Assessment of bioavailable hydrocarbons in Pribilof Island rock sandpiper fall staging areas and overwintering habitat.

At present, significant adverse hydrocarbon influence on the Pribilof Island rock sandpiper (Calidris ptilocnemis ptilocnemis) is unlikely. Almost the entire population overwinters in Cook Inlet and breeds on four Bering Sea islands. Passive samplers deployed several times in a three year period and corresponding sediment and soft tissue samples on St. Paul Island and in Cook Inlet generally accumulated small quantities of polycyclic aromatic hydrocarbons (PAHs). Composition was consistent with oil in <15% of the passive samplers and rarely in soft tissue. Total PAH concentrations in corresponding sediment were very low (<42ng/g dry weight); composition was consistent with oil in 39% of these samples and biomarker composition confirmed this on St. Paul Island. However, composition was dominated by normal alkanes from natural sources.

Polynuclear Aromatic Hydrocarbons in Port Valdez Shrimp and Sediment.

Polynuclear aromatic hydrocarbons (PAHs) from oil were present in some shrimp from Port Valdez, site of a ballast water treatment facility at the Alyeska Alaska Marine Terminal (AMT). Low-level petrogenic PAH concentrations were generally restricted to shrimp eggs in the vicinity of the AMT and extended along the southern shore of Port Valdez to Anderson Bay. Eggs had greater lipid content than other tissues and thus were the most vulnerable biological compartment to hydrocarbon accumulation. Petrogenic hydrocarbons were not observed in shrimp muscle and cephalothoraxes; thus, these tissues do not pose a human health risk. Risk for children older than age 2 years and adults consuming eggs also was low except for two unusual samples (of 32), collected about 17 km west of the treatment facility. In general, PAH loads were consistent with local time series data in other species. We infer that the accumulation mechanism was dissolved uptake from water, consistent with passive sampler observations completed more than a decade earlier. Hydrocarbon levels in the majority of samples were below toxic thresholds. Total PAH accumulation was substantially greater in some pink shrimp than in other species, thus differences in habitat utilization (muddy vs. rocky substrate) are potentially important.

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.

Very low embryonic crude oil exposures cause lasting cardiac defects in salmon and herring.

The 1989 Exxon Valdez disaster exposed embryos of pink salmon and Pacific herring to crude oil in shoreline spawning habitats throughout Prince William Sound, Alaska. The herring fishery collapsed four years later. The role of the spill, if any, in this decline remains one of the most controversial unanswered questions in modern natural resource injury assessment. Crude oil disrupts excitation-contraction coupling in fish heart muscle cells, and we show here that salmon and herring exposed as embryos to trace levels of crude oil grow into juveniles with abnormal hearts and reduced cardiorespiratory function, the latter a key determinant of individual survival and population recruitment. Oil exposure during cardiogenesis led to specific defects in the outflow tract and compact myocardium, and a hypertrophic response in spongy myocardium, evident in juveniles 7 to 9 months after exposure. The thresholds for developmental cardiotoxicity were remarkably low, suggesting the scale of the Exxon Valdez impact in shoreline spawning habitats was much greater than previously appreciated. Moreover, an irreversible loss of cardiac fitness and consequent increases in delayed mortality in oil-exposed cohorts may have been important contributors to the delayed decline of pink salmon and herring stocks in Prince William Sound.

Spilled Oils: Static Mixtures or Dynamic Weathering and Bioavailability?

Polynuclear aromatic hydrocarbons (PAHs) from sequestered MV Selendang Ayu oil were biologically available in 2008, 3.6 y after it was spilled along Unalaska Island, Alaska. Thermodynamically driven weathering was the most probable mechanism of organism exposure to PAHs. Alkane and PAH composition in oil changed over time as smaller constituents were preferentially lost, indicative of weathering. In contrast, composition of the largest compounds (biomarkers) including triterpanes, hopanes, and steranes remained unchanged. Smaller molecules (the PAHs) lost from stranded oil were observed in indigenous mussels and passive samplers deployed in July 2008. Concentration and composition of PAHs were significantly different than in a non-oiled reference area and patterns observed in mussels were repeated in passive samplers deployed in three zones (intertidal, subtidal, and water). Thus, hydrocarbons lost from one compartment (sequestered whole oil) were detectable in another (mussels and passive samplers) implying aqueous transfer. Quantities of mobile oil constituents were small, yielding uptake concentrations that are likely inconsequential for mussels, but the sensitivity provided by bioaccumulation and passive sampler uptake ensured that dissolved hydrocarbons were detectable.

Sublethal exposure to crude oil during embryonic development alters cardiac morphology and reduces aerobic capacity in adult fish.

Exposure to high concentrations of crude oil produces a lethal syndrome of heart failure in fish embryos. Mortality is caused by cardiotoxic polycyclic aromatic hydrocarbons (PAHs), ubiquitous components of petroleum. Here, we show that transient embryonic exposure to very low concentrations of oil causes toxicity that is sublethal, delayed, and not counteracted by the protective effects of cytochrome P450 induction. Nearly a year after embryonic oil exposure, adult zebrafish showed subtle changes in heart shape and a significant reduction in swimming performance, indicative of reduced cardiac output. These delayed physiological impacts on cardiovascular performance at later life stages provide a potential mechanism linking reduced individual survival to population-level ecosystem responses of fish species to chronic, low-level oil pollution.

