{"title":"Carbonate radicals in environmental systems: mechanistic insights and engineering applications","authors":"Zhantao Cai, Gancheng Zuo, Liping Huang, Xiaoyu Lou, Guoyang Zhang, Huan He, Shujuan Zhang","doi":"10.1016/j.watres.2025.124703","DOIUrl":null,"url":null,"abstract":"Carbonate radical (CO<sub>3</sub><sup>•−</sup>) is prevalent in both natural environments and engineered water treatment systems, originating from reactions between carbonate species (CO<sub>3</sub><sup>2−</sup>/HCO<sub>3</sub><sup>−</sup>) and free radicals or triplet states of dissolved organic matter (<sup>3</sup>DOM*). Its significant roles in environmental oxidation, advanced oxidative water treatment, and cellular oxidative damage are increasingly recognized. Despite extensive research on CO<sub>3</sub><sup>•−</sup>, a gap remains in comprehensive reviews addressing its kinetics and mechanisms in pollutant removal and environmental impact. This review synthesizes previous studies, tracing the historical recognition of CO<sub>3</sub><sup>•−</sup> in environmental sciences and comparing various detection methods. The reaction rate constants of CO<sub>3</sub><sup>•−</sup> with organic contaminants (<em>k</em><sub>CO3•−</sub>) are summarized, and the relationship between pollutant structure and reactivity is explored. Reaction mechanisms and the selectivity of CO<sub>3</sub><sup>•−</sup> are critically evaluated in comparison to other common radicals, such as hydroxyl (HO<sup>•</sup>) and sulfate (SO<sub>4</sub><sup>•−</sup>). Furthermore, the dual roles of CO<sub>3</sub><sup>•−</sup> as both primary and secondary radicals in advanced oxidation processes (AOPs), along with its impact on degradation pathways and byproduct toxicity, are assessed. Finally, the environmental implications of CO<sub>3</sub><sup>•−</sup>, including its contributions to self-purification, metal transport, and biological oxidative damage, are discussed. This review aims to offer a comprehensive framework for understanding CO<sub>3</sub><sup>•−</sup> in environmental contexts, enhancing its application in AOP systems and natural remediation.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"54 1","pages":""},"PeriodicalIF":12.4000,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Water Research","FirstCategoryId":"93","ListUrlMain":"https://doi.org/10.1016/j.watres.2025.124703","RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, ENVIRONMENTAL","Score":null,"Total":0}
引用次数: 0
Abstract
Carbonate radical (CO3•−) is prevalent in both natural environments and engineered water treatment systems, originating from reactions between carbonate species (CO32−/HCO3−) and free radicals or triplet states of dissolved organic matter (3DOM*). Its significant roles in environmental oxidation, advanced oxidative water treatment, and cellular oxidative damage are increasingly recognized. Despite extensive research on CO3•−, a gap remains in comprehensive reviews addressing its kinetics and mechanisms in pollutant removal and environmental impact. This review synthesizes previous studies, tracing the historical recognition of CO3•− in environmental sciences and comparing various detection methods. The reaction rate constants of CO3•− with organic contaminants (kCO3•−) are summarized, and the relationship between pollutant structure and reactivity is explored. Reaction mechanisms and the selectivity of CO3•− are critically evaluated in comparison to other common radicals, such as hydroxyl (HO•) and sulfate (SO4•−). Furthermore, the dual roles of CO3•− as both primary and secondary radicals in advanced oxidation processes (AOPs), along with its impact on degradation pathways and byproduct toxicity, are assessed. Finally, the environmental implications of CO3•−, including its contributions to self-purification, metal transport, and biological oxidative damage, are discussed. This review aims to offer a comprehensive framework for understanding CO3•− in environmental contexts, enhancing its application in AOP systems and natural remediation.
期刊介绍:
Water Research, along with its open access companion journal Water Research X, serves as a platform for publishing original research papers covering various aspects of the science and technology related to the anthropogenic water cycle, water quality, and its management worldwide. The audience targeted by the journal comprises biologists, chemical engineers, chemists, civil engineers, environmental engineers, limnologists, and microbiologists. The scope of the journal include:
•Treatment processes for water and wastewaters (municipal, agricultural, industrial, and on-site treatment), including resource recovery and residuals management;
•Urban hydrology including sewer systems, stormwater management, and green infrastructure;
•Drinking water treatment and distribution;
•Potable and non-potable water reuse;
•Sanitation, public health, and risk assessment;
•Anaerobic digestion, solid and hazardous waste management, including source characterization and the effects and control of leachates and gaseous emissions;
•Contaminants (chemical, microbial, anthropogenic particles such as nanoparticles or microplastics) and related water quality sensing, monitoring, fate, and assessment;
•Anthropogenic impacts on inland, tidal, coastal and urban waters, focusing on surface and ground waters, and point and non-point sources of pollution;
•Environmental restoration, linked to surface water, groundwater and groundwater remediation;
•Analysis of the interfaces between sediments and water, and between water and atmosphere, focusing specifically on anthropogenic impacts;
•Mathematical modelling, systems analysis, machine learning, and beneficial use of big data related to the anthropogenic water cycle;
•Socio-economic, policy, and regulations studies.