Long term monitoring for oil in the Exxon Valdez spill region

In the aftermath of the 1989 Exxon Valdez oil spill, a Long Term Environmental Monitoring Program (LTEMP) has been regularly sampling mussels (and some sediments) for polycyclic aromatic and saturated hydrocarbons (PAH and SHC) at sites in Port Valdez, Prince William Sound, and the nearby Gulf of Alaska region. After 1999, a decreasing trend appears in total PAH (TPAH) in tissues at all sites with current values below 100 ng/g dry weight (many below 50 ng/g). Currently, most samples reflect a predominantly dissolved-phase signal. This new low in TPAH likely represents ambient background levels. Synchrony in TPAH time-series and similarities in the hydrocarbon signatures portray regional-scale dynamics. The five inner Prince William Sound sites show similar composition and fluctuations that are different from the three Gulf of Alaska sites. The two Port Valdez sites represent a unique third region primarily influenced by the treated ballast water discharge from the Alyeska Marine Terminal. Prince William Sound has reverted to a stable environment of extremely low level contamination in which local perturbations are easily detected.     

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.     

Oil persistence on beaches in Prince William Sound - a review of SCAT surveys conducted from 1989 to 2002

In 2002, 13 years after the Exxon Valdez oil spill (EVOS), 39 selected sites in Prince William Sound (PWS) were re-surveyed following established shoreline cleanup assessment team (SCAT) field observation procedures to document surface and sub-surface oiling conditions in shoreline sediments and to compare results with those from previous Shoreline Cleanup Assessment Team (SCAT) surveys and other surveys in PWS. The selected sites are locations where EVOS oil persisted in 1992, at the time the Federal and State On-Scene Coordinators determined that the cleanup was complete and that further cleanup activities would provide no net environmental benefit. These sites had been included in a 2001 NOAA survey of shoreline oiling conditions and account for 88% of the sub-surface oil residues (SSO) oil documented by that study. The 2002 field survey found isolated occurrences of residual EVOS surface oil residues (SO) in the form of weathered asphalt pavement at 15 of the 39 sites. This residual SO typically consisted of asphalt in mixed sand/gravel substrate, located within a wave shadow effect created by boulders or bedrock in the upper intertidal to supratidal zone. Residual SO, expressed as a continuous oil cover, was less than 200 m(2) within the approximately 111,120 m(2) surveyed. A total of 1182 pits were dug at locations where SSO residues were present in 1992. Six of the 39 sites and 815 (68%) of the pits contained no residual SSO. Eighty-three percent of pits with SSO residues were found primarily in middle to upper intertidal locations. SSO residues commonly occurred in a discontinuous approximately 3 cm thick band 5-10 cm below the boulder/cobble or pebble/gravel veneer. The SO and SSO occurrences in the 2002 survey closely match the locations where they were found in 1992 and earlier surveys; however, in 2002 residual SSO patches are more discontinuous and thinner than they were in the earlier surveys. These sites are biased toward SSO persistence; those that have SSO residues represent less than 0.5% of the originally oiled shorelines in PWS. Despite evidence of continued oil weathering, both at the surface and in the sub-surface, it is clear that the natural cleaning processes at these particular locations are slow. The slow weathering rates are a consequence of the oil residue being incorporated in finer sediments (fine sand, silt, mix) and isolated from active weathering processes as boulders and outcrops, shallow bedrock asperities, or boulder-armoring create wave shadows and limit effective physical action on shorelines.     

PCB exposure in sea otters and harlequin ducks in relation to history of contamination by the Exxon Valdez oil spill

Exposure to contaminants other than petroleum hydrocarbons could confound interpretation of Exxon Valdez oil spill effects on biota at Prince William Sound, Alaska. Hence, we investigated polychlorinated biphenyls (PCBs) in blood of sea otters and harlequin ducks sampled during 1998. PCB concentrations characterized by lower chlorinated congeners were highest in sea otters from the unoiled area, whereas concentrations were similar among harlequin ducks from the oiled and unoiled area. Blood enzymes often elevated by xenobiotics were not related to PCB concentrations in sea otters. Only sea otters from the unoiled area had estimated risk from PCBs, and PCB composition or concentrations did not correspond to reported lower measures of population performance in sea otters or harlequin ducks from the oiled area. PCBs probably did not influence limited sea otter or harlequin duck recovery in the oiled area a decade after the spill.     

