously low level of pollution. A rather exceptional prevalence of low molecular weight PAHs was substantiated: nearly 80% of SigmaPAHs include naphthalene (15.19%) and phenanthrene (64.47%). Carcinogenic compounds were present in very low (BaP, BkF, BaA and DBA) or negligible (BbF and Inp) concentrations. As indicated by the Phen/Ant molar ratio, the main source of PAHs is petrogenic, probably due to oil spills from shipping. The low/high molecular weight ratio (ranging between 1.2 and 26) distinguishes the sediments of the tourist harbor from those of the commercial/industrial harbor. Moreover, a slight but meaningful pyrolytic contribution to pollution was found in the tourist harbor, which has the most polluted sediments in the whole harbor. Finally, good linear correlations were found between a selected PAH (Phen and Naph) and selected sums of PAHs (i.e. the total amount of the other 15 US EPA and the sum of low molecular weight PAHs).     

The Gladstone (Australia) oil spill - impacts on intertidal areas: baseline and six months post-spill

In January 2006, 25 tonnes of heavy fuel oil spilled into the Port of Gladstone in Queensland, Australia, from the breached hull of a bulk carrier ship. While approximately 18 tonnes of the oil was recovered, a certain amount of oil was deposited in the intertidal areas of Port Curtis leaving a highly visible, viscous residue. The objectives of this research were to assess the short-term (one month post-spill) and medium-term (six months post-spill) impacts on the intertidal habitat.Sediment polycyclic aromatic hydrocarbons (PAHs) and metal concentrations, mangrove communities and intertidal macroinvertebrates were assessed at oil impacted sites, adjacent sites which were not visibly impacted and reference sites which were located outside the recorded distribution of the oil spill.At one month post-spill, highest PAH concentrations were found at the impacted sites, with concentrations of some PAHs exceeding Australian and New Zealand sediment quality guidelines (SQG) [ANZECC/ARMCANZ, 2000. Sediment Quality Guidelines. Australia and New Zealand Environment and Conservation Council and Agriculture and Resource Management Council of Australia and New Zealand]. However, by six months post-spill PAH concentrations had significantly decreased. PAH concentrations tended to be higher in the back (upper) intertidal zone than at the front of the mangrove stand, and sediment cores indicated that PAH contaminants had remained in the top 4 cm of the sediment. These results indicate that the overall decreased PAH concentrations are likely to be due to evaporation, photoxidation and tidal flushing of the residual oil in these impacted sites.During the initial survey, the impact site contained very few or no crabholes in the high intertidal area, indicating a low crab density in comparison to reference sites. However, at six months post-spill mangrove crab communities appeared to be fully recovered with crabhole densities in impact sites similar to reference sites.While little immediate impact was evident on mangrove parameters, significantly higher seedling mortality and defoliation was apparent at six months post-spill, particularly in the upper intertidal zone. Intertidal macrobenthic communities did not appear to be impacted, either immediately or at six months post-spill. Monitoring of these oil impacted intertidal areas will continue to examine the long-term impacts/recovery from the oil spill.     

Biodegradation of toxic chemicals in Guayanilla Bay,Puerto Rico

Studies were conducted to assess the factors that may influence the rate and extent of biodegradation of biphenyl, naphthalene, phenanthrene, pentachlorophenol (PCP) and p-nitrophenol in water samples collected from the Guayanilla Bay (18 degrees N; 67.45 degrees W), southwest of Puerto Rico. In vitro studies mediated slow degradation of biphenyl, naphthalene and phenanthrene substrates by natural microbial flora present in the Bay. Addition of KNO(3) as a source of inorganic N greatly enhanced the degradation of phenanthrene but not of naphthalene, suggesting that effects on degradation due to nutrient limitation were compound specific. The rate and extent of degradation of naphthalene and PCP were higher in water samples collected closer to the source of contamination, i.e. the petrochemical complex. The identity of a phenanthrene degrading bacterium, previously identified by conventional phenotypic method (Zaidi et al., Utilizing Nature's Advanced Materials, Oxford Unviersity Press, 1999) as Alteromonas sp., was confirmed by partial DNA sequencing of the small subunit rRNA gene.     

Induction of DNA strand breaks in the mussel (Mytilus trossulus) and clam (Protothaca staminea) following chronic field exposure to polycyclic aromatic hydrocarbons from the Exxon Valdez spill

In 2002, 13 years after the Exxon Valdez spill, mussels and clams were examined for lingering oil exposure and damage. Known oil patches were sampled at four locations, and compared to nearby reference areas (same bay), and were also compared to "hot reference" sites to verify the methods used (Cordova harbor and fresh diesel spill at Port Chalmers). Passive samplers deployed for a month at the sites, along with tissue samples, confirmed that the oiled sites were oiled (fingerprinting back to Exxon Valdez oil) and that reference sites were clean. The highest PAH loads were detected in sub-surface interstitial waters at oiled sites. Exposure at the surface was generally low level, and probably intermittent. DNA damage was assessed in blood cells using sensitive comet analyses. DNA strand breakage was detected in both mussels and clams, with the highest level of damage detected at "hot reference" sites of Cordova harbor and Port Chalmers. Bioavailability and DNA damage at the oiled sties was low, indicating there has been substantial progress in recovery from the spill 13 years before, yet low level bioavailability and damage were still detectable.