The largest fresh water body in North America, Lake Superior, has the potential to both accumulate and serve as a secondary source of persistent bioaccumulative toxins, such as polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). Polyethylene passive samplers (PEs) were thus simultaneously deployed at 19 sites in surface water and near surface atmosphere across Lake Superior to determine air and water concentrations and air-water gradients of 18 PCBs and 24 OCPs. PCBs in the air and water were characterized by penta- and hexachlorobiphenyls with distribution along the coast correlated with proximity to developed areas. Surface water and atmospheric concentrations were dominated by α-HCH (average 250 pg L-1 and 4.2 pg m-3, respectively), followed by HCB (average 17 pg L-1 and 89 pg m-3, respectively). Decreases in open lake concentrations of PCBs in water and air from spring to summer were consistent with ongoing volatilization from the surface layer as the main cause. Conversely, α-endosulfan was consistently deposited into the surface water of Lake Superior. Results indicated that PCBs were depleted in the surface mixed layer, implying a physical limit on evasive fluxes. This was corroborated with measurements from a vertical profile, displaying greater PCB concentrations at depth.