Anthropogenically sourced low concentration PAHS: In situ bioavailability to juvenile Pacific salmon.

Gill 7-ethoxyresorufin O-deethylase (EROD) activity of juvenile Chinook salmon caged in Auke Lake, AK was used as a biomarker of polycyclic aromatic hydrocarbon (PAH) exposure. Biomarker measurements in conjunction with a comprehensive sampling program that included grab water and sediment samples, and passive sampling devices were used to determine PAH concentrations, source(s), bioavailability, and resulting biological response. PAHs were detected at all lake locations except the reference site upstream of anthropogenic activity. Water samples were the best predictor of a biological response and EROD activity correlated to corresponding parts per trillion water pyrene concentrations (r(2)=0.9662; p=0.0004). Sediment samples yielded the clearest indication of PAH sources and amalgamated contaminant magnitude, and passive samplers served as accumulators of retrospective aqueous conditions. Results suggest that salmon stocks are being exposed to chronic low-concentrations of anthropogenically sourced PAHs during sensitive life-stages, which may be in part a contributor to their declining numbers.

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.

Fish embryos are damaged by dissolved PAHs, not oil particles.

To distinguish the toxicity of whole oil droplets from compounds dissolved in water, responses of zebrafish embryos exposed to particulate-laden, mechanically dispersed Alaska North Slope crude oil (mechanically dispersed oil (MDO)) were compared to those of embryos protected from direct oil droplet contact by an agarose matrix. Most polycyclic aromatic hydrocarbons (PAHs) in MDO were contained in oil droplets; about 16% were dissolved. The agarose precluded embryo contact with particulate oil but allowed diffusive passage of dissolved PAHs. The incidence of edema, hemorrhaging, and cardiac abnormalities in embryos was dose-dependent in both MDO and agarose and the biological effects in these compartments were identical in character. Although mean total PAH (TPAH) concentrations in MDO were about 5-9 times greater than in agarose, dissolved PAH concentrations were similar in the two compartments. Furthermore, mean differences in paired embryo responses between compartments were relatively small (14-23%, grand mean 17%), typically with a larger response in embryos exposed to MDO. Therefore, the embryos reacted only to dissolved PAHs and the response difference between compartments is explained by diffusion. Averaged over 48 h, the estimated mean TPAH concentration in agarose was about 16% less than the dissolved TPAH concentration in MDO. Thus, PAHs dissolved from oil are toxic and physical contact with oil droplets is not necessary for embryotoxicity.

Assessment of the significance of direct and indirect pollution inputs to a major salmon-producing river using polyethylene membrane devices.

Conventional passive sampling devices for monitoring pollution input often prove to be cost-prohibitive when assessing large spatial and temporal scales. The Kenai River, a major salmon-producing river in Alaska (USA), served as the perfect laboratory to test the utility of polyethylene membrane devices for assessing chronic nonpoint-source inputs to a large riverine watershed. Comparison of the relative levels of polycyclic aromatic hydrocarbons (PAHs) at a large number of locations over time allowed us to assess the significance and potential source of these compounds in the river. Concentrations of PAH were greatest near urban areas and peaked during the late winter, when streams flows and dilution were low. Vessel activity and PAH levels peaked in July and were heaviest in the lower 16 km of the river, where fishing activity was concentrated. Nearly one-third of the vessels observed on the river were powered by two-stroke engines, which release a higher proportion of unburned fuel into the water than the cleaner burning four-stroke engines. The low concentrations of hydrocarbons upriver of the boat traffic suggest very little remote delivery of these contaminants to the watershed. Polyethylene strips proved to be an excellent, low-cost tool for determining the PAH patterns in a large watershed.

Monitoring polynuclear aromatic hydrocarbons in aqueous environments with passive low-density polyethylene membrane devices.

Low-density polyethylene membranes, typically filled with triolein, have been previously deployed as passive environmental samplers designed to accumulate nonpolar hydrophobic chemicals from water, sediments, and air. Hydrocarbons in such samplers, known as semipermeable membrane devices (SPMDs), diffuse through pores in the membranes and are trapped in the central hydrocarbon matrix, mimicking uptake by living organisms. Here, we describe laboratory and field verification that low-density polyethylene membrane devices (PEMDs) without triolein provide reliable, relatively inexpensive, time-integrated hydrocarbon sampling from water. For comparison, polynuclear aromatic hydrocarbon (PAH) uptake in SPMDs and pink salmon eggs also was studied. Total concentrations of PAH accumulated by PEMDs were highly correlated with concentrations in water (r2 > or = 0.99) and linear over the range tested (0-17 microg/L). Higher-molecular-mass PAH preferentially accumulated in PEMDs and in pink salmon eggs, but the source of oil in PEMDs remained identifiable. Accumulations of PAH were highly similar to those in SPMDs. The PEMDs retained approximately 78% of accumulated total PAH for 40 d in clean water. Thus, a simple plastic membrane can be conveniently used for environmental monitoring, particularly during situations in which contaminant concentrations are low (in the parts-per-billion range), variable, and intermittent.