TY - JOUR

T1 - Experimental determination and QSAR analysis of the rate constants for SO5•- reactions with aromatic micropollutants in water

AU - Zhang, Yihui

AU - Lu, Kun

AU - Wang, Wenyu

AU - Guo, Juntao

AU - Zou, Yongrong

AU - Xu, Jing

AU - Li, Jinjun

AU - Pozdnyakov, Ivan P

AU - Wu, Feng

N1 - This work was supported by National Natural Science Foundation of China (No. 22061132001), and Russian Science Foundation (Grant RSFNSFC No. 21-43-00004). The author appreciates helpful comments from the editors and reviewers. Copyright © 2023 Elsevier Ltd. All rights reserved.

PY - 2024/1

Y1 - 2024/1

N2 - S(IV)-based systems used for advanced oxidation processes (AOPs) have been constructed for the degradation of organic contaminants via oxysulfur radicals, including SO3•-, SO4•-, and SO5•-. Although SO5•- is proposed as an active species in AOPs processes, research on the reactivity of SO5•- has remained unclear. In this work, 53 target aromatic micropollutants (AMPs), including 13 phenols, 27 amines, and 13 PPCPs were selected to determine the second-order reaction rate constants for SO5•- using the competitive kinetics method, in which the [Formula: see text] values, observed at pH 4 ranged from (2.44 ± 0.00) × 105 M-1 s-1 to (4.41 ± 0.28) × 107 M-1 s-1. Quantitative structure-activity relationship (QSAR) models for the oxidation of AMPs by SO5•- were developed based on 40 [Formula: see text] values of amines and phenols, and their molecular descriptors, using the stepwise multiple linear regression method. This comprehensive model exhibited the excellent goodness-of-fit (Radj2 = 0.802), robustness (QLOO2 = 0.749), and predictability (Qext2 = 0.656), and the one-electron oxidation potential (Eox), energy of the highest occupied molecular orbital energy (EHOMO), and most positive net atomic charge on the carbon atoms (qC+) were considered the most influential descriptors for the comprehensive model, indicating that SO5•- oxidizes pollutants via single electron transfer reaction and exhibits a strong oxidation capacity, especially for pollutants containing electron-donating groups. Moreover, the [Formula: see text] values of 13 PPCPs were predicted using this comprehensive model, which suggested the practical application significance of the QSAR model. This study emphasizes the direct oxidation capacity of SO5•-, which is important to evaluate and simulate AOPs based on S(IV).

AB - S(IV)-based systems used for advanced oxidation processes (AOPs) have been constructed for the degradation of organic contaminants via oxysulfur radicals, including SO3•-, SO4•-, and SO5•-. Although SO5•- is proposed as an active species in AOPs processes, research on the reactivity of SO5•- has remained unclear. In this work, 53 target aromatic micropollutants (AMPs), including 13 phenols, 27 amines, and 13 PPCPs were selected to determine the second-order reaction rate constants for SO5•- using the competitive kinetics method, in which the [Formula: see text] values, observed at pH 4 ranged from (2.44 ± 0.00) × 105 M-1 s-1 to (4.41 ± 0.28) × 107 M-1 s-1. Quantitative structure-activity relationship (QSAR) models for the oxidation of AMPs by SO5•- were developed based on 40 [Formula: see text] values of amines and phenols, and their molecular descriptors, using the stepwise multiple linear regression method. This comprehensive model exhibited the excellent goodness-of-fit (Radj2 = 0.802), robustness (QLOO2 = 0.749), and predictability (Qext2 = 0.656), and the one-electron oxidation potential (Eox), energy of the highest occupied molecular orbital energy (EHOMO), and most positive net atomic charge on the carbon atoms (qC+) were considered the most influential descriptors for the comprehensive model, indicating that SO5•- oxidizes pollutants via single electron transfer reaction and exhibits a strong oxidation capacity, especially for pollutants containing electron-donating groups. Moreover, the [Formula: see text] values of 13 PPCPs were predicted using this comprehensive model, which suggested the practical application significance of the QSAR model. This study emphasizes the direct oxidation capacity of SO5•-, which is important to evaluate and simulate AOPs based on S(IV).

KW - Aromatic micropollutants

KW - Competitive kinetic method

KW - Peroxymonosulfate radical

KW - Quantitative structure-activity relationship

KW - S(IV)-based AOPs

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85176357403&origin=inward&txGid=0bf8c081e0e79bb24e13e0fe9450eee2

UR - https://www.mendeley.com/catalogue/4d0d0405-83e3-3abf-a2c8-2ae2c602a02c/

U2 - 10.1016/j.chemosphere.2023.140598

DO - 10.1016/j.chemosphere.2023.140598

M3 - Article

C2 - 37926161

VL - 346

JO - Chemosphere

JF - Chemosphere

SN - 0045-6535

M1 - 140598

ER -