A Quantitative Comparison of Oil Sources on Shorelines of Prince William Sound, Alaska, 17 Years After the Exxon Valdez Oil Spill.

Environmental damage caused by accidental discharges of pollutants depends in part on the degree of prior contamination, in that increased pollution of an already heavily contaminated region will usually be considered less detrimental than equivalent pollution of a pristine region. Quantitative comparisons of specific pollution events with the extent and severity of prior contamination are rare, owing to difficulties in identifying and assessing contaminants remaining from prior pollution events, and in some cases contaminants from natural sources. The 1989 Exxon Valdez oil spill (EVOS) presents an unusual opportunity to quantitatively evaluate residual contaminants from petroleum sources on shorelines of Prince William Sound (PWS), Alaska. Here, we evaluate surface oil contamination from Monterey Formation petroleum-derived residues (released into PWS from ruptured storage tanks during the 1964 earthquake) on 200 shoreline segments selected at random within the EVOS spill path. We compare these results with previously estimated contamination from the EVOS and from other human activities. Our results indicate that residual shoreline contamination from the EVOS is more than ~ 50% greater than the sum total from human activity sites, that residual contamination by Monterey Formation sources is negligible in comparison to that from the EVOS, and that most of the shorelines in PWS were as close to pristine prior to the EVOS as is likely to be found anywhere else worldwide.

Anomalously High Recruitment of the 2010 Gulf Menhaden (Brevoortia patronus) Year Class: Evidence of Indirect Effects from the Deepwater Horizon Blowout in the Gulf of Mexico.

Gulf menhaden (Brevoortia patronus) exhibited unprecedented juvenile recruitment in 2010 during the year of the Deepwater Horizon well blowout, exceeding the prior 39-year mean by more than four standard deviations near the Mississippi River. Abundance of that cohort remained exceptionally high for two subsequent years as recruits moved into older age classes. Such changes in this dominant forage fish population can be most parsimoniously explained as consequences of release from predation. Contact with crude oil induced high mortality of piscivorous seabirds, bottlenose dolphin (Tursiops truncatus), waders, and other fish-eating marsh birds, all of which are substantial consumers of Gulf menhaden. Diversions of fresh water from the Mississippi River to protect coastal marshes from oiling depressed salinities, impairing access to juvenile Gulf menhaden by aquatic predators that avoid low-salinity estuarine waters. These releases from predation led to an increase of Gulf menhaden biomass in 2011 to 2.4 million t, or more than twice the average biomass of 1.1 million t for the decade prior to 2010. Biomass increases of this magnitude in a major forage fish species suggest additional trophically linked effects at the population-, trophic-level and ecosystem scales, reflecting an heretofore little appreciated indirect effect that may be associated with major oil spills in highly productive marine waters.

Advances in Understanding the Fate and Effects of Oil from Accidental Spills in the United States Beginning with the Exxon Valdez.

Scientific studies of the environmental effects of oil spills in the United States have produced a steady stream of unexpected discoveries countering prior and often simplistic assumptions. In this brief review, I present how major discoveries from scientific studies of oil spill effects on marine ecosystems and environments, beginning with the 1989 Exxon Valdez, have led to a more informed appreciation for the complexity and the severity of the damage that major spills can do to marine ecosystems and to an increasing recognition that our ability to evaluate those damages is very limited, resulting in a structural bias toward underestimation of adverse environmental effects.

Unlike PAHs from Exxon Valdez crude oil, PAHs from Gulf of Alaska coals are not readily bioavailable.

In the wake of the 1989 Exxon Valdez oil spill, spatially and temporally spill-correlated biological effects consistent with polycyclic aromatic hydrocarbon (PAH) exposure were observed. Some works have proposed that confounding sources from local source rocks, prominently coals, are the provenance of the PAHs. Representative coal deposits along the southeast Alaskan coast (Kulthieth Formation) were sampled and fully characterized chemically and geologically. The coals have variable but high total organic carbon content technically classifying as coals and coaly shale, and highly varying PAH contents. Even for coals with high PAH content (approximately 4000 ppm total PAHs), a PAH-sensitive bacterial biosensor demonstrates nondetectable bioavailability as quantified, based on naphthalene as a test calibrant. These results are consistent with studies indicating that materials such as coals strongly diminish the bioavailability of hydrophobic organic compounds and support previous work suggesting that hydrocarbons associated with the regional background in northern Gulf of Alaska marine sediments are not appreciably bioavailable.

Semipermeable membrane devices link site-specific contaminants to effects: PART II - A comparison of lingering Exxon Valdez oil with other potential sources of CYP1A inducers in Prince William Sound, Alaska.

