Exxon Valdez. Carls et al. (1999) exposed Pacific herring eggs for 16 days to weathered Alaska North Slope crude oil and observed that exposure to initial aqueous concentrations as low as 0.7 ppb PAH caused developmental malformations, genetic damage, mortality, decreased size at hatching, and impaired swimming. Concentrations as low as 0.4 ppb caused premature hatching and yolk-sac edema. Exposure to less weathered oil produced similar results but at higher exposure concentrations (9.1 ppb).

Other investigators have observed developmental effects on fish and invertebrates exposed to low concentrations of petroleum hydrocarbons (Capuzzo et al., 1988). The high toxicity of weathered oil reported by Heintz et al. (1999) and Carls et al. (1999), however, suggests that higher concentrations of one or more constituents in weathered fractions relative to total PAH contribute to the increased toxicity.

Bioavailability, Bioaccumulation, and Metabolism

The concept of bioavailability is extremely important in understanding and describing the environmental fates and biological effects of petroleum in the marine environment. A concise definition of what is meant in this context by bioavailability is essential. In aquatic toxicology, bioavailability usually is defined as the extent to which a chemical can be absorbed or adsorbed by a living organism by active (biological) or passive (physical or chemical) processes. A chemical is said to be bioavailable if it is in a form that can move through or bind to the surface coating (e.g., skin, gill epithelium, gut lining, cell membrane) of an aquatic organism (Kleinow et al., 1999).

Accumulation of petroleum hydrocarbons by marine organisms is dependent on the biological availability of hydrocarbons, the length of exposure, and the organism’s capacity for metabolic transformations. There are two aspects of petroleum hydrocarbon bioavailability that are important in understanding the behavior of oil in the environment: environmental availability, and biological availability. Environmental availability is the physical and chemical form of the chemical in the environment and its accessibility to biological receptors. Generally, chemicals in true solution in the ambient water are considered more bioavailable than chemicals in solid or adsorbed forms. Petroleum hydrocarbons of the types found in the marine environment may be present in true solution, complexed with dissolved organic matter and colloids, as dispersed micelles, adsorbed on the surface of inorganic or organic particles, occluded within particles (e.g., in soot, coal, or tar), associated with oil droplets, and in the tissues of marine organisms (Readman et al., 1984; Gschwend and Schwarzenbach, 1992). The hydrocarbons in the different phases are exchangeable but, at any given moment, only a fraction of the total hydrocarbons in water, sediments, and biota is in bioavailable forms.

The dissolved hydrocarbons are the most bioavailable, followed by those in tissues of marine organisms (if the organisms are eaten) or associated with liquid, unweathered oil droplets. Thus, bioavailability of PAH from sediments and food is less than that from solution in the water (Pruell et al., 1987). Particulate PAH associated with soot or weathered oil particles (e.g., tarballs) have a low bioavailability (Farrington, 1986; Gustafsson et al., 1997a,b; Baumard et al., 1999). As oil weathers, its viscosity and average molecular weight increase, decreasing the rate of partitioning of higher molecular weight PAH from the oil phase into water in contact with the oil, decreasing the accessibility of these PAH to aquatic organisms (McGrath et al., 2001). Soot-associated PAH are not bioaccumulated in the tissues of aquatic animals. Maruya et al. (1996) showed that sediment-associated animals in San Francisco Bay, CA, were not able to bioaccumulate PAH from the very fine-grained particles (identified as soot) in the sediments. Pruell et al. (1986) showed that the bioaccumulation of PAH from contaminated sediments by mussels correlated with the concentration of dissolved but not particulate PAH in the sediments.

The other aspect of environmental availability is accessibility. Petroleum hydrocarbons that are buried deep in sediments or sequestered in solid, highly weathered oil deposits on the shore are not accessible to marine and terrestrial organisms and, therefore have a low bioavailability. Biological availability depends on the rate at which a chemical is assimilated into the tissues of the organism and accumulates at the sites of toxic action in the organism. This depends on the physical/chemical properties of the chemical in contact with the organism, the relative surface area of permeable epithelia in the organism, and the ability of the organism to excrete or detoxify the chemical. Nonpolar (hydrophobic) organic chemicals such as petroleum hydrocarbons, have a low aqueous solubility and a high lipid solubility. Hydrocarbons in solution in water diffuse down an activity or fugacity gradient from the water phase into lipid-rich tissues of marine organisms in contact with the water. According to equilibrium partitioning theory (Davies and Dobbs, 1984; Bierman, 1990), when an aquatic animal is exposed to a nonpolar organic chemical dissolved in the ambient water, the chemical partitions across permeable membranes into tissue lipids until an equilibrium, approximated by the octanol/ water partition coefficient (Kow) for the chemical is reached. At equilibrium, the rates of absorption into and desorption from the lipid phase of the organism are equal. Toxic responses in the organism occur when the concentration of nonpolar organic chemicals in the tissues reach a critical concentration (McCarty and Mackay, 1993). The log Kow of PAH increases with increasing molecular weight (Neff and Burns, 1996). However, bioavailability, measured as log bioconcentration factor (BCF: concentration in tissues/concentration in water at equilibrium), does not increase in a linear fashion with increasing PAH log Kow (Baussant et al., 2001a,b). The sediment organic carbon-water coefficient, Koc is also useful in predicting uptake of sediment-associated hydrocarbons (Fisher, 1995; Meador et al. 1995; DiToro

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