Formation of perfluorocarboxylic acids from photodegradation of tetrahydroperfluorocarboxylic acids in water

Highlights: • 2H,2H,3H,3H-PFCAs photoreactivity increases with carbon chain length. • 2H,2H,3H,3H-PFCAs degrade much faster than corresponding PFCAs. • High pH and HA is not favorable for 2H,2H,3H,3H-PFCAs photodegradation. • Main reactions involve α-oxidation, decarboxylation, hydroxylation, elimination. -- Abstract: Tetrahydroperfluorocarboxylic acids (2H,2H,3H,3H-PFCAs) have aroused the interest of scholars worldwide due to their potential to generate perfluorinated compounds. In this work, we systematically examined the photodegradation kinetics and mechanisms of typical 2H,2H,3H,3H-PFCAs (C_nF_2n+1C₂H₄COOH, n = 6, 7, 8) in aqueous solution by a 500 W Hg lamp. The photodecomposition of 2H,2H,3H,3H-PFCAs all followed pseudo-first-order kinetics, and the photolysis rate coefficients increased with the increasing carbon chain length. Under the same reaction condition, 2H,2H,3H,3H-PFCAs degraded much faster than the corresponding PFCAs. The photodecomposition rate coefficient of C₈F₁₇CH₂CH₂COOH was accelerated by low pH and Fe³⁺ addition, but decreased by the existence of humic acid, carbonate and bicarbonate. Compared with ultrapure water, a decreased removal of 2H,2H,3H,3H-PFCAs was observed in four types of natural waters, i.e., tap water, Jiuxiang river water, primary effluent and secondary effluent. According to mass analysis, C₈F₁₇CH₂CH₂COOH was mainly decomposed into 8:2 fluorotelomer acid (C₈F₁₇CH₂COOH), shorter-chain perfluorocarboxylic acids (PFCAs), perfluoro-1-enes (C_nF_2n) and perfluoroketenes (C_nF_2n+1CF = C = O). Thus, α-oxidation, decarboxylation and elimination reaction were proposed as reaction pathways. ECOSAR predictions showed that photolysis generally decreased the aquatic toxicity of C₈F₁₇CH₂CH₂COOH.