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Continuous atmospheric sampling was conducted between 2010–2015 at Casey station in Wilkes Land, Antarctica, and throughout 2013 at Troll Station in Dronning Maud Land, Antarctica. Sample extracts were analyzed for polybrominated diphenyl ethers (PBDEs), and the naturally converted brominated compound, 2,4,6-Tribromoanisole, to explore regional profiles. This represents the first report of seasonal resolution of PBDEs in the Antarctic atmosphere, and we describe conspicuous differences in the ambient atmospheric concentrations of brominated compounds observed between the two stations. Notably, levels of BDE-47 detected at Troll station were higher than those previously detected in the Antarctic or Southern Ocean region, with a maximum concentration of 7800 fg/m³. Elevated levels of penta-formulation PBDE congeners at Troll coincided with local building activities and subsided in the months following completion of activities. The latter provides important information for managers of National Antarctic Programs for preventing the release of persistent, bioaccumulative, and toxic substances in Antarctica.