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.     

Cytochrome P450 isozyme protein verified in the skin of southern hemisphere humpback whales (Megaptera novaeangliae): implications for biochemical biomarker assessment

Large mysticete whales represent a unique challenge for chemical risk assessment. Few epidemiological investigations are possible due to the low incidence of adult stranding events. Similarly their often extreme life-history adaptations of prolonged migration and fasting challenge exposure assumptions. Molecular biomarkers offer the potential to complement information yielded through tissue chemical analysis, as well as providing evidence of a molecular response to chemical exposure. In this study we confirm the presence of cytochrome P450 reductase (CPR) and cytochrome P450 isoenzyme 1A1 (CYP1A1) in epidermal tissue of southern hemisphere humpback whales (Megaptera novaeangliae). The detection of CYP1A1 in the integument of the humpback whale affords the opportunity for further quantitative non-destructive investigations of enzyme activity as a function of chemical stress.     

Recovery of interior brackish marshes seven years after the chalk point oil spill

Seven years after the April 2000 spill of 140,000 gallons of a mixture of No. 6 and No. 2 fuel oils in the Patuxent River, Maryland, heavily oiled brackish marshes showed continuing effects. Stem density and stem height were significantly lower in oiled versus unoiled sites for Spartina alterniflora but not Spartina cynosuroides habitats. In contrast, belowground biomass was significantly lower in S. cynosuroides habitats but not S. alterniflora habitats. Total PAH concentrations were up to 453 mg/kg in surficial soils (0-10 cm) and 2921 mg/kg with depth (10-20 cm). The oil had lost 22-76% of its initial PAH content after seven years, although the oil in marsh soils has undergone little to no additional weathering since Fall 2000. Based on amphipod acute toxicity tests and sediment quality guidelines, 25% of the soils in the marsh are expected to be toxic (ESB-TU_FCV values > 3.0; P_Max > 0.65).     

Chronic exposure of adults and embryos of Pandalus borealis to oil causes PAH accumulation, initiation of biomarker responses and an increase in larval mortality

Adult shrimps (Pandalus borealis) and their embryos were exposed to an oil-water dispersion (OWD) at concentrations of 0.015, 0.06 and 0.25 mg/L using a continuous flow system. Lysosomal membrane stability was analysed in haemocytes using the neutral red retention assay and an alkaline unwinding assay was used to measure DNA damage in hepatopancreas tissue. Exposure to oil induced concentration and time dependent biomarker responses in adult shrimps together with the accumulation of PAH in their tissues. Oil exposure of shrimp embryos caused increased mortality in the resultant larvae, even if the larvae were kept in clean water after hatching. There were minor differences observed in larval stage development times in the first part of the experiments. The fatty acid composition of embryos exposed to oil was different to that of non-exposed larvae. PAH tissue concentration and biomarker responses correlated to the reduced survival of the shrimp larvae.     

Enzymatic and cellular responses in relation to body burden of PAHs in bivalve molluscs: A case study with chronic levels of North Sea and Barents Sea dispersed oil

Mytilus edulis and Chlamys islandica were exposed to nominal dispersed crude oil concentrations in the range 0.015–0.25 mg/l for one month. Five biomarkers (enzymatic and cellular responses) were analysed together with bioaccumulation of PAHs at the end of exposure. In both species, PAH tissue residues reflected the exposure concentration measured in the water and lipophylicity determined the bioaccumulation levels. Oil caused biomarker responses in both species but more significant alterations in exposed C. islandica were observed. The relationships between exposure levels and enzymatic responses were apparently complex. The integrated biomarker response related against the exposure levels was U-shaped in both species and no correlation with total PAH body burden was found. For the monitoring of chronic offshore discharges, dose- and time-related events should be evaluated in the selection of biomarkers to apply. From this study, cellular damages appear more fitted than enzymatic responses, transient and more complex to interpret.     

