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.     

Persistence of 10-year old Exxon Valdez oil on Gulf of Alaska beaches: the importance of boulder-armoring

Oil stranded as a result of the 1989 Exxon Valdez spill has persisted for >10 years at study sites on Gulf of Alaska shores distant from the spill's origin. These sites were contaminated by "oil mousse", which persists in these settings due to armoring of underlying sediments and their included oil beneath boulders. The boulder-armored beaches that we resampled in 1999 showed continued contamination by subsurface oil, despite their exposure to moderate to high wave energies. Significant declines in surface oil cover occurred at all study sites. In contrast, mousse has persisted under boulders in amounts similar to what was present in 1994 and probably in 1989. Especially striking is the general lack of weathering of this subsurface oil over the last decade. Oil at five of the six armored-beach sites 10 years after the spill is compositionally similar to 11-day old Exxon Valdez oil. Analysis of movements in the boulder-armor that covers the study beaches reveals that only minor shifts have occurred since 1994, suggesting that over the last five, and probably over the last 10 years, boulder-armors have remained largely unmoved at the study sites. These findings emphasize the importance of particular geomorphic parameters in determining stranded oil persistence. Surface armoring, combined with stranding of oil mousse, results in the unexpectedly lengthy persistence of only lightly to moderately weathered oil within otherwise high-energy wave environments.     

Using tolerance intervals to assess recovery of mussel beds impacted by the Exxon Valdez oil spill

Polycyclic aromatic hydrocarbons (PAH) have been measured in mussel tissues in early spring and summer since 1993 throughout Prince William Sound (PWS) and the Gulf of Alaska (GOA). Season-specific thresholds were established at reference sites to identify ‘above background’ total PAH levels. Thresholds were estimated using one-sided 99% tolerance limits. Thresholds were similar across reference sites but differed by an order of magnitude across seasons. Trends in total PAH since 1998 were assessed for sites impacted by the 1989 Exxon Valdez oil spill or the Alyeska Marine Terminal. Summer samples exhibited no trends; early spring samples declined. In early spring, all sites were judged ‘recovered’ by 2004; in summer, one site in western Prince William Sound and two in the western GOA exceeded thresholds by 11 ng/g dry weight or less. Robust estimation methods prevented bias from observations affected by unknown releases or laboratory errors.     

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.     

Comparison of mussels and semi-permeable membrane devices as intertidal monitors of polycyclic aromatic hydrocarbons at oil spill sites

Side-by-side comparisons of polycyclic aromatic hydrocarbon (PAH) concentrations in resident blue mussels (Mytilus trossulus) and in semi-permeable membrane devices (SPMDs) were made at four sites in Prince William Sound, Alaska. SPMDs were deployed for approximately 30 days on the surface of the beach sediment at three tidal elevations on each shore and in 0.5 m deep open pits in the middle intertidal zone. Total PAH (TPAH) concentrations in mussels and in SPMDs were correlated, but the PAH compositions were different. The lower molecular weight PAH were relatively more abundant in the SPMDs than in the mussels at oiled and HA sites. TPAH concentrations in SPMDs deployed in pits and mussels collected adjacent to those pits at oiled sites were higher than in SPMDs and mussels from non-pitted SPMD locations approximately 3-15 m from the pits. Pitting released buried oil making its PAH bioavailable. SPMDs deployed in the supratidal zone (+4.0 m tidal elevation) were exposed to atmospheric contaminants for a large fraction of the deployment time and accumulated primarily pyrogenic (combustion-sourced) PAH from the atmosphere. The SPMD strips supplied by the manufacturer contained significant amounts (approximately 125 ng/strip) of primarily alkylated 2-3 ring PAH. These blank levels make SPMDs unsuitable for shoreline assessments when environmental PAH concentrations are low. Consequently, where available, mussels are recommended for use in assessments of the bioavailability of buried oil residues sequestered in intertidal sediments following an oil spill. Mussels are the preferred monitoring tool when the assessments involve food-chain effects. At locations where the absence of mussels necessitates the use of SPMDs or other passive sampling devices, their limitations need to be carefully considered in the interpretation of results.     

