A nationwide monitoring of atmospheric POPs (persistent organic pollutants) was conducted in Ghana between May and July 2010, applying polyurethane foam (PUF) disk passive air samplers (PAS). Reported here are preliminary findings on PCNs, an industrial organic contaminant currently under review for possible listing under the global chemical treaty. The present results constitute the first set of nationwide data on air PCNs from a West African country. Contrary to expectation, air PCNs levels were quite high in Ghana, at an average of 49 ± 5.4 pg/m(3). The coastal (southern) zone of Ghana appeared the most impacted, with crude open burning of waste, industrial emissions, and the harbor environment identified among possible emission factors. Tri- and tetra-CNs (the lowly chlorinated homologues) predominated in the atmosphere, altogether constituting approximately 90% of total PCN homologues composition. Increased volatilization under tropical conditions was presumed a key factor that contributed to this high atmospheric input of lowly chlorinated homologues. We further observed a significant level of fractionation of PCN homologues across the breadth of the country. The percentage composition of the lowly chlorinated homologues increased northwards, probably because of their transportation in the direction of prevailing winds. From congener profile analysis, PCN-45/36 is proposed as a possible source marker for emissions preempted by uncontrolled waste burning activities. Dioxin-like toxicity of air PCNs in Ghana was estimated to range 0.49-5.6 fg TEQ/m(3). This study brought to the fore the emerging problems of nonagricultural organohalogens that covertly might be confronting the environment in African nations like Ghana.