Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: Environmental legacy after twelve years of the Gulf war oil spill

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU_FCV,43). Samples were assigned to risk categories according to ESBTU_FCV,43 values: no-risk (≤1), low (>1-≤2), low-medium (>2-≤3), medium (>3-≤5) and high-risk (>5). Sixty seven percent of samples had ESBTU_FCV,43 > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30-<60 cm layer from heavily oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War.     

Two years of oil disaster in the Arabian Gulf

In January–February 1991, about 1 million m³ of crude oil were released into the Arabian Gulf as a means of ecological warfare. A stretch of 644 km along the Saudi Arabian coast was heavily polluted over a width between a few meters and more than one kilometer. In four studies performed between March 1991 and April 1993 the state of representative areas of the affected coast was examined with the result that only minor changes were found in those oiled zones which are seldom inundated by the tides. Technical measures up to 1993 did not exceed the test level. A biological regeneration process is in progress which was not recognized as such in analyses of previous coastal oil pollution. Cyanobacterial mats, containing hydrocarbon-degrading bacteria, grow on oiled sediments which are regularly reached by tidal water. Shrinking and fracturing of the stable tar crusts starts a process of loosening and degrading of aged hydrocarbons.     

The effects of oil spill and clean-up on dominant US Gulf coast marsh macrophytes: a review

The objective of this review was to synthesize existing information regarding the effects of petroleum hydrocarbons on marsh macrophytes in a manner that will help guide research and improve spill-response efficiency. Petroleum hydrocarbons affect plants chemically and physically. Although plants sometime survive fouling by producing new leaves, even relatively non-toxic oils can stress or kill plants if oil physically prevents plant gas-exchange. Plant sensitivity to fouling varies among species and among populations within a species, age of the plant, and season of spill. Physical disturbance and compaction of vegetation and soil associated with clean-up activities following an oil spill appear to have detrimental effects on the US Gulf coast marshes. Other techniques, including the use of chemicals such as cleaners or bioremediation, may be necessary to address the problem. Clean-up may also be beneficial when timely removal prevents oil from migrating to more sensitive habitats.     

Bioaccumulation of nickel and vanadium by clams (Meretrix meretrix) living in different salinities along the Saudi coast of the Arabian Gulf

The objective of this study was to investigate bioaccumulation of nickel (Ni) and vanadium (V) in clams living in different salinity regimes along the Saudi coast of the Arabian Gulf. Several hundred clam (Meretrix meretrix), sediment, and seawater samples were collected from 12 locations. Concentrations of Ni and V were determined in these samples using an inductively coupled argon plasma analyzer. Concentrations of Ni and V in the clams varied between 0.35 and 2.61 mg kg(-1) and between 0.13 and 0.35 mg kg(-1) wet tissue, respectively. Analysis of variance of the data revealed significant (P<0.01) inter- and intra-station variations in Ni concentrations in clams. In contrast, the mean concentration of V in clams from all the stations were statistically similar. Correlation between the biometric characteristics of clams and Ni and V concentrations were not statistically significant. Significant (P<0.05) geographical variations in Ni and V concentrations in the sediment samples were found, with relatively higher concentrations in the northern part of the Gulf where there are many oil fields. Ni and V in the sediments were significantly (P<0.05) correlated, suggesting a common contamination source for these elements. Interactions between Ni and V in clams and sediment were poor.     

The effect of crude oil and oil spill chemicals on nitrogen fixation in the cyanobacteria Nostoc sp

The effects of crude oil and three oil spill dispersants (Corexit 9600, 9550 and 7664) on nitrogenase activity in the cyanobacteria Nostoc sp. were examined. The addition of oil to Nostoc sp. cultures resulted in a catastrophic decline in nitrogenase activity with activity ceasing 7 h after treatment. The addition of a dispersant with the oil did not ameliorate this effect. Cultures exposed to high concentrations of dispersants showed lower rates on nitrogenase activity than untreated cultures. However, it is unlikely that dispersant concentrations of this magnitude would occur in the field. At the lowest concentration tested, which approximates the manufacturer's recommended application rate, the effects of the dispersant appear to be negligible.     