An evaluation of marine bird population trends following the Exxon Valdez oil spill, Prince William Sound, Alaska

We examined post-spill trends (1989-1998) of marine bird populations in Prince William Sound (PWS) following the Exxon Valdez oil spill (EVOS) to evaluate recovery of injured taxa. Two criteria were employed. First, we examined population trends of injured taxa only in the oiled area of PWS using regression models. Second, we examined population trends of injured taxa in the oiled area relative to the unoiled area using homogeneity of the slopes tests. We considered a population recovering if there was a positive trend using either criteria. We considered a population not recovering if there was no trend using either criteria or a negative trend in the oiled area. A significant negative trend in the oiled area relative to the unoiled area was considered a continuing and increasing effect. Most taxa for which injury was previously demonstrated were not recovering and some taxa showed evidence of increasing effects nine years after the oil spill. Four taxa (loons Gavia spp, Harlequin Duck Histrionicus histrionicus, Bufflehead Bucephala spp, and North-western Crow Corvus caurinus) showed weak to very weak evidence of recovery. None of these taxa showed positive trends in both winter and summer. Nine taxa (grebes Podiceps spp, cormorants Phalacrocorax spp, Black Oystercatcher Haematopus bachmani, Mew Gull Larus canus, Glaucous-winged Gull Larus glaucescens, terns Sterna spp, murres Uria spp, Pigeon Guillemot Cepphus columba, and murrelets Brachyramphus spp) showed no evidence of recovery during summer or winter. Four taxa (scoters Melanitta spp, mergansers Mergus spp, goldeneyes Bucephala spp, and Black-legged Kittiwaka Rissa tridactyla) showed evidence of continuing, increasing effects. We showed evidence of slow recovery, lack of recovery, and divergent population trends in many taxa which utilize shoreline and nearshore habitats where oil is likely to persist. Potential lingering spill effects and natural variability appear to be acting in concert in delaying recovery of many PWS bird populations.     

Feasibility of High Pressure Injection of Chemicals into the Subsurface for the Bioremediation of the Exxon Valdez Oil

Delivery of dissolved chemicals to bioremediate oil from the Exxon Valdez oil spill was investigated at Beach EL056C of Eleanor Island, Prince William Sound, Alaska. The delivery technique was high pressure injection (HPI) of an inert tracer, lithium, at the approximate depth of 1.0 m into the beach near the mid‐tide line. The results revealed that the maximum injection flow rate was 3.0 L/min and the associated pressure was around 196 kPa. Therefore, exceeding any of these values would probably cause failure of the injection system. The injected tracer was monitored at multiple depths of four surrounding observation wells, and the results showed that the tracer plume occupied an area of 12 m² within 24 h. The tracer plume traveled at the average speeds of 10 m/d in the seaward direction and 1.7 m/d in other directions. The rapid movement under HPI and the large diameter of influence (3.0 m) indicated that bioremediation of the Exxon Valdez oil on this beach via injection of chemicals is logistically feasible.     

Results from a sixteen year study on the effects of oiling from the Exxon Valdez on adult pink salmon returns

For sixteen years following the 1989 Exxon Valdez oil spill adult returns of pink salmon in Prince William Sound, Alaska were monitored to assess spill effects on survival. No evidence of spill effects was detected for either intertidal or whole-stream spawning fish. From 1989 through 2004 mean densities for oiled and reference streams tracked each other, illustrating similar responses of oiled and reference stream adult populations to naturally changing oceanographic and climactic conditions. Hatchery fish strayed into the study streams, but similar incursions occurred in oiled and reference streams, and their presence was compensated for to eliminate their influence on determining the success of the returning natural populations. These results, showing no detectable effects of oiling on pink salmon spawning populations, are supported by published field studies on pink salmon incubation success in oiled streams.     

