Nontarget Discovery of Per- and Polyfluoroalkyl Substances in Atmospheric Particulate Matter and Gaseous Phase Using Cryogenic Air Sampler

Novel per- and polyfluoroalkyl substances (PFASs) have become a key issue in global environmental studies. Although several novel PFASs have been discovered in atmospheric particulate matter through nontarget analysis, information on the environmental occurrence of novel PFASs in atmospheric gaseous phases and conventional sampling techniques is somewhat deficient. Therefore, this Article describes a new type of air sampler, the cryogenic air sampler (CAS), which was used to collect all atmospheric components simultaneously. Nontarget analysis then was performed through PFASs homologue analysis. A total of 117 PFAS homologues (38 classes) were discovered, 48 of which (13 classes) were identified with confidence Level 4 or above. Eleven chlorinated perfluoropolyether alcohols (3 classes) and four chlorinated perfluoropolyether carboxylic acids (2 classes) have been reported for the first time in this Article. This Article is also the first report of 12 hydrosubstituted perfluoroalkyl carboxylates (H-PFCAs) in the atmosphere. H-PFCAs and chlorinated perfluoropolyether carboxylic acids were mainly distributed in the particular phase. These results are evidence that novel chlorinated polyether PFASs should be the focus of future study.