Zihan Yang, Yi Zhou, Yiqian Jiang, Peiqing Zhao, Xu Meng
{"title":"Reconsideration of the role of hydrogen peroxide in peroxymonocarbonate-based oxidation system for pollutant control","authors":"Zihan Yang, Yi Zhou, Yiqian Jiang, Peiqing Zhao, Xu Meng","doi":"10.1016/j.watres.2024.122750","DOIUrl":null,"url":null,"abstract":"Advanced oxidation processes that utilize peroxymonocarbonate (HCO<sub>4</sub><sup>-</sup>), generated in-situ through the reaction of HCO<sub>3</sub><sup>-</sup> and H<sub>2</sub>O<sub>2</sub>, are employed for the removal of pollutants in water. Nevertheless, the precise role of H<sub>2</sub>O<sub>2</sub> in these processes remains a subject of debate. This study established a HCO<sub>4</sub><sup>-</sup>-based oxidation system using NaHCO<sub>3</sub> and H<sub>2</sub>O<sub>2</sub> for the degradation of acetaminophen and investigated the activation mechanisms of coexisting oxidants. Under thermal activation conditions, the O-O bond in HCO<sub>4</sub><sup>-</sup> (HO-OCOO<sup>-</sup>) was more readily cleaved than the O-O bond in the co-existing oxidant H<sub>2</sub>O<sub>2</sub> (HO-OH), leading to the generation of reactive oxygen species (ROS). Based on kinetics and ROS evaluation, H<sub>2</sub>O<sub>2</sub> primarily served to form HCO<sub>4</sub><sup>-</sup> rather than converting to ·OH or O<sub>2</sub>, with HCO<sub>4</sub><sup>-</sup> acting as the primary oxidant for degradation through the formation of <span><math><msubsup is=\"true\"><mtext is=\"true\">CO</mtext><mrow is=\"true\"><mn is=\"true\">3</mn></mrow><mrow is=\"true\"><mo is=\"true\">·</mo><mo is=\"true\">−</mo></mrow></msubsup></math></span>and <strong>·</strong>OH. In this oxidation system, H<sub>2</sub>O<sub>2</sub> utilization efficiency for <strong>·</strong>OH production reached 27.34%, <strong>·</strong>OH yield reached 24.15% and acetaminophen degradation efficiency realized 83% at 60 °C with 20 mM HCO<sub>3</sub><sup>-</sup> and 20 mM H<sub>2</sub>O<sub>2</sub>. The apparent activation energy of acetaminophen degradation and HCO<sub>4</sub><sup>-</sup> activation were calculated as 90.83 kJ mol<sup>-1</sup> and 18.81 kJ mol<sup>-1</sup>, respectively. Moreover, a novel CO<sub>2</sub>-derived HCO<sub>4</sub><sup>-</sup>-based system led to a comparable acetaminophen degradation efficiency of 82% and a higher k<em><sub>obs</sub></em> of 0.028 min<sup>-1</sup>. The system optimization and ROS evaluation suggest that high concentration of H<sub>2</sub>O<sub>2</sub> inhibited the degradation and quenched <span><math><msubsup is=\"true\"><mtext is=\"true\">CO</mtext><mrow is=\"true\"><mn is=\"true\">3</mn></mrow><mrow is=\"true\"><mo is=\"true\">·</mo><mo is=\"true\">−</mo></mrow></msubsup></math></span> and <strong>·</strong>OH to yield <strong>·</strong>O<sub>2</sub><sup>-</sup> and <sup>1</sup>O<sub>2</sub>. Furthermore, EPR analysis and quenching experiments indicate that <span><math><msubsup is=\"true\"><mtext is=\"true\">CO</mtext><mrow is=\"true\"><mn is=\"true\">3</mn></mrow><mrow is=\"true\"><mo is=\"true\">·</mo><mo is=\"true\">−</mo></mrow></msubsup></math></span> was mainly responsible for acetaminophen degradation. This work provides fundamental understanding of the HCO<sub>4</sub><sup>-</sup>-based oxidation system.","PeriodicalId":443,"journal":{"name":"Water Research","volume":null,"pages":null},"PeriodicalIF":11.4000,"publicationDate":"2024-11-05","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.2024.122750","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
Advanced oxidation processes that utilize peroxymonocarbonate (HCO4-), generated in-situ through the reaction of HCO3- and H2O2, are employed for the removal of pollutants in water. Nevertheless, the precise role of H2O2 in these processes remains a subject of debate. This study established a HCO4--based oxidation system using NaHCO3 and H2O2 for the degradation of acetaminophen and investigated the activation mechanisms of coexisting oxidants. Under thermal activation conditions, the O-O bond in HCO4- (HO-OCOO-) was more readily cleaved than the O-O bond in the co-existing oxidant H2O2 (HO-OH), leading to the generation of reactive oxygen species (ROS). Based on kinetics and ROS evaluation, H2O2 primarily served to form HCO4- rather than converting to ·OH or O2, with HCO4- acting as the primary oxidant for degradation through the formation of and ·OH. In this oxidation system, H2O2 utilization efficiency for ·OH production reached 27.34%, ·OH yield reached 24.15% and acetaminophen degradation efficiency realized 83% at 60 °C with 20 mM HCO3- and 20 mM H2O2. The apparent activation energy of acetaminophen degradation and HCO4- activation were calculated as 90.83 kJ mol-1 and 18.81 kJ mol-1, respectively. Moreover, a novel CO2-derived HCO4--based system led to a comparable acetaminophen degradation efficiency of 82% and a higher kobs of 0.028 min-1. The system optimization and ROS evaluation suggest that high concentration of H2O2 inhibited the degradation and quenched and ·OH to yield ·O2- and 1O2. Furthermore, EPR analysis and quenching experiments indicate that was mainly responsible for acetaminophen degradation. This work provides fundamental understanding of the HCO4--based oxidation system.
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.