Ultrasound
degrades “legacy” per- and polyfluoroalkyl
substances (PFAS) via thermolysis at the interface of cavitation bubbles.
However, compared to “legacy” PFAS, polyfluoroalkyl
substances have a lesser affinity to the interface and may react with •OH. To understand the effect of size on degradation
kinetics and mechanism of polyfluoroalkyl substances, this work compared
ultrasonic treatment (f = 354 kHz) of n:2 fluorotelomer sulfonates (FTSAs) of varying chain lengths (n = 4, 6, 8). Of the congeners tested, 4:2 fluorotelomer
sulfonate (FtS) degraded the fastest in individual solutions and in
mixtures. Sonolytic rate constants correlated to diffusion coefficients
of FTSAs, indicating that diffuse short-chain FTSAs outcompete long-chain
FTSAs to adsorb and react at the bubble interface. Interestingly,
4:2 and 8:2 FtS had different evolutions of fluoride-to-sulfate ratios,
[F–]/[SO4
2–], over
time. Initially, [F–]/[SO4
2–]4:2 FtS and [F–]/[SO4
2–]8:2 FtS were respectively
higher and lower than theoretical ratios. This difference was attributed
to the lower maximum surface excess of 8:2 FtS, hindering its ability
to pack and, consequently, defluorinate at the interface. In the presence
of an •OH scavenger, FTSAs had similar %F– release compared to no scavenger, whereas %SO4
2– release was drastically diminished. Therefore, thermolysis is the
primary degradation pathway of FTSAs; •OH supplements
SO4
2– formation. These results indicate
that ultrasound directly cleaves C–F bonds within the fluoroalkyl
chain. This work shows that ultrasound efficiently degrades FTSAs
of various sizes and may potentially treat other classes of polyfluoroalkyl
substances.