Petroleum biomarkers as tracers of Exxon Valdez oil.

Over the past quarter century, petroleum biomarkers have persisted in sequestered Exxon Valdez oil in Prince William Sound and the Gulf of Alaska (USA), and hence the oil has remained identifiable. These biomarkers are molecular fossils derived from biochemicals in previously living organisms. Novel pattern matching indicated the presence of Alaska North Slope crude oil (ANSCO) over the entire observation period at most sites (7 of 9) and distinguished this source from several other potential sources. The presence of ANSCO was confirmed with Nordtest forensics, demonstrating the veracity of the new method. The principal advantage of the new method is that it provides sample-specific identification, whereas the Nordtest approach is based on multisample statistics. Biomarkers were conserved relative to other constituents, and thus concentrations (per g oil) in initial beach samples were greater than those in fresh oil because they were lost more slowly than more labile oil constituents such as straight-chain alkanes and aromatic hydrocarbons. However, biomarker concentrations consistently declined thereafter (1989-2014), although loss varied substantially among and within sites. Isoprenoid loss was substantially greater than tricyclic triterpane, hopane, and sterane loss. Environ Toxicol Chem 2016;35:2683-2690. © 2016 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC. This article is a US government work and as such, is in the public domain in the United States of America.

Sampling design for long-term regional trends in marine rocky intertidal communities.

Probability-based designs reduce bias and allow inference of results to the pool of sites from which they were chosen. We developed and tested probability-based designs for monitoring marine rocky intertidal assemblages at Glacier Bay National Park and Preserve (GLBA), Alaska. A multilevel design was used that varied in scale and inference. The levels included aerial surveys, extensive sampling of 25 sites, and more intensive sampling of 6 sites. Aerial surveys of a subset of intertidal habitat indicated that the original target habitat of bedrock-dominated sites with slope ≤30° was rare. This unexpected finding illustrated one value of probability-based surveys and led to a shift in the target habitat type to include steeper, more mixed rocky habitat. Subsequently, we evaluated the statistical power of different sampling methods and sampling strategies to detect changes in the abundances of the predominant sessile intertidal taxa: barnacles Balanomorpha, the mussel Mytilus trossulus, and the rockweed Fucus distichus subsp. evanescens. There was greatest power to detect trends in Mytilus and lesser power for barnacles and Fucus. Because of its greater power, the extensive, coarse-grained sampling scheme was adopted in subsequent years over the intensive, fine-grained scheme. The sampling attributes that had the largest effects on power included sampling of "vertical" line transects (vs. horizontal line transects or quadrats) and increasing the number of sites. We also evaluated the power of several management-set parameters. Given equal sampling effort, sampling more sites fewer times had greater power. The information gained through intertidal monitoring is likely to be useful in assessing changes due to climate, including ocean acidification; invasive species; trampling effects; and oil spills.

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.

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.