Accumulation of polycyclic aromatic hydrocarbons by Neocalanus copepods in Port Valdez, Alaska

Sampling zooplankton is a useful strategy for observing trace hydrocarbon concentrations in water because samples represent an integrated average over a considerable effective sampling volume and are more representative of the sampled environment than discretely collected water samples. We demonstrate this method in Port Valdez, Alaska, an approximately 100 km(2) basin that receives about 0.5-2.4 kg of polynuclear aromatic hydrocarbons (PAH) per day. Total PAH (TPAH) concentrations (0.61-1.31 microg/g dry weight), composition, and spatial distributions in a lipid-rich copepod, Neocalanus were consistent with the discharge as the source of contamination. Although Neocalanus acquire PAH from water or suspended particulate matter, total PAH concentrations in these compartments were at or below method detection limits, demonstrating plankton can amplify trace concentrations to detectable levels useful for study.     

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.     

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.     

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).     

Feasibility of Deep Nutrients Delivery into a Prince William Sound Beach for the Bioremediation of the Exxon Valdez Oil Spill

Delivery of dissolved chemicals to potentially bioremediate oil from the Exxon Valdez oil spill was investigated at Smith Island, Prince William Sound, Alaska. Two transects for tracer application were installed: one at a clean area and another at an oiled area. Tracer delivery occurred under ambient pressure through manifolds. Lithium in LiBr/sea water solution was the inert tracer, and the solution (82.6 mg/L of lithium) was released at a flow rate of 0.23 L/min for 58.5 h. While maintaining the flow rate, the solution was switched to sea water (i.e., 0.0 mg/L of lithium) for 16 h. The results show that the tracer moved landward with rising tides and seaward with falling tides. The plume got deeper moving landward and shallower moving seaward of the manifold. Thus, in situations where oil biodegradation is limited by the availability of nutrients or oxygen, applying these chemicals by this technique would allow them to reach entrapped oil seaward of the manifold from below. The seaward plume traveling speed (around 2.0 m/d) suggests that this technique is logistically feasible from a hydraulic point of view.     

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.     

Hebei Spirit oil spill monitored on site by fluorometric detection of residual oil in coastal waters off Taean, Korea

The spatiotemporal distributions of dissolved and/or dispersed oil in seawater and pore water were monitored on site by fluorometric detection method after the Hebei Spirit oil spill. The oil concentrations in intertidal seawater, 15 days after the spill, were as high as 16,600 μg/L and appeared to decrease below the Korean marine water quality standard of 10 μg/L at most sites 10 months after the spill. Fluorometric detection of oil in pore water was introduced to eliminate the effects of grain size for the quantification of oil in sediments and to better explain spatial and temporal distribution of oil pollution at sandy beaches. The fluorescence detection method was compared with the conventional laboratory technique of total petroleum hydrocarbon analysis using gas chromatography. The method of fluorescence detection of oil was capable of generating results much faster and more cost-effectively than the traditional GC technique.     

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.     

Size-selective mortalities of clams in an oil spill site

Mixed No. 2 fuel oil and JP5 jet fuel, following an oil spill into Long Cove, Searsport, Maine, U.S.A., in March 1971 became concentrated locally at levels up to more than 250 ppm in intertidal sediments from 15 to 25 cm below the surface and continued until 1976 to kill successive year class juvenile clams as in normal growth behaviour they burrowed down through redistributed overlying clean sediments into the oil concentration beneath.     

Are sea otters being exposed to subsurface intertidal oil residues from the Exxon Valdez oil spill?

Twenty years after the Exxon Valdez oil spill, scattered patches of subsurface oil residues (SSOR) can still be found in intertidal sediments at a small number of shoreline locations in Prince William Sound, Alaska. Some scientists hypothesize that sea otters continue to be exposed to SSOR by direct contact when otters dig pits in search of clams. This hypothesis is examined through site-specific examinations where SSOR and otter-dug pits co-occur. Surveys documented the exact sediment characteristics and locations on the shore at the only three subdivisions where both SSOR and otter pits were found after 2000. Shoreline characteristics and tidal heights where SSOR have persisted are not suitable habitat for sea otters to dig pits during foraging. There is clear separation between areas containing SSOR and otter foraging pits. The evidence allows us to reject the hypothesis that sea otters encounter and are being exposed by direct contact to SSOR.