Refining PAH and PCB bioavailability predictions in industrial sediments using source-fingerprinting, particle size,...

Nearshore marine sediments in a Puget Sound, Washington industrial embayment had elevated levels of PAHs, PCBs and DDTs. Chemical fingerprints implicated nearshore sources including creosote, industrial oil and tar waste, and a landfill. Elevated concentrations were confined to an approximate 300-m shoreline buffer in the industrial waterfront, suggesting high site fidelity and limited along-shore or off-shore transport. Total PAH concentrations approximately doubled when including alkylated compounds. The industrial sediments often exceeded toxicity criteria; however, chemicals were likely less bioavailable than predicted, in part, due to assumed strong sorption to anthropogenic carbon like coal tar. Analyses of separated particle-size fractions showed that approximately half of PAHs were associated with particles greater than 500 μm, suggesting that a wide range of particle sizes are relevant to occurrence and transport. Predicted freely dissolved chemical concentrations in sediment pore water were unrealistically high using a bulk organic carbon sorption coefficient. When reduced to environmentally reasonable levels by applying a high-sorption partition coefficient applicable to contaminated sediments, predicted freely dissolved concentrations in some industrial sediments exceeded sublethal effect levels or surface water quality standards. Chemical assemblages predicted in the freely dissolved aqueous fraction, which is relevant for biotic uptake from water, shifted to predominantly low molecular weight as compared to sediment, highlighting the role of exposure pathways in bioavailability. Insights from chemical fingerprinting coupled with co-analysis of bulk carbon and grain size allowed refinement of bioavailability assessments of complex chemical mixtures in contaminated nearshore environments that are relevant for ecosystem health and restoration.