Radiocarbon-based assessment of fossil fuel-derived contaminant associations in sediments

Hydrophobic organic contaminants (HOCs) are associated with natural organic matter (OM) in the environment via mechanisms such as sorption or chemical binding. The latter interactions are difficult to quantitatively constrain, as HOCs can reside in different OM pools outside of conventional analytical windows. Here, we exploited natural abundance variations in radiocarbon (C-14) to trace various fossil fuel-derived HOCs (C-14- free) within chemically defined fractions of contemporary OM (modern C-14 content) in 13 samples including marine and freshwater sediments and one dust and one soil sample. Samples were sequentially treated by solvent extraction followed by saponification. Radiocarbon analysis of the bulk sample and resulting residues was then performed. Fossil fuel-derived HOCs released by these treatments were quantified from an isotope mass balance approach as well as by gas chromatography-mass spectrometry. For the majority of samples (n = 13), 98-100% of the total HOC pool was solvent extractable. Nonextracted HOCs are only significant (29% of total HOC pool) in one sample containing pp-2,2-bis(chlorophenyl)1,1,1-trichloroethane and its metabolites. The infrequency of significant incorporation of HOCs into nonextracted OM residues suggests that most HOCs are mobile and bioavailable in the environment and, as such, have a greater potential to exert adverse effects.