AbstractEleven particle-size-segregated samples were taken to investigate the particle-size distribution of perfluoroalkyl substances (PFASs) using two five stage impactors in parallel. Samples were extracted with methanol and detected by HPLC/MS–MS. Investigation yielded reproducible results for the parallel samples over the entire sampling period. Particle-size distribution varied between perfluorooctane sulfonate (PFOS) and other perfluoroalkyl sulfonates (PFSAs), perfluorooctane carboxylate (PFOA) and other perfluoroalkyl carboxylates (PFCAs) and n-methyl-perfluorooctanesulfonamido ethanol (MeFOSE). Whereas PFOA and MeFOSE were predominantly observed in smallest size fraction (<0.14 μm), maximum PFOS mass fractions were observed in the coarser size fractions between 1.38 and 3.81 μm. The reason for this different behaviour remained unclear and indicated a complex atmospheric PFAS processing and sampling which should be further investigated and optimized, respectively.