Role of cyanobacteria in the biodegradation of crude oil by a tropical cyanobacterial mat

Cyanobacterial mats are ubiquitous in tropical petroleum-polluted environments. They form a high biodiversity microbial consortium that contains efficient hydrocarbons degraders. A cyanobacterial mat collected from a petroleum-contaminated environment located in Indonesia was studied for its biodegradation potential. In the field, the natural mat was shown to degrade efficiently the crude oil present in the environment. This natural mat demonstrated also a strong activity of degradation on model crude oil under laboratory conditions. In axenic cultures, the monospecific cyanobacterium Phormidium animale that constitute the bulk of the biomass did not exhibit any degradative capacity on hydrocarbons in the range of C13-C35 carbon atom number either in autotrophic or heterotrophic conditions. It was concluded that this cyanobacterial strain living on a heavily contaminated site had no direct effect on biodegradation of crude oil, the degradation activity being exclusively achieved by the other microorganisms present in the microbial consortium of the mat.     

Assessment of crude oil biodegradation in arctic seashore sediments: effects of temperature,salinity, and crude oil concentration

The expected increase in offshore oil exploration and production in the Arctic may lead to crude oil spills along arctic shorelines. To evaluate the potential effectiveness of bioremediation to treat such spills, oil spill bioremediation in arctic sediments was simulated in laboratory microcosms containing beach sediments from Barrow (Alaska), spiked with North Slope Crude, and incubated at varying temperatures and salinities. Biodegradation was measured via respiration rates (CO₂ production); volatilization was quantified by gas chromatography/mass spectrophotometry (GC/MS) analysis of hydrocarbons sorbed to activated carbon, and hydrocarbons remaining in the sediment were quantified by GC/flame ionization detector (FID). Higher temperature leads to increased biodegradation by naturally occurring microorganisms, while the release of volatile organic compounds was similar at both temperatures. Increased salinity had a small positive impact on crude oil removal. At higher crude oil dosages, volatilization increased, however CO₂ production did not. While only a small percentage of crude oil was completely biodegraded, a larger percentage was volatilized within 6–9 weeks.     

原油及油制品中多环芳烃化学指纹的分布规律研究

利用原油及油制品中的多环芳烃(PAHs)化学指纹特征进行溢油鉴别是确定海上溢油事故污染源的重要技术.使用气相色谱一质谱联用方法测定了汽油E90#、汽油E93#、润滑油150SN、轻柴油-10#、柴油5#、重柴油180#、重柴油380#、俄罗斯原油及大庆原油的PAHs化学指纹图谱.结果表明,在各种PAHs中,萘(Nap)、2-甲基萘(2-MN)和1-甲基萘(1-MN)的含量最高,三者总和占52%～86%(质量分数,下同).轻质油(汽油、轻柴油、柴油和润滑油)和重质油(原油和重柴油)的化学指纹图谱存在明显差异:重质油中2-MN平均为28%,轻质油中Nap平均为42%.Nap/2-MN(Nap与2-MN质量比,以下各物质表述意义同)和Nap/1-MN的比值关系区分的趋势类似,并且存在典型的线性相关性(R=0.92,p<0.01).表明原油及油制品中的Nap、1-MN和2=MN的含量相对固定,使用Nap/2-MN和Nap/1-MN比值方法鉴别油类品种具有较高的可靠性.应用主成分分析方法对9种油样的PAHs化学指纹特征进行了分析,结果表明该方法是一种有效和有潜力的溢油鉴别方法.     

Photocatalytic pre-treatment with food-grade TiO2 increases the bioavailability and bioremediation potential of weathered oil from the Deepwater Horizon oil spill in the Gulf of Mexico

Using the 2010 Deepwater Horizon oil spill in the Gulf of Mexico as an impetus, we explored the potential for TiO₂-mediated photocatalytic reactive oxygen species (ROS) generation to increase the bioavailability (solubility) and biodegradability of weathered oil after a spill. Food grade TiO₂, which is FDA approved for use as food additive in the United States, was tested as a photocatalyst for this novel application. Photocatalytic pre-treatment (0.05 wt.% TiO₂, UV irradiation 18 W m^?2, 350–400 nm) for 24 h in a bench top photoreactor increased the soluble organic carbon content of weathered oil by 60%, and enhanced its subsequent biodegradation (measured as O₂ consumption in a respirometer) by 37%. Photocatalytic pre-treatment was also tested outdoors under sunlight illumination, but no significant increase in solubility or biodegradation was observed after 11 d of exposure. Although sunlight irradiation of food-grade TiO₂ generated ROS (assessed by the degradation of 4-chlorophenol as a probe compound), the efficacy of weathered oil pre-treatment was apparently hindered by sinking of the photocatalysts under quiescent conditions and illumination occlusion by the oil. Overall, results indicate that photocatalytic pre-treatment to stimulate bioremediation of weathered oil deserves further consideration, but controlling the buoyancy and surface hydrophobicity of the photocatalysts will be important for future efforts to enable ROS generation in proximity to the target compounds.     