Lab tests on the biodegradation of chemically dispersed oil should consider the rapid dilution that occurs at sea

Most crude oils spread on open water to an average thickness as low as 0.1 mm. The application of dispersants enhances the transport of oil as small droplets into the water column, and when combined with the turbulence of 1 m waves will quickly entrain oil into the top 1 m of the water column, where it rapidly dilutes to concentrations less than 100 ppm. In less than 24 h, the dispersed oil is expected to mix into the top 10 m of the water column and be diluted to concentrations well below 10 ppm, with dilution continuing as time proceeds. Over the multiple weeks that biodegradation takes place, dispersed oil concentrations are expected to be below 1 ppm. Measurements from spills and wave basin studies support these calculations. Published laboratory studies focused on the quantification of contaminant biodegradation rates have used concentrations orders of magnitude greater than this, as it was necessary to ensure the concentrations of hydrocarbons and other chemicals were higher than the detection limits of chemical analysis. However, current analytical methods can quantify individual alkanes and PAHs (and their alkyl homologues) at ppb and ppm levels. To simulate marine biodegradation of dispersed oil at dilute concentrations commonly encountered in the field, laboratory studies should be conducted at similarly low hydrocarbon concentrations.     

Re-evaluating the use of beached bird oiling rates to assess long-term trends in chronic oil pollution

The oiling rate (oiled birds/total birds) has become the international standard to analyze beached bird survey data. However, this index may not reliably track long-term changes in marine oil pollution in regions where other activities that kill seabirds vulnerable to oil, such as hunting and gill-netting, are also changing. We compare the oiling rate from beached bird surveys conducted in southeastern Newfoundland between 1984 and 2006 to an alternative approach, namely trends derived from a model examining the linear density of oiled birds (birds/km). In winter, there was no change in the oiling rate since 1984, while in summer oiling rates significantly increased. In contrast, the number of oiled birds/km showed a significant decline in both winter and summer. The discrepancy in these trends was attributed to steep declines in the number of unoiled birds found in both seasons. In winter, the decline in unoiled birds/km was related to a reduction in the legal murre hunt and less onshore winds, while in summer a reduced cod fishery resulting in fewer murres drowning in nets and warming summers may have lead to the decline. The significant declines in oiled birds/km over the past three decades are hopefully an indication of less oil being present in the marine environment. Although oiled bird densities since 2000 have remained relatively low for the region (winter: 0.58 birds/km, summer: 0.27 birds/km), they still exceed densities reported elsewhere in the world.     

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.     

Metallothionein in intestine of red mullet, Mullus barbatus as a biomarker of copper exposure in the coastal marine areas

Dietary metal exposure in fish is studied in native red mullet, Mullus barbatus, involving metallothionein (MT) response in the intestine, a primary site for metal uptake. Intestinal MTs (microg mg(-1) proteins), total proteins (mgml(-1) S50), Cu, Zn, Fe, Mn and Cd (microg ml(-1) S50) are considered as indicators of metal exposure in specimens from near-shore and off-shore locations of the Eastern Adriatic Sea. Metallothionein and Cu are statistically significantly higher in 68 specimens from the Kastela Bay, a near-shore area (30.0+/-6.71microg MT mg(-1) proteins; 0.30+/-0.08microg Cu ml(-1) S50), in comparison to 51 specimens from off-shore area, Solta Island (25.9+/-4.21microg MT mg(-1) proteins; 0.26+/-0.09microg Cu ml(-1) S50). Cytosolic Cu, a MT inducer, is significantly correlated (p<0.05, r=0.44) with MT in specimens from the Kastela Bay, independent on fish biometry. Our study indicates that cytosolic intestinal Cu and MT represent a measurable biochemical response in red mullet specimens, dwelling above sediments contaminated with Cu.     

