Chemical fate and transport models that simulate sediment-water exchange of contaminants typically employ empirically determined sediment-water exchange coefficients for the dissolved fraction to describe the net effect of poorly understood mechanisms. This paper presents field-derived observations of the coefficient for 12 PCB congeners and two PCB mixtures in the Thompson Island Pool, Hudson River, and also presents an evaluation of a theoretical sediment-water exchange model. An extensive PCB data set was used to compute apparent coefficients for PCBs in the pool. Average exchange coefficients for the 12 congeners ranged from 2.6 to 18.8 cm/ day, and results showed a strong seasonal dependence. Peak coefficient values occurred in mid-May to early July, preceding peak water temperatures by 1 month and lagging the spring high-flow period. The coefficients increase with increasing partition coefficients, suggesting a dependence on congener properties. The large magnitude of the coefficients and the variation among the congeners is inconsistent with the pore-water molecular-diffusion transport process. A theory-based, mechanistic two-layer model reproduces the nonlinear relationship between the sediment-water exchange coefficients and partition coefficients. This model includes transfer through the mixed sediment layer by bioturbation and diffusion transfer through a water-side boundary layer governed by flow velocity. Results suggest that this algorithm can provide increased accuracyto future system-level fate and transport models for hydrophobic chemicals. The seasonal variation in the transfer coefficient appears to be a poorly understood interaction of physical and biological processes and merits further study.