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Advanced hydrocarbon fingerprinting methods and improved analytical methods make possible the quantitative discrimination of the multiple sources of hydrocarbons in the benthic sediments of Prince William Sound (PWS) and the Gulf of Alaska. These methods measure an extensive range of polycyclic aromatic hydrocarbons (PAH) at detection levels that are as much as two orders of magnitude lower than those obtained by standard Environmental Protection Agency methods. Nineteen hundred thirty six (1 936) subtidal sediment samples collected in the sound and the eastern Gulf of Alaska in 1989, 1990, and 1991 were analyzed. Fingerprint analyses of gas chromatography-mass spectrometry data reveal a natural background of petrogenic and biogenic PAH. The petrogenic background is derived largely from oil seeps in the eastern Gulf of Alaska. Age-dated (210pb) sediment cores indicate that significant input of seep hydrocarbons into Prince William Sound has been going on for at least 160 years and probably for thousands of years. Superimposed on this natural background are locally elevated concentrations of anthropogenic hydrocarbons from sources such as diesel fuel and pyrogenic PAH that are found primarily adjacent to active or historical sites of human use. Exxon Valdez crude, its weathering products, and diesel fuel refined from Alaska North Slope crude are readily distinguished from the natural seep petroleum background and from each other because of theirdistinctive PAH distributions. Mixing models were developed to calculate the PAH contributions from each source to each sediment sample. These calculations show that most of the seafloor in PWS contains no detectable hydrocarbons from the Exxon Valdez spill, although elevated concentrations of PAH from seep sources are widespread. In those areas where they were detected, spill hydrocarbons were generally a small increment to the natural petroleum hydrocarbon background. Low levels of Exxon Valdez crude residue were present in 1989 and again in 1990 in nearshore subtidal sediments off some shorelines that had been heavily oiled. By 1991 these crude residues were heavily degraded and even more sporadically distributed.

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Part two of a three-part series, this paper describes chemical and toxicological results of a comprehensive shoreline ecology program that was designed to assess recovery in Prince William Sound following the Exxon Valdez oil spill of March 24, 1989. The program is an application of the “sediment quality triad” approach, combining chemical, toxicological, and biological measurements. Other parts of the program are described in Part 1: Study Design and Methods (Page et al., this volume) and Part 3: Biology (Gilfillan et al., this volume). The study was designed so that results could be extrapolated to the entire spill zone in the sound and projected forward in time. It combined one-time sampling of 64 randomly chosen study sites representing four major habitats and four oiling levels (including unoiled reference sites), with periodic sampling at 12 subjectively chosen “fixed” sites. Sediment samples—or when conditions required, filter-wipes from rock surfaces—were collected in each of three intertidal zones and from subtidal stations up to 30-m deep. Oil removal was generally quite rapid: by 1991 the concentration of oil spilled from the Exxon Valdez had been dramatically reduced on the majority of shorelines by both natural processes and cleanup efforts. Moderate concentrations of petroleum residues remain only in limited, localized areas; however, most of these residues are highly asphaltic, not readily bioavailable, and not toxic to marine life. Acute sediment toxicity from oil (as measured by standard toxicity tests) was virtually absent by 1990–'91, except at a small number of isolated locations. The petroleum residues had degraded below the threshold of acute toxic effects. Measurable polycyclic aromatic hydrocarbon (PAH) levels are, in general, well below those conservatively associated with adverse effects, and biological recovery has been considerably more rapid than the removal of the last chemical remnants. The remaining residues continue to degrade and are, in general, predicted to become indistinguishable from background hydrocarbon levels by 1993 or 1994. Localized residues of weathered oil will no doubt exist beyond 1994 at certain locations, but their environmental significance will be negligible compared with other stresses ongoing in the sound. Samples of nearshore subtidal sediments showed surprisingly low concentrations of oil residue, as an increment to the natural petrogenic hydrocarbon background. Sediment toxicity tests showed that they were essentially non toxic. It appears that most of the oil leaving the shoreline was swept away and dissipated at sea. It is concluded that long-term ecological effects resulting from shoreline oiling or subtidal contamination are highly unlikely.

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The dominant sources of the petrogenic hydrocarbon background in benthic sediments of Prince William Sound, AK (PWS), site of the 1989 Exxon-Valdez oil spill, are eroding Tertiary shales and residues of natural oil seepage. Mass balance considerations and statistical analyses of hydrocarbon fingerprints independently indicate that coal contributes generally less than 1% of the polycyclic aromatic hydrocarbons (PAH) and chemical biomarkers in this background. This is environmentally significant because of presumed differences in the bioavailability of PAH in coal, seep oil residues, and shales. Coal particles are present in PWS sediments, but their PAH and chemical biomarker contributions are overwhelmed by those of seep oil residues and organic particles from shales of low-to-high thermally maturity. In the late Tertiary or early Quaternary, the currently exposed and eroding shale formations were heated into the oil-generation window and, consequently, are now relatively rich in extractable PAH and chemical biomarkers. The exposed and eroding coals in the area, in contrast, experienced long hot burial and are now thermally overmature with respect to oil generation. The concentrations of thermally sensitive PAH and biomarker compounds in PWS sediments are not consistent with a mature coal origin but are consistent with the low-to-high maturity shales and seep oils in the area.

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Abstract-Bioavailable hydrocarbons in the Exxon Valdez oil spill zone in Prince William Sound (PWS; AK, USA) shorelines were at or near background levels in 2002, as indicated by low concentrations of polycyclic aromatic hydrocarbons (PAHs) in mussels (Mytilus trossulus) collected from sites throughout PWS. Total PAH (TPAH) minus parent naphthalene concentrations in mussels collected in 1998 to 2002 from sites oiled in 1989 were at or near reference-site values. Both oiled and reference sites included locations associated with past human and industrial activity (HA). Inclusion of the unoiled HA sites in the range of reference sites that define prespill conditions is consistent with federal regulations. For the period from 1998 to 2002, the geometric mean of TPAH concentrations for 218 mussel samples collected from 72 sites, including four HA sites that had been heavily oiled in 1989, is 54 ng/g dry weight (range, 2-1,190 ng/g). The maximum mussel TPAH concentrations are equivalent to a weatheredoil exposure dose to intertidal foragers that is one to three orders of magnitude less than the doses shown to cause sublethal effects in surrogate species. The geometric mean of TPAH concentrations for mussel samples from 28 locations not oiled in 1989 and unaffected by human use (NHA sites) is 28 ng/g (range, 3-355 ng/g), whereas the geometric mean of TPAH concentrations for mussel samples from 14 locations not oiled in 1989 and affected by human use (HA sites) is 106 ng/g (range, 2-12,056 ng/g). The range of data for the unoiled HA and NHA sites defines the background of bioavailable PAHs to mussels on western PWS shorelines that would have prevailed if the oil spill had not occurred. The low PAH concentrations in mussels from sites known to have subsurface oil residues demonstrates the low bioavailability of these spill remnants and, thus, are a low additional risk to foraging wildlife. The present study shows continuous exposure from four-to six-ring PAHs originating at HA sites in western PWS. At low concentrations, these PAHs are known to cause adverse biological effects. However, in the context of PWS, oiled and HA sites represent a small percentage (ϳ0.1-0.2%) of the total PWS shoreline.