Cholinesterase and glutathione S-transferase activities of three mollusc species from the NW Portuguese coast in relation to the ‘Prestige’ oil spill

In November 2002, the tanker ‘Prestige’ released about 19,000 tonnes of a heavy fuel oil (no. 6) before sinking with about 58,000 tonnes of its cargo, 135 miles from Cabo Finisterra (Spain). A considerable part of the released fuel oil reached the Galician coast, causing a heavy black tide and an ecological disaster. Although the black tide did not reach the NW coast of Portugal, it is possible that some of the fuel oil or its components also arrived to this area directly through the sea water and/or indirectly through the food chain. Therefore, the aim of this study was to investigate possible changes in two widely used biomarkers, the activity of the enzymes cholinesterases (ChE) and glutathione S-transferases (GST), of three molluscs (Mytilus galloprovincialis, Nucella lapillus and Monodonta lineata) from wild populations of the NW Portuguese coast in relation to the ‘Prestige’ oil spill. Molluscs were collected seasonally before (autumn 2002) and after (winter 2002/2003), spring and summer 2003) the oil spill at several sites along the Portuguese NW coast. Enzymatic activities determined before the accident were compared with those determined at different times after the oil spill taking into consideration abiotic factors. Information from different parameters was integrated by Redundancy Analysis and Principal Response Curves (PRC). Results show that GST and ChE activities were influenced by abiotic factors. Despite this influence, the results of PRC analysis also suggest that some of the fuel oil reached the NW Portuguese coast changing the patterns of ChE and GST activities of local populations of rocky shore species. Furthermore, the present study highlights the need of long-term monitoring with wild populations to assess both historical and punctual effects of pollution in the marine environment.     

Burial,exportation and degradation of acyclic petroleum hydrocarbons following a simulated oil spill in bioturbated Mediterranean coastal sediments

A field study was conducted in a French Mediterranean littoral (Gulf of Fos) in order to determine the role of bioturbation processes during the bioremediation of oil-contaminated sediments. Inert particulate tracers (luminophores) and Arabian light crude oil were deposited at the surface of sediment cores incubated in situ for 2, 6 and 12 months. After incubation, luminophores and hydrocarbons presented roughly similar depth distributions in the sediment, showing a continuous burial of material until 55 mm depth. Short-chain (< or = n-C25) n-alkanes were totally removed from the sedimentary column after 6 months, whereas approximately 20% of heavier n-alkanes (e.g. n-C30) and of isoprenoid hydrocarbons (pristane (Pr) and phytane (Ph)) remained at the end of the experiment. The determination of the degradation constant and the turn-over rate of individual hydrocarbon indicated that C17-25 n-alkanes were degraded two to three times faster than longer homologues and than pristane and phytane. Using the 17alpha,21beta-C30-hopane as an internal inert reference, we could demonstrate that, after 12 months of in situ incubation, 55% of the losses of the n-alkanes < or = C25 and 35% of the losses of the heavier n-alkanes and of Pr and Ph were due to biodegradation processes. These results demonstrate that the activity of benthic organisms can have a significant influence on the qualitative and quantitative fate of acyclic hydrocarbons following a petroleum contamination in marine coastal sediments.     

Sediment contamination, bioavailability and toxicity of sediments affected by an acute oil spill: Four years after the sinking of the tanker Prestige (2002)

Sediment contamination and three bioassays were used to determine the sediment quality four years after an oil spill (Prestige, 2002): the Microtox test, a 10-day bioassay using the amphipod Ampelisca brevicornis, and a polychaete 10-day toxicity test with the lugworm Arenicola marina. In addition, bioaccumulation of PAHs was examined in the polychaete after 10 days of exposure. The results obtained from the toxicity tests and bioaccumulation analyses were statistically compared to the sediment chemical data, in order to assess the bioavailability of the contaminants, their effects, and their relationship with the oil spill. The sediments studied were from two areas of the Galician Coast (NW Spain): the Bay of Corme-Laxe and the Cíes Island, located in the Atlantic Island National Park. The results point to a decrease in contamination with respect to previous studies and to the disappearance of the acute toxicity four years after the oil spill. However an important bioaccumulation of PAHs was detected in the organisms exposed to sediments from Corme-Laxe, suggesting that despite the recovery of the environmental quality of the area, effects in the biota might be occurring.     

