Per- and polyfluoroalkyl substances (PFASs) in precipitation from mainland China: Contributions of unknown precursors and short-chain (C2C3) perfluoroalkyl carboxylic acids.

A nationwide survey was conducted on per- and polyfluoroalkyl substances (PFASs) in precipitation across mainland China. Twenty-two PFASs, including precursors to perfluoroalkyl acids (pre-PFAAs), were investigated in thirty-nine precipitation samples collected from twenty-eight cities. Trifluoroacetate (TFA), perfluorooctanoic acid, and perfluorooctane sulfonic acid (PFOS) were ubiquitous in precipitation. TFA displayed the highest concentrations (8.8-1.8 × 103  ng/L), which were particularly elevated in coastal cities. 6:2 chlorinated polyfluorinated ether sulfonic acid, an alternative to PFOS, was detected for the first time in precipitation at a frequency of 43%. Polyfluoroalkyl phosphoric acid diesters and 6:2 fluorotelomer sulfonic acid were also occasionally detected. PFAS fluxes in the northeastern area (C4C12; 2.0 × 102 -3.4 × 103  ng/m2 /d) with major PFAS manufacturing facilities were higher than those in the southwestern area (63-1.7 × 103  ng/m2 /d). Using total oxidizable precursor (TOP) assay, the occurrence of unknown pre-PFAAs was for the first time uncovered in precipitation with maximum estimated fluxes of C6 and C8 pre-PFAAs at 3.1 × 103 and 4.3 × 103  ng/m2 /d, respectively. The relative contribution of ultrashort-chain PFCAs (C2C3) ranged from 22% to 91% of ∑PFASs, while unknown pre-PFAAs accounted for 6%-56% of the total molar concentrations of PFASs. This bears critical concerns on underestimation of PFAS mass load from precipitation to surface environment ascribed to monitoring data solely on known PFASs. Unknown precursors of PFAAs in the atmosphere are yet to be identified for their chemical structures and relevant environmental risks as well.