The occurrence of the major components of the decabromodiphenyl ether (deca-BDE) flame retardant and other PBDEs was investigated in daily air particulate samples from 17th April to 20th May 2004 at a semi-rural site in north-west England. BDE-209 was found at between b0.49 and 100 pg m−3 (median 13 pg m−3), and other higher-brominated PBDE congeners were also found, particularly the nona-BDEs (e.g. BDE-207: b0.042–79 pg m−3, median 2.5 pg m−3). Deca- and nona-BDEs dominated the median particulate sample congener profile: 60% BDE-209, 16% BDE-207, 6% BDE-208 and 4% BDE-206. Nona-BDEs were greatly enriched, relative to BDE-209, compared to the deca-BDE commercial mixture, which may suggest degradation of BDE-209 between source and sampling site, or release from older deca-BDE commercial mixtures, which may have contained higher proportions of nona-BDEs. The highest PBDE concentrations occurred when air-masses passed over urban and industrial areas to the SSW–SW, though small local influences may also be seen. PBDE concentrations appear to have been influenced mainly by particle levels: 1–3 μm diameter particles for BDE-153, and 3–10 μm particles for BDEs with 7–10 Br atoms. BDE-153 may either be released from combustion sources, or re-condense onto small particles after emission, whereas BDE-209 and nona-BDEs appear to be associated with larger dust particles from industrial or domestic sources.