We deployed semipermeable membrane devices (SPMDs) on beaches for 28 days at 53 sites in Prince William Sound (PWS), Alaska, to evaluate the induction potential from suspected sources of cytochrome P450 1A (CYP1A)-inducing contaminants. Sites were selected to assess known point sources, or were chosen randomly to evaluate the region-wide sources. After deployment, SPMD extracts were analyzed chemically for persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAH). These results were compared with hepatic CYP1A enzyme activity of juvenile rainbow trout injected with the same extracts prior to clean-up for the chemical analyses. Increased CYP1A activity was strongly associated with PAH concentrations in extracts, especially chrysene homologues but was not associated with POPs. The only apparent sources of chrysene homologues were lingering oil from Exxon Valdez, asphalt and bunker fuels released from storage tanks during the 1964 Alaska earthquake, creosote leaching from numerous pilings at one site, and PAH-contaminated sediments at Cordova Harbor. Our results indicate that PWS is remarkably free of pollution from PAH when nearby sources are absent as well as from pesticides and PCBs generally.

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.

Slightly weathered Exxon Valdez oil persists in Gulf of Alaska beach sediments after 16 years.

Oil stranded by the 1989 Exxon Valdez spill has persisted in subsurface sediments of exposed shores for 16 years. With annualized loss rates declining from approximately 68% yr(-1) prior to 1992 to approximately 4% yr(-1) after 2001, weathering processes are retarded in both sediments and residual emulsified oil ("oil mousse"), and retention of toxic polycyclic aromatic hydrocarbons is prolonged. The n-alkanes, typically very readily oxidized by microbes, instead remain abundant in many stranded emulsified oil samplesfrom the Gulf of Alaska. They are less abundant in Prince William Sound samples, where stranded oil was less viscous. Our results indicate that, at some locations, remaining subsurface oil may persist for decades with little change.

Vertical distribution and probability of encountering intertidal Exxon Valdez oil on shorelines of three embayments within Prince William Sound, Alaska.

We examined 32 shorelines selected at random in 2003 from shorelines in Herring Bay, Lower Pass, and Bay of Isles in Prince William Sound, Alaska, to examine the vertical distribution of oil remaining from the 1989 Exxon Valdez oil spill and to estimate the probability that sea otters and ducks would encounter oil while foraging there. On each shoreline, sampling was stratified by 1-m tide height intervals and randomly located 0.25 m2 sampling quadrats were examined for evidence of surface and subsurface oil. Oil from the T/V Exxon Valdezwasfound on 14 shorelines, mainly in Herring Bay and Lower Pass, with an estimated 0.43 ha covered by surface oil and 1.52 ha containing subsurface oil. Surface and subsurface oil were most prevalent near the middle of the intertidal and had nearly symmetrical distributions with respect to tide height. Hence, about half the oil is in the biologically rich lower intertidal, where predators may encounter it while disturbing sediments in search of prey. The overall probability of encountering surface or subsurface oil is estimated as 0.0048, which is only slightly greaterthan our estimated probability of encountering subsurface oil in the lower intertidal of Herring Bay or Lower Pass. These encounter probabilities are sufficient to ensure that sea otters and ducks that routinely excavate sediments while foraging within the intertidal would likely encounter subsurface oil repeatedly during the course of a year.

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.

Assessment of the phototoxicity of weathered Alaska North Slope crude oil to juvenile pink salmon.

Petroleum products are known to have greater toxicity to the translucent embryos and larvae of aquatic organisms in the presence of ultraviolet radiation (UV) compared to toxicity determined in tests performed under standard laboratory lighting with minimal UV. This study assessed the acute phototoxicity of the water accommodated fractions of weathered Alaska North Slope crude oil (ANS) to juvenile pink salmon, which are a heavily pigmented life stage. Fish in the highest ANS treatments exhibited melanosis, less mobility, reduced startle response, erratic swimming, and loss of equilibrium. Gills from fish exposed to ANS had elevated levels of hydroperoxides in oil-only, UV-only, and oil+UV treatments compared to control fish, which was indicative of increased lipid peroxidation in gill tissue. Under the test conditions of moderate salinity, low UV and high short-term oil exposure there were no indications of photoenhanced toxicity as assessed by elevation of mortality, behavioral impairment, or gill lipid peroxidation in oil+UV treatments. The results of this study suggest that pink salmon may be at less risk from photoenhanced toxicity compared to the translucent early-life stages of several other Alaska species.

Estimate of oil persisting on the beaches of Prince William Sound 12 years after the Exxon Valdez oil spill.

