In previous studies unexpectedly high air concentrations of polychlorinated biphenyls (PCBs) were observed in shipbased measurements made similar to 400 km off parts of the West African coast. To investigate further (i) samples were taken on board the RV Polarstern during a cruise from Germany to South Africa in October-November 2007; (ii) samples were obtained on Cape Verde Island during the same period to monitor airflows from Africa; and (iii) passive samplers were deployed in four West African countries to try to characterize potential sources on land. Results were as follows: on Cape Verde and on the ship air masses came predominantly (similar to 95 from the African continent; the shipboard Sigma(29)PCB concentrations off West Africa ranged from 10 to 360 pg m(-3) and from 6 to 99 pg m(-3) in Cape Verde; the highest land-based concentrations were observed in Ivory Coast and the Gambia (up to 300 pg m(-3)) and the lowest was observed in Ghana (9 pg m-3). Taken together, these and previous studies indicate there are more major emission(s) of PCBs and different source types in parts of West Africa than accounted for in current global atmospheric emissions estimates. Results from the FLEXPART model and PAH measurements show that emission inventories and biomass burning cannot fully explain the high PCB concentrations. Potential sources of the high PCB levels to the African regions are discussed, namely illegal dumping of PCB containing waste with release via volatilization and uncontrolled burning, and the storage and breakup of old ships.