Heterogeneous photooxidation of 6:2 polyfluoroalkyl phosphoric acid diester on dust mineral components under simulated sunlight and the influence of relative humidity and oxygen
By Yiming Yao, Yue Meng, and Hongwen Sun
Chemosphere
June 1, 2021
DOI: 10.1016/j.chemosphere.2021.130713
Polyfluoroalkyl phosphoric acid diesters (diPAPs) have been widely and increasingly detected in various environmental mediums. The degradation of diPAPs brings perfluoroalkyl carboxylic acids (PFCAs) concerned of adverse health effects. DiPAPs mainly occur in particulate matter in ambient air and their photo-degradation behaviors have not been investigated. In this study, heterogeneous photo-degradation of 6:2 diPAP was studied on four model mineral components in ambient dust. 6:2 diPAP was found to undergo a fast degradation on titanium dioxide (TiO) particles as well as on artificial mineral dust containing TiO (2.67% in mass) to produce C5-C7 PFCAs and other intermediates. Based on monitored intermediates and further degradation tests on important intermediates, thermodynamic calculation of energy barrier and Gibbs Free Energy was used to explain the observed degradation patterns and accordingly the degradation pathways of diPAPs were proposed. The increase in relative humidity promotes the production of hydroxyl radicals, which enhances the hydrolysis of 6:2 mono- and di-PAPs and the yield of C5 and C7 PFCAs. Oxygen is critical for radical formation, which bypasses the production of fluorotelomer carboxylic acid. Results of this study for the first time demonstrate that diPAP may account for additional PFCA sources in both indoor and outdoor environments and the heterogeneous degradation pathways were different from those of volatile fluorotelomer alcohols.
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