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  4. Kinetic and mechanistic understanding of chlorite oxidation during chlorination: Optimization of ClO2 pre-oxidation for disinfection byproduct control
 
research article

Kinetic and mechanistic understanding of chlorite oxidation during chlorination: Optimization of ClO2 pre-oxidation for disinfection byproduct control

Rouge, Valentin
•
Lee, Yunho
•
von Gunten, Urs  
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July 15, 2022
Water Research

Chlorine dioxide (ClO2) applications to drinking water are limited by the formation of chlorite (ClO2-) which is regulated in many countries. However, when ClO2 is used as a pre-oxidant, ClO2- can be oxidized by chlorine during subsequent disinfection. In this study, a kinetic model for the reaction of chlorine with ClO2- was developed to predict the fate of ClO2- during chlorine disinfection. The reaction of ClO2- with chlorine was found to be highly pH-dependent with formation of ClO3- and ClO2 in ultrapure water. In presence of dissolved organic matter (DOM), 60-70% of the ClO2- was transformed to ClO3- during chlorination, while the in situ regenerated ClO2 was quickly consumed by reaction with DOM. The remaining 30-40% of the ClO2- first reacted to ClO2 which then formed chlorine from the DOM-ClO2 reaction. Since only part of the ClO2- was transformed to ClO3-, the sum of the molar concentrations of oxychlorine species (ClO2- + ClO3-) decreased during chlorination. By kinetic modelling, the ClO2- concentration after 24 h of chlorination was accurately predicted in synthetic waters but was largely overestimated in natural waters, possibly due to a ClO2- decay enhanced by high concentrations of chloride and in situ formed bromine from bromide. Understanding the chlorine-ClO2 reaction mechanism and the corresponding kinetics allows to potentially apply higher ClO2 doses during the pre-oxidation step, thus improving disinfection byproduct mitigation while keeping ClO2-, and if required, ClO3- below the regulatory limits. In addition, ClO2 was demonstrated to efficiently degrade haloacetonitrile precursors, either when used as pre-oxidant or when regenerated in situ during chlorination.

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Type
research article
DOI
10.1016/j.watres.2022.118515
Web of Science ID

WOS:000815828400006

Author(s)
Rouge, Valentin
Lee, Yunho
von Gunten, Urs  
Allard, Sebastien
Date Issued

2022-07-15

Publisher

PERGAMON-ELSEVIER SCIENCE LTD

Published in
Water Research
Volume

220

Article Number

118515

Subjects

Engineering, Environmental

•

Environmental Sciences

•

Water Resources

•

Engineering

•

Environmental Sciences & Ecology

•

chlorine dioxide

•

chlorite

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chlorate

•

disinfection byproducts

•

kinetic modelling

•

solid-phase microextraction

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natural organic-matter

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drinking-water

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hypochlorous acid

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dioxide preoxidation

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chlorate ion

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bromine

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chloramination

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reactivity

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removal

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LTQE  
Available on Infoscience
July 18, 2022
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/189364
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