Electrochemical Oxidation of 6:2 Polyfluoroalkyl Phosphate Diester-Simulation of Transformation Pathways and Reaction Kinetics with Hydroxyl Radicals.
Environ Sci Technol
; 2021 Jul 30.
Article
in En
| MEDLINE
| ID: mdl-34327989
ABSTRACT
Polyfluoroalkyl phosphate diesters (diPAPs) are widely used for paper and cardboard impregnation and discharged via waste streams from production processes and consumer products. To improve the knowledge about the environmental fate of diPAPs, electrochemical oxidation (EO) was used to characterize the transformation pathways and reaction kinetics. 62 diPAP was transformed electrochemically to perfluorocarboxylic acids (C5-C7 PFCAs) and two intermediates (62 fluorotelomer carboxylic acid, FTCA, and 62 fluorotelomer unsaturated carboxylic acid, FTUCA). EO of potential intermediates 62 monoPAP and 62 fluorotelomer alcohol (FTOH) showed similar transformation products but with different ratios. We show that 62 diPAP is initiated by OH radical (â¢OH) reactions, as evidenced by the measured steady-state concentrations of â¢OH with the probe molecule terephthalic acid, quenching experiments, and pH dependency of the reaction. PFHpA was the main product of 62 diPAP oxidation, and it was formed in a pseudo-first-order reaction for which a bimolecular rate constant was estimated to be kOâ¢H,diPAPformPFHpA = 9.4(±1.4) × 107 M-1 s-1 by an initial rate approach. This can be utilized to estimate the environmental half-life of 62 diPAP for the reaction with â¢OH and the formation kinetics of persistent PFCAs.
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MEDLINE
Language:
En
Year:
2021
Type:
Article