The concentrations, congener profiles, and phase-specific distribution profiles of 27 polybrominated diphenyl ethers and 10 hydroxylated and 18 methoxylated brominated diphenyl ethers (OH- and MeO-BDEs; later called structural analogues of PBDEs) were determined in surface soil, water, air, and vegetation from the southeastern city of Busan, Korea for 2010-2011. The total PBDE concentrations were 0.18-7.7 ng/g in soil, 6.3-87 pg/L [corrected] in water, 5.3-16 pg/m(3) in air, and 0.06-0.22 ng/g in vegetation. The OH- and MeO-BDE concentrations were lower than the parent PBDE concentrations in soil samples but OH-BDEs were much greater in the water samples and MeO-BDEs were much greater in the air samples. The relative concentrations of the PBDEs and their structural analogues varied depending on the type and homologue of the degradation product, the substituent position, and the characteristics of the environmental medium. In particular, the OH-BDEs were not found in air samples and the OH-penta BDEs were not detected in any of the matrices. The dominance of the ortho-substituted structural analogues found in water and vegetation suggested that they may have natural sources, but different substituent patterns were found in the air and soil samples, suggesting that the structural analogues had different formation mechanisms in these media.