The sorption of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to organic carbon (OC) and black carbon (BC) was measured in two sediment cores taken near the Diamond Alkali superfund site (DA) in the Passaic River and Newark Bay, New Jersey (U.S.A.). An OC partitioning model and a BC-inclusive, Freundlich distribution model were used to interpret measurements of freely dissolved PCDD/Fs using passive samplers in sediment incubations, together with measured sedimentary concentrations of OC, BC, and PCDD/Fs. Samples were also analyzed for polycyclic aromatic hydrocarbons (PAHs) as controls on the two distribution models. The OC partitioning model underpredicted the distribution of PAHs and PCDD/Fs by 10-100-fold. The Freundlich model predicted the distribution of PAHs at the DA to within a factor of 2-3 of observations. Black carbon-water partition coefficients (K(iBC)) for PCDD/Fs, derived from literature results of both field and laboratory studies differed up to 1000-fold from values derived from this study. Contrary to expectations, PCDDs displayed stronger sorption than either PCDFs or PAHs relative to their subcooled liquid aqueous solubilities. Even though the presence of BC in the sediments reduced the overall bioavailability of PCDD/Fs by >90%, the sediments at 2 m depth continue to display the highest pore water activities of PCDD/Fs.