Comparison of chemical and biological degradation of sulfonamides: Solving the mystery of sulfonamide transformation

Abstract

Sulfonamides (SAs) are widespread in aquatic environments and pose serious environmental risks. The removal efficiencies and degradation mechanisms of SAs in both chemical and biological degradation systems were comprehensively reviewed. Density functional theory (DFT) was utilized to decipher the reaction types and reactive sites of both degradation mechanisms at the electron level. In chemical degradation, the rate of the reactive oxidants to degrade SAs follows the order SO₄•^- ≈ •OH > O₃ > ¹O₂ > ClO₂ ≈ Fe(VI) ≈ HOCl > peroxymonosulfate. pH affects the oxidation-reduction potentials of oxidants, the reactivity of SAs, and the intermolecular force between oxidants and SAs, thereby affecting the chemical degradation efficiencies and mechanisms. In biological degradation, oxidoreductase produced by bacteria, fungi, algae, and plants can degrade SAs. The catalytic activity of the enzyme is affected by the enzyme system, reaction conditions, and type of SAs. Despite the different reaction modes and removal efficiencies of SAs in chemical degradation and biological degradation, the transformation pathways and products show commonalities. Modification of the amino (N¹H₂-) moiety and destruction of sulfonamide bridge (-SO₂-N¹¹H-) moiety are the main pathways for both chemical and biological degradation of SAs. Most oxidants or enzymes can react with the N¹H₂- moiety. Reactions of the -SO₂-N¹¹H- moiety are mainly initiated by the cleavage of S-N bonds for five-membered heterocyclic ring-substituted SAs, and by SO₂ extrusion for six-membered heterocyclic ring-substituted SAs. Chlorine substitution and coupling on the N¹H₂- moiety, hydroxylation of the benzene moiety, oxidation of methyl, and isomerization of the R substituents are the transformation pathways unique to chemical degradation. Formylation/acetylation, glycosylation, pterin conjugation, and deamination of the N¹H₂- moiety are the transformation pathways unique to biological degradation. DFT studies revealed the same reaction types and the same reactive sites of SAs in chemical and biological degradation. Electrophiles are mostly prone to attack the N¹ atom on the amino moiety of neutral SAs and the N¹¹ atom on the sulfonamide bridge moiety of anionic SAs, leading to nitration or electrophilic substitution of the amino moiety and the cleavage of S-N bonds or SO₂ extrusion of the sulfonamide bridge moiety. Reactions on the -SO₂-N¹¹H- moiety eliminate antibacterial activity in the SA degradation process. This review elucidated SA transformation by comparing the chemical and biological degradation of SAs. This could provide theoretical guidance for the development of more efficient and economical treatment technologies for SAs.

Keywords: Antibiotics removal; Density function theory; Electrophilic reaction; Functional enzyme; Reactive oxidants; SO(2) extrusion.