We estimated the amount of oil remaining in Prince William Sound, Alaska, 12 yr after the 1989 Exxon Valdez spill to assess its importance as a long-term reservoir of toxic hydrocarbons. We found oil on 78 of 91 beaches randomly selected according to their oiling history. Surface oiling was recorded for randomly placed quadrats, which were then excavated and examined for subsurface oil. The cumulative area of beach contaminated by surface or subsurface oil was estimated at 11.3 ha. Surface oil varied little with tide height, but subsurface oil was more prevalent at the middle tide heights. The mass of remaining subsurface oil is conservatively estimated at 55 600 kg. Analysis of terpanes indicated that over 90% of the surface oil and all of the subsurface oil was from the Exxon Valdez and that Monterey Formation oil deposited after the 1964 Alaska earthquake accounted for the remaining surface oil. These results indicate that oil from the Exxon Valdez remains by far the largest reservoir of biologically available polycyclic aromatic hydrocarbons on beaches impacted by the spill and that biota dependent on these beaches risk continued exposure.

Long-term ecosystem response to the Exxon Valdez oil spill.

The ecosystem response to the 1989 spill of oil from the Exxon Valdez into Prince William Sound, Alaska, shows that current practices for assessing ecological risks of oil in the oceans and, by extension, other toxic sources should be changed. Previously, it was assumed that impacts to populations derive almost exclusively from acute mortality. However, in the Alaskan coastal ecosystem, unexpected persistence of toxic subsurface oil and chronic exposures, even at sublethal levels, have continued to affect wildlife. Delayed population reductions and cascades of indirect effects postponed recovery. Development of ecosystem-based toxicology is required to understand and ultimately predict chronic, delayed, and indirect long-term risks and impacts.

Photoenhanced toxicity of aqueous phase and chemically dispersed weathered Alaska North Slope crude oil to Pacific herring eggs and larvae.

The photoenhanced toxicity of weathered Alaska North Slope crude oil (ANS) was investigated in the eggs and larvae of Pacific herring (Clupea pallasi) with and without the chemical dispersant Corexit 9527. Oil alone was acutely toxic to larvae at aqueous concentrations below 50 microg/L total polycyclic aromatic hydrocarbons (tPAH), and median lethal (LC50s) and effective concentrations (EC50s) decreased with time after initial oil exposure. Brief exposure to sunlight (approximately 2.5 h/d for 2 d) significantly increased toxicity 1.5- to 48-fold over control lighting. Photoenhanced toxicity only occurred when oil was present in larval tissue and increased with increasing tPAH concentration in tissue. Ultraviolet radiation A (UVA) treatments were less potent than natural sunlight, and UVA + sunlight caused greater toxicity than sunlight alone. The toxicity of chemically dispersed oil was similar to oil alone in control and UVA treatments, but oil + dispersant was significantly more toxic in the sunlight treatments. The chemical dispersant appeared to accelerate PAH dissolution into the aqueous phase, resulting in more rapid toxicity. In oil + dispersant exposures, the 96-h no-observed-effect concentrations in the UVA + sunlight treatment were 0.2 microg/L tPAH and 0.01 microg/g tPAH. Exposure of herring eggs to oil caused yolk sac edema, but eggs were not exposed to sun and UVA treatment did not cause phototoxicity. These results are consistent with the hypothesis that weathered ANS is phototoxic and that UV can be a significant and causative factor in the mortality of early life stages of herring exposed to oil and chemically dispersed oil.

Photoenhanced toxicity of weathered Alaska North Slope crude oil to the calanoid copepods Calanus marshallae and Metridia okhotensis.

This study investigated the synergistic toxicity of aqueous polyaromatic compounds (PAC) dissolved from crude oil and ultraviolet radiation (UV) in natural sunlight to the calanoid copepods Calanus marshallae and Metridia okhotensis. These copepods were first exposed to low doses (approximately 2 microg of total PAC/L) of the water-soluble fraction of weathered Alaska North Slope crude oil for 24 h and subsequently to low or high levels of natural sunlight. Responses included mortality, impairment of swimming ability, and discoloration of lipid sacs. There was 80-100% mortality and morbidity of C. marshallae exposed to UV and oil as compared to less than 10% effect in oil-only or UV-only treatments. In M. okhotensis, 100% mortality occurred in the UV and oil treatment, 43% mortality and 27% morbidity in the UV-only treatment, and less than 5% effect in the oil-only treatment. Bioaccumulation factors were approximately 8000 for C. marshallae and approximately 2000 for M. okhotensis. The interaction of the effect of PAC and UV radiation was highly significant (P < 0.005) in both experiments.