Bottom sediments of the Arabian Gulf--II. TPH and TOC contents as indicators of oil pollution and implications for the effect and fate of the Kuwait oil slick

Measurements of total petroleum hydrocarbon (TPH) concentrations in 77 core samples collected in 1992 from the bottom sediments of the Arabian Gulf were used to delineate oil pollution levels and their distribution in the region. Seven chronic moderately (TPH 50-89 microg g(-1)) and heavily (TPH 266-1448 microg g(-1)) polluted areas were identified; three in the northern part of the region and four in the southern part. Oil pollution in these areas was attributed to natural oil seepage, accidental damage to pipelines, accidental spillage from tankers, the Nowruz oil slick, and tanker deballasting. Present-day intermediate (TPH 50-114 microg g(-1)) and high (TPH 200-1122 microg g(-1)) pollution levels were identified in 10 areas. Of these, three polluted areas in the northeastern corner, offshore Saudi Arabia and offshore Bahrain, Qatar and United Arab Emirates are probably directly affected by the Kuwait oil slick. A new scenario is suggested for the movement and fate of the oil slick, in which additional large oil discharges from northern sources, as well as substantial quantities of eroded oiled sediments and oil floating from heavily impacted tidal flats along the Saudi Arabian coastline, serve as sources of oil pollution. A definite relationship exists between the grain-size distribution and the TPH content of bottom sediments, with the highest TPH concentrations in the muddy sediments, suggesting that adsorption onto muds is the primary mechanism of oil pollutant accumulation in the Arabian Gulf. Total organic carbon measurements do not correlate positively with the grain-size distribution and TPH contents of the sediments, and hence cannot be used as indicators for petroleum hydrocarbon pollution in the Arabian Gulf.     

Field investigation on the toxicity of Alaska North Slope crude oil (ANSC) and dispersed ANSC crude to Gulf killifish, Eastern oyster and white shrimp

A field investigation was conducted on a Louisiana Spartina alterniflora shoreline to evaluate the toxic effects of crude oil (Alaska North Slope crude oil, ANSC) and dispersed oil (ANSC + dispersant Corexit 9,500) on three aquatic species indigenous to the Gulf of Mexico: Fundulus grandis (Gulf killifish), Crassostrea virginica (Eastern oyster), and Litopenaeus setiferus (white shrimp). Results indicated that total hydrocarbons concentration value in oiled treatments decreased rapidly in 3h and were below 1 ppm at 24h after initial treatment. Corexit 9,500 facilitated more ANSC fractions to dissolve and disperse into the water column. L. setiferus showed short-term sensitivity to the ANSC and ANSC + 9,500 at 30 ppm. However, most test organisms (>83%) of each species survived well after 24h exposure to the treatments. Laboratory tests conducted concurrent with the field investigation indicated that concentrations of crude oil higher than 30 ppm were required for any significant toxic effect on the juvenile organisms tested.     

The effects of crude oil and the effectiveness of cleaner application following oiling on US Gulf of Mexico coastal marsh plants

Field studies were conducted in two different marsh habitats in Louisiana coastal wetlands to evaluate the effects of oiling (using South Louisiana Crude oil, SLC) and the effectiveness of a shoreline cleaner (COREXIT 9580) in removing oil from plant canopies. The study sites represented two major marsh habitats; the brackish marsh site was covered by Spartina patens and the freshwater marsh was covered by Sagittaria lancifolia. Field studies were conducted in each habitat using replicated 5.8 m2 plots that were subjected to three treatments; oiled only, oiled + cleaner (cleaner was used 2 days after oiling), and a control. Plant gas exchange responses, survival, growth, and biomass accumulation were measured. Results indicated that oiling led to rapid reductions in leaf gas exchange rates in both species. However, both species in 'oiled + cleaned' plots displayed improved leaf conductance and CO2 fixation rates. Twelve weeks after treatment initiation, photosynthetic carbon fixation in both species had recovered to normal levels. Over the short-term, S. patens showed more sensitivity to oiling with SLC than S. lancifolia as was evident from the data of the number of live shoots and above-ground biomass. Above-ground biomass remained significantly lower than control in S. patens under 'oiled' and 'oiled + cleaned' treatments while it was comparable to controls in S. lancifolia. These studies indicated that the cleaner removed oil from marsh grasses and alleviated the short-term impact of oil on gas exchange function of the study plants. However, use of cleaner had no detectable effects on above-ground biomass production or regeneration at the end of the first growing season in S. patens. Similarly, no beneficial effects of cleaner on carbon fixation and number of live shoots were apparent beyond 12 weeks in S. lancifolia.     