Effects of chronic exposure to dispersed oil on selected reproductive processes in adult blue mussels (Mytilus edulis) and the consequences for the early life stages of their larvae

Mussels (Mytilus edulis) were continuously exposed to dispersed crude oil (0.015-0.25 mg/l) for 7 months covering the whole gamete development cycle. After 1 month exposure to 0.25 mg oil/l, the level of alkali-labile phosphates (ALP) and the volume density of atretic oocytes in female gonads were higher than those in the gonads of control females, indicating that oil affected the level of vitellogenin-like proteins and gamete development. Spawning of mussels was induced after 7 months oil exposure. Parental oil exposure did not affect subsequent fertilization success in clean seawater but this was reduced in 0.25 mg oil/l. Parental exposure to 0.25 mg oil/l caused both slow development and a higher percentage of abnormalities in D-shell larvae 2 days post-fertilization; reduced growth 7 days post-fertilization. These effects were greatly enhanced when larval stages were maintained at 0.25 mg oil/l. Similar studies are warranted for risk assessment prognosis.     

The dose-response relationship between No. 2 fuel oil and the growth of the salt marsh grass,Spartina alterniflora

The effect of No. 2 fuel oil on the biomass production of the salt marsh plant, Spartina alterniflora, was studied in a greenhouse dose-response experiment. S. alterniflora were transplanted into soil with 10 dosage levels of No. 2 fuel oil ranging from 0 to 456 mg g(-1) dry soil. Three months after transplantation, values for plant biomass, stem density, and shoot height decreased significantly with increasing fuel oil level in a dose-response fashion. Evapo-transpiration rates were correlated with the total biomass response. Relative to the control, a significant decrease in total (above- plus below-ground) plant biomass was observed at concentrations above 57 mg g(-1) dry soil. Within the 3-month experimental period, detrimental effects on below-ground biomass accumulation and bioluminescence of the marine bacterium Viberio fisheri in the Microtox Solid Phase Test were observed at oil concentrations >29 mg g(-1) dry soil, suggesting that biological effects of oil within the sediment matrix may be more pronounced than on above-ground biomass, requiring a dosage 228 mg g(-1) dry soil to elicit a significant detrimental effect. Hence, measurements of oil effects with biological end-points based solely on above-ground responses may underestimate the potential impacts of petroleum hydrocarbon spills, especially when the oil has penetrated the soil. While S. alterniflora was proved to be relatively tolerant to the No. 2 fuel oil spills, its effectiveness in phytoremediation operations may be limited at fuel oil levels 228 mg g(-1) dry soil, as both plant growth and microbial activity may be constrained.     

A multibiomarker approach in barramundi (Lates calcarifer) to measure exposure to contaminants in estuaries of tropical North Queensland

A suite of biomarkers were measured in barramundi (Lates calcarifer) from five North Queensland estuaries along a perceived pollution gradient. The biomarkers selected were 7-ethoxyresorufin-O-deethylase (EROD), cytochrome P450, fluorescent aromatic compounds (FACs), DNA integrity, RNA:DNA ratio, cholinesterase activity (ChE), condition factor and hepatosomatic index. The resulting database was subjected to uni- and multi-variate analyses in order to assess the most suitable biomarkers to assess pollution in North Queensland estuaries and to classify the environmental quality of the sites. Principal components analysis (PCA) on the biochemical markers revealed that EROD, EROD/P450, DNA damage and to a lesser extent ChE and FACs were found to be responsive to contaminants in the environment while cytochrome P450, condition factor and the hepatosomatic index were found to be less responsive biomarkers. This study has demonstrated the utility of applying a multibiomarker approach in conjunction with traditional analysis of contaminants in providing valuable information in environmental risk assessment.     

The glutathione antioxidant system as a biomarker suite for the assessment of heavy metal exposure and effect in the grey mangrove, Avicennia marina (Forsk.) Vierh

Alterations in the glutathione antioxidant system and lipid peroxidation in Avicennia marina were studied under laboratory and field conditions. The activity of glutathione peroxidase (GPx) was found to respond to Zn exposure, and a significant positive relationship between leaf Zn concentration and GPx activity was observed after 96 h and 8 weeks. Lipid hydroperoxides increased proportionally with increasing leaf Zn concentration after 2 and 8 weeks, while no changes in total glutathione were observed. Induction of GPx at 96 h predicted effects at the individual level at a later time interval (reduced biomass at 8 weeks). Results from the field revealed that increasing leaf metal concentration (Zn, Cu or Pb) produced a proportional increase in GPx activity whereas lipid hydroperoxides and total glutathione were not affected. The utility of GPx as an early warning biomarker is suggested, since GPx activity increases in a dose-dependant fashion in response to accumulated leaf metals, and is predictive of later effects on growth.     

