Legacy and emerging per- and polyfluoroalkyl substances (PFAS) in the atmosphere: A comprehensive review

With long-term production and widespread application, per- and polyfluoroalkyl substances (PFAS) have been detected in various media worldwide, including the atmosphere. Since the gradual restriction and phase-out of C₈ perfluoroalkyl acids (PFAAs), environmental contamination by emerging PFAS substitutes such as short-chain PFAA homologues, perfluoroether carboxylic, and sulfonic acids has been reported. Although there has been extensive monitoring of emerging PFAS substitutes in the aquatic environment, few studies have conducted target analysis and nontarget screening (NTS) of emerging unknown PFAS in the atmosphere over the past decade. To fill the gap, this review focused on emerging PFAS in the atmosphere in addition to legacy PFAS. The reported sampling, pretreatment, and instrumental analysis methods for target analysis and NTS of both neutral and ionic PFAS in the atmosphere are summarized, along with the advantages and current limitations of different sampling and NTS methods for PFAS in the atmosphere. The global levels, composition, and spatiotemporal distribution characteristics of legacy and emerging PFAS in the atmosphere are summarized and their transport, transformation, and dry/wet deposition are elucidated. The review highlights the importance of developing and applying the all-in-one strategy integrating target, suspect screening, and NTS to gain insights into emerging PFAS in the atmosphere and provide a reference for future research.