In this paper, the long-term monitoring results for hydrophobic organic compounds, specifically polycyclic aromatic hydrocarbons (PAHs), from a field demonstration of capping contaminated sediments at the Anacostia River in Washington DC are presented and analyzed. In situ pore water concentrations in field-contaminated sediments in the demonstration caps were quantified using a polydimethylsiloxane (PDMS)-based passive sampling device. High resolution vertical pore water concentration profiles were measured using the device and were used to infer fate and transport of polycyclic aromatics hydrocarbons (PAHs) at the site. The derived pore water concentrations were compared with observed bioaccumulation and solid-phase concentration profiles to infer contaminant migration rates and mechanisms. Observed pore water concentrations were found to be a better predictor of bioaccumulation than solid-phase concentrations. Solid-phase concentrations were low in cores which implied containment of contamination; however pore water profiles showed that contaminant migration had occurred in the first few years after cap placement. The discrepancy is the result of the low sorption capacity of the sand. Because of surface re-contamination, low sorption capacity in the demonstration caps and strong tidal pumping effects, steady state contaminant profiles were reached in the caps several years after placement. Despite re-contamination at the surface, steady state concentrations in the capped areas showed decreased contamination levels relative to the control area.