Impact of crude oil exposure on nitrogen cycling in a previously impacted Juncus roemerianus salt marsh in the northern Gulf of Mexico

This study investigated potential nitrogen fixation, net nitrification, and denitrification responses to short-term crude oil exposure that simulated oil exposure in Juncus roemerianus salt marsh sediments previously impacted following the Deepwater Horizon accident. Temperature as well as crude oil amount and type affected the nitrogen cycling rates. Total nitrogen fixation rates increased 44 and 194 % at 30 °C in 4,000 mg kg^?1 tar ball and 10,000 mg kg^?1 moderately weathered crude oil treatments, respectively; however, there was no difference from the controls at 10 and 20 °C. Net nitrification rates showed production at 20 °C and consumption at 10 and 30 °C in all oil treatments and controls. Potential denitrification rates were higher than controls in the 10 and 30?ºC treatments but responded differently to the oil type and amount. The highest rates of potential denitrification (12.7?±?1.0 nmol N g^?1 wet h^?1) were observed in the highly weathered 4,000 mg kg^?1 oil treatment at 30 °C, suggesting increased rates of denitrification during the warmer summer months. These results indicate that the impacts on nitrogen cycling from a recurring oil spill could depend on the time of the year as well as the amount and type of oil contaminating the marsh. The study provides evidence for impact on nitrogen cycling in coastal marshes that are vulnerable to repeated hydrocarbon exposure.     

Bottom sediments of the Arabian Gulf--III. Trace metal contents as indicators of pollution and implications for the effect and fate of the Kuwait oil slick

The trace metal contents of 71 core samples collected in 1992 from the bottom sediments of the Arabian Gulf are used to determine the regional distribution of concentration and pollution levels of these substances in the region. Chronic contamination was recorded in seven locations: the northwestern area (Fe), the northeastern area (Fe, V and Ni), the north-central area (V and Ni), the central area (Fe, Pb, V and Ni), the south-central area (Cu), the eastern area (Cu) and the southeastern area (Fe, V and Ni). Present-day contamination was identified in three locations only: the north-central area (V), the central area (Pb, V and Ni) and the southeastern area (Fe, V and Ni). Diversified natural and anthropogenic inputs may have provided the sources of this contamination. The V/Ni ratios of recent marine sediments cannot be used in identifying oil spillages or in oil-sediment correlation studies. Positive correlations are found between increasing trace metal concentration and decreasing carbonate content and grain size, verifying that adsorption onto muds is the primary mechanism of trace metal concentration in marine sediments. Correlations with TOC (total organic carbon) contents indicate that organic matter is a significant concentrator only in the case of Pb and Cu. With the exception of the Fe contamination in the northwest area due to river transport, all chronic and present-day trace metal concentrations are within the permissible natural background levels in the western offshore areas, including the two areas thought to be polluted by the Kuwait oil slick, thereby supporting the idea that airborne fallout from oil fires was deposited in a limited coastal area between Kuwait and Bahrain, and verifying that the oil slick had minimal effect on the state of pollution by trace metals in the Arabian Gulf.     

Seabird feathers as monitors of the levels and persistence of heavy metal pollution after the Prestige oil spill

We measured heavy metal concentrations in yellow-legged gulls (n = 196) and European shags (n = 189) in order to assess the temporal pattern of contaminant exposure following the Prestige oil spill in November 2002. We analysed Pb, Cu, Zn, Cr, Ni and V levels in chick feathers sampled at four colonies during seven post-spill years (2003-2009), and compared results with pre-spill levels obtained from feathers of juvenile shag corpses (grown in spring/summer 2002). Following the Prestige wreck, Cu (4.3-10 μg g⁻¹) and Pb concentrations (1.0-1.4 μg g⁻¹) were, respectively, between two and five times higher than pre-spill levels (1.5-3.6 and 0.1-0.4 μg g⁻¹), but returned to previous background concentrations after three years. Our study highlights the suitability of chick feathers of seabirds for assessing the impact of oil spills on heavy metal contamination, and provides the best evidence to date on the persistence of oil pollution after the Prestige incident.     

Distribution and source of plutonium in sediments from the southern Gulf of Mexico

Environmental Science and Pollution Research - Here, we report on new data (75 analyses) of plutonium (Pu) isotopes to elucidate activity concentrations, inventories, sources, and their transport...