Experimental and theoretical insights into the photochemical decomposition of environmentally persistent perfluorocarboxylic acids.

Decomposition of perfluorocarboxylic acids (PFCAs) is of great significance due to their global distribution, persistence and toxicity to organisms. In this study, the photodegradation of a series of PFCAs (∼C2C12) in water by a medium-pressure mercury lamp was experimentally and theoretically examined. We found that photolysis of PFCAs all follow pseudo-first-order kinetics with the rate constant (kapp) increasing with carbon chain lengths, except for trifluoroacetic acid (TFA) which cannot be degraded by the polychromatic irradiation. Product analysis showed that the PFCAs were mainly decomposed into shorter carbon chain length PFCAs in a stepwise manner, with the accumulation of TFA and fluoride ions as the end products. Moreover, a small amount of perfluoroolefins (CnF2n) was determined as gas-phase products. Wiberg bond order calculations confirmed the cleavage of the CC bond between carboxylic carbon and the adjacent carbon as the first reaction step, and density functional theory-based calculations revealed that kapp value is correlated with some molecular structural parameters. In the case of mixture irradiation, the evolution profiles of individual PFCAs were different from that in single-component systems, due to the dynamic balance between production and degradation. This work reveals the main molecular descriptors controlling the degradation rate of different PFCAs species, and improves the general understanding on the photodegradation mechanisms, which will provide useful information for future researches.