AbstractAn air sampling campaign was conducted at a wastewater treatment plant (WWTP) to investigate air concentrations and particle–gas partitioning of polyfluoroalkyl compounds (PFCs). Samples were collected at an aeration tank and a secondary clarifier using both active high volume samplers and passive samplers comprising sorbent-impregnated polyurethane foam (SIP) disks. Water to air transport of PFCs was believed to be enhanced at the aeration tank owing to aerosol-mediated transport caused by surface turbulence induced by aeration. Mean air concentrations of target PFCs at the aeration tank were enriched relative to the secondary clarifier by factors of ~19, ~4 and ~3 for ∑fluorotelomer alcohols (FTOHs) (11 000 v. 590 pg m–3), ∑perfluorooctane sulfonamides & perfluorooctane sulfonamidoethanols (FOSAs & FOSEs) (120 v. 30 pg m–3) and ∑perfluoroalkyl carboxylates & perfluoroalkyl sulfonates (PFCAs & PFSAs) (4000 v. 1300 pg m–3) respectively. The particle associated fraction in the atmosphere increased with increasing chain length for PFCAs (from 60 to 100%) and PFSAs were predominantly bound to particles (~98%). Lower fractions on particles were found for FTOHs (~3%), FOSAs (~30%) and FOSEs (~40%). The comparison of the active and passive air sampling showed good agreement.