AbstractConcentrations of neutral poly- and perfluoroalkyl substances (PFASs), such as fluorotelomer alcohols (FTOHs), perfluoroalkane sulfonamides (FASAs), perfluoroalkane sufonamidoethanols (FASEs), and fluorotelomer acrylates (FTACs), have been simultaneously determined in surface seawater and the atmosphere of the North Sea. Seawater and air samples were taken aboard the German research vessel Heincke on the cruise 303 from 15 to 24 May 2009. The concentrations of FTOHs, FASAs, FASEs, and FTACs in the dissolved phase were 2.6–74, <0.1–19, <0.1–63, and <1.0–9.0 pg L−1, respectively. The highest concentrations were determined in the estuary of the Weser and Elbe rivers and a decreasing concentration profile appeared with increasing distance from the coast toward the central part of the North Sea. Gaseous FTOHs, FASAs, FASEs, and FTACs were in the range of 36–126, 3.1–26, 3.7–19, and 0.8–5.6 pg m−3, which were consistent with the concentrations determined in 2007 in the North Sea, and approximately five times lower than those reported for an urban area of Northern Germany. These results suggested continuous continental emissions of neutral PFASs followed by transport toward the marine environment. Air–seawater gas exchanges of neutral PFASs were estimated using fugacity ratios and the two-film resistance model based upon paired air–seawater concentrations and estimated Henry's law constant values. Volatilization dominated for all neutral PFASs in the North Sea. The air–seawater gas exchange fluxes were in the range of 2.5 × 103–3.6 × 105 pg m−2 for FTOHs, 1.8 × 102–1.0 × 105 pg m−2 for FASAs, 1.1 × 102–3.0 × 105 pg m−2 for FASEs and 6.3 × 102–2.0 × 104 pg m−2 for FTACs, respectively. These results suggest that the air–seawater gas exchange is an important process that intervenes in the transport and fate for neutral PFASs in the marine environment.