Enhanced Degradation of Micropollutants in a Peracetic Acid–Fe(III) System with Picolinic Acid

Activation of peracetic acid (PAA) with iron species is an emerging advanced oxidation process (AOP). This study investigates the use of the chelating agent picolinic acid (PICA) to extend the pH range and enhance the performance of the PAA–Fe(III) AOP. Compared to the PAA–Fe(III) system, the PAA–Fe(III)–PICA system degrades various micropollutants (MPs: methylene blue, naproxen, sulfamethoxazole, carbamazepine, trimethoprim, diclofenac, and bisphenol-A) much more rapidly at higher pH, achieving almost complete removal of parent compounds within 10 min. PAA significantly outperforms the coexistent H₂O₂ and is the key oxidant for rapid compound degradation. Other chelating agents, EDTA, NTA, citric acid, proline, and nicotinic acid, could not enhance MP degradation in the PAA–Fe(III) system, while 2,6-pyridinedicarboxylic acid with a structure similar to PICA moderately enhanced MP degradation. Experiments with scavengers (tert-butyl alcohol and methyl phenyl sulfoxide) and a probe compound (benzoic acid) confirmed that high-valent iron species [Fe(IV) and/or Fe(V)], rather than radicals, are the major reactive species contributing to MP degradation. The oxidation products of methylene blue, naproxen, and sulfamethoxazole by PAA–Fe(III)–PICA were characterized and supported the proposed mechanism. This work demonstrates that PICA is an effective complexing ligand to assist the Fenton reaction of PAA by extending the applicable pH range and accelerating the catalytic ability of Fe(III).