Watershed processing of atmospheric polychlorinated biphenyl inputs

Indirect atmospheric deposition of PCBs was examined in subwatersheds of the Delaware River Estuary. Tributary PCB loads and atmospheric PCB concentrations were used to understand the pass-through efficiencies for nine rivers/ creeks for which PCB inputs appeared to be dominated by atmospheric deposition. The pass-through efficiency, E, was calculated from tributary loads and atmospheric deposition fluxes. Unfortunately, uncertainties in the gaseous and dry particle deposition velocities, vg and vd, respectively, render the calculated atmospheric deposition fluxes highly uncertain. In order to circumvent this problem, export of PCBs from the watershed was related directly to atmospheric PCB concentrations via a new mass transfer coefficient, the watershed delivery rate or vws, which describes the process by which the watershed transfers PCBs from the airto the River's main stem. vws increases with increasing chlorination and is significantly correlated with vapor pressure. This trend suggests that the transfer of PCBs from the atmosphere to the River via the watershed is more efficient for high molecular weight PCBs than for low molecular weight PCBs. This may indicate that the selected watersheds are at or close to equilibrium with respect to gaseous exchange of PCBs, such that lower molecular weight congeners undergo substantial revolatilization after deposition. The magnitude of the pass-through efficiency, E, depends on the deposition velocities used to calculate the atmospheric deposition flux, but when congener-specific deposition velocities are used, E is independent of vapor pressure and is relatively constant at about 3%.