Acetaminophen degradation by hydroxyl and organic radicals in the peracetic acid-based advanced oxidation processes: Theoretical calculation and toxicity assessment

Abstract

The research on the mechanisms and kinetics of radical oxidation in peracetic acid-based advanced oxidation processes was relatively limited. In this work, HO^• and organic radicals mediated reactions of acetaminophen (ACT) were investigated, and the reactivities of important organic radicals (CH₃COO^• and CH₃COOO^•) were calculated. The results showed that initiated reaction rate constants of ACT are in the order: CH₃COO^• (5.44 × 10¹⁰ M^-1 s^-1) > HO^• (7.07 × 10⁹ M^-1 s^-1) > CH₃O^{• (}1.57 × 10⁷ M^-1 s^-1) > CH₃COOO^• (3.65 × 10⁵ M^-1 s^-1) >> ^•CH₃ (5.17 × 10² M^-1 s^-1) > CH₃C^•O (1.17 × 10² M^-1 s^-1) > CH₃OO^• (11.80 M^-1 s^-1). HO^•, CH₃COO^• and CH₃COOO^• play important roles in ACT degradation. CH₃COO^• is another important radical in the hydroxylation of aromatic compounds in addition to HO^•. Reaction rate constants of CH₃COO^• and aromatic compounds are 1.40 × 10⁶ - 6.25 × 10¹⁰ M^-1 s^-1 with addition as the dominant pathway. CH₃COOO^• has high reactivity to phenolate and aniline only among the studied aromatic compounds, and it was more selective than CH₃COO^•. CH₃COO^•-mediated hydroxylation of aromatic compounds could produce their hydroxylated products with higher toxicity.

Keywords: Acetoxyl radical; Acetylperoxy radical; Density functional theory; Kinetics; Mechanism.