A comparison of acute and chronic toxicity tests used to examine the temporal stability of a gradient in copper tolerance of Hediste diversicolor from the Fal estuary, Cornwall, UK

The aim of this study was to use two different toxicity tests to verify the existence of a gradient in tolerance along Rostronguet Creek. Hediste diversicolor was collected from five populations in the Fal estuary previously shown to vary in copper tolerance. Exposure to 4 mgL(-1) of copper in an acute assay demonstrated that Mylor Creek worms were sensitive (LT(50) 86 h) and the tolerance of Rostronguet Creek worms increased moving upstream from the mouth of the creek (LT(50)s 100-258 h). There was no significant difference in tolerance between Mylor worms and worms from the mouth of Rostronguet Creek. This is in agreement with a previous study [Grant, A., Hateley, J.G., Jones, N.V., 1989. Mapping the ecological impact of heavy metals on the estuarine polychaete Nereis diversicolor using inherited metal tolerance. Marine Pollution Bulletin 20, 235-238] and demonstrates temporal stability of the gradient. Copper tolerance was also measured using a chronic toxicity test run for 90 d using step-wise increases in challenge concentration. A significant difference in tolerance was shown between populations from Mylor Creek and those at the mouth of Rostronguet Creek, which has not been reported previously. Experimental protocol was therefore an important factor in detecting population variation in tolerance.     

Comparing an estimate of seabirds at risk to a mortality estimate from the November 2004 Terra Nova FPSO oil spill

On 21 November 2004, about 1000 barrels of crude oil were accidentally released from the Terra Nova FPSO (floating production, storage and offloading) onto the Grand Banks, approximately 340 km east-southeast of St. John's, Newfoundland. We estimated the number of vulnerable seabirds (murres (Uria spp.) and dovekies (Alle alle)) at risk from this incident by multiplying observed densities of seabirds with the total area covered by the slick, estimated at 793 km(2). A mean density of 3.46 murres/km(2) and 1.07 dovekies/km(2) on the sea surface was recorded during vessel-based surveys on 28 and 29 November 2004, with a mean density of 6.90 murres/km(2) and 13.43 dovekies/km(2) combining those on the sea and in flight. We calculated a mean of 9858 murres and dovekies were at risk of being oiled, with estimates ranging from 3593 to 16,122 depending on what portion of birds in flight were assumed to be at risk. A mortality model based on spill volume was derived independently of the risk model, and estimated that 4688 (CI 95%: 1905-12,480) birds were killed during this incident. A low mortality estimate based strictly on spill volume would be expected for this incident, which occurred in an area of relatively high seabird densities. Given that the risk and mortality estimates are statistically indistinguishable, we estimate that on the order of 10,000 birds were killed by the Terra Nova spill.     

Comparison of benthic invertebrate assemblages at Spartina alterniflora marshes reestablished after an oil spill and existing marshes in the Arthur Kill (NY/NJ)

In January 1990, an oil spill damaged salt marshes along the banks of the Arthur Kill (New York and New Jersey, USA). In the years following the spill, Spartina alterniflora seedlings were planted at a number of the oil damaged sites and successfully reestablished at these sites. In 1996, the National Marine Fisheries Service began a study to compare the benthic invertebrate assemblages at the reestablished S. alterniflora marshes to those at nearby existing marshes in the Arthur Kill. Oligochaetes, nematodes, and the small tube-building polychaete, Manayunkia aestuarina were the dominant taxa in the study. Significant differences were found in the abundances of all invertebrate individuals, oligochaetes, and nematodes between the September and May sampling times but not between reestablished and existing marshes. Although benthic invertebrate community structure was similar at reestablished and existing marshes three to four years after planting, the functional similarity of these marshes was not assessed in this study.