Role of pH in the Transformation of Perfluoroalkyl Carboxylic Acids by Activated Persulfate: Implications from the Determination of Absolute Electron-Transfer Rates and Chemical Computations

Perfluoroalkyl carboxylic acids (PFCAs) are ubiquitous contaminants known for their bioaccumulation, toxicological harm, and resistance to degradation. Remediating PFCAs in water is an ongoing challenge with existing technologies being insufficient or requiring additional disposal. An emergent approach is using activated persulfate, which degrades PFCAs through sequential scission of CF2 equivalents yielding shorter-chain homologues, CO2 and F-. This transformation is thought to be initiated by single electron transfer (SET) from the PFCA to the activate oxidant, SO4 center dot-. A pronounced pH effect has been observed for thermally activated persulfate PFCA transformation. To evaluate the role of pH during SET, we directly determined absolute rate constants for perfluorobutanoic acid and trifluoroacetic acid oxidation by SO4 center dot- in the pH range of 0.5-4.0 using laser flash photolysis. The average of the rate constants for both substrates across all pH values was 9 +/- 2 x 10(3) M-1 s(-1) (+/- 2 sigma), implying that acid catalysis of thermal persulfate activation may be the primary culprit of the observed pH effect, instead of pH influencing the SET step. In addition, density functional theory was used to investigate if SO4 center dot- protonation might enhance PFCA transformation kinetics. We found that when calculations include explicit water molecules, direct SO4 center dot- protonation does not occur.