Particle-scale understanding of the bioavailability of PAHs in sediment.

This study reports results of sediment bioslurry treatment and earthworm bioaccumulation for polycyclic aromatic hydrocarbon (PAH) contaminants found in sediment dredged from Milwaukee Harbor. A significant finding was that bioslurry treatment reduced PAHs on the sediment clay/silt fraction but not on the sediment coal-derived fraction and that PAH reduction in the clay/silt fraction correlated with substantial reduction in earthworm PAH bioaccumulation. These findings are used to infer PAH bioavailability from characterization of particle-scale PAH distribution, association, and binding among the principal particle fractions in the sediment. The results are consistent with work showing that the sediment comprised two principal particle classes for PAHs, coal-derived and clay/silt, each having much different PAH levels, release rates, and desorption activation energies. PAH sorption on coal-derived particles is associated with minimal biodegradation, slow release rates, and high desorption activation energies, while PAH sorption on clay/silt particles is associated with significant potential biodegradability, relatively fast release rates, and lower desorption activation energies. These characteristics are attributed to fundamental differences in the organic matter to which the PAHs are sorbed. Although the majority of the PAHs are found preferentially on coal-derived particles, the PAHs on the clay/silt sediment fraction are more mobile and available, and thus potentially of greater concern. This study demonstrates that a suite of tests comprising both bioassays and particle-scale investigations provide a basis to assess larger-scale phenomena of biotreatment of PAH-impacted sediments and bioavailability and potential toxicity of PAH contaminants in sediments. Improved understanding of contaminant bioavailability aids decision-making on the effectiveness of biotreatment of PAH-impacted sediments and the likelihood for possible reuse of dredged sediments as reclaimed soil or fill.