Fangyuan Cheng , Tingting Zhang , Hao Yang , Jiao Qu , Weihua Song , Ya-nan Zhang
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The secondary reaction rate constant of DMPZ with Br<sub>2</sub><sup>•−</sup> was determined to be 1.68 × 10<sup>7</sup> M<sup>−1</sup> s<sup>−1</sup>. The steady-state concentration of Br<sub>2</sub><sup>•−</sup> ([Br<sub>2</sub><sup>•−</sup>]ss) produced by DOM in water with seawater-level concentrations of halides (540 mM Cl<sup>−</sup> + 0.8 mM Br<sup>−</sup>) under simulated sunlight irradiation was determined to be at the level of 10<sup>−18</sup> M using DMPZ as a probe. Meanwhile, the [Br<sub>2</sub><sup>•−</sup>]ss in natural seawater was measured to be at the level of 10<sup>−20</sup> M. Furthermore, preliminary exploration of Br<sub>2</sub><sup>•−</sup> generation using DOM model compounds suggested that aromatic ketones and electron-rich chromophores may contribute to Br<sub>2</sub><sup>•−</sup> formation. These findings confirm the feasibility of using DMPZ as a quantitative probe for Br<sub>2</sub><sup>•−</sup> in seawater under light conditions, thereby enhancing our understanding of bromine radical formation in water and the complex environmental processes involved.</div></div>","PeriodicalId":443,"journal":{"name":"Water Research","volume":"285 ","pages":"Article 124102"},"PeriodicalIF":11.4000,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Quantitative probe detection of photosensitized dibromide radical anions generated from dissolved organic matter in aquatic systems\",\"authors\":\"Fangyuan Cheng , Tingting Zhang , Hao Yang , Jiao Qu , Weihua Song , Ya-nan Zhang\",\"doi\":\"10.1016/j.watres.2025.124102\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Dibromide radical anions (Br<sub>2</sub><sup>•−</sup>) are prevalent in marine and estuarine waters, significantly influencing the photochemical transformation of pollutants. Despite their importance, the lack of probes to quantitatively detect Br<sub>2</sub><sup>•−</sup> greatly hampers the understanding of their environmental behavior. In this study, we demonstrated that 3,5-dimethyl-1-H-pyrazole (DMPZ) can detect Br<sub>2</sub><sup>•−</sup> in aqueous solutions containing dissolved organic matter (DOM) and halide ions under simulated sunlight irradiation. The formation of Br-DMPZ through the reaction of DMPZ with Br<sub>2</sub><sup>•−</sup> serves as a reliable indicator of Br<sub>2</sub><sup>•−</sup> presence. The secondary reaction rate constant of DMPZ with Br<sub>2</sub><sup>•−</sup> was determined to be 1.68 × 10<sup>7</sup> M<sup>−1</sup> s<sup>−1</sup>. 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引用次数: 0
摘要
二溴基阴离子(Br2•−)在海洋和河口水域中普遍存在,对污染物的光化学转化有重要影响。尽管它们很重要,但缺乏定量检测Br2•−的探针,极大地阻碍了对它们环境行为的理解。在这项研究中,我们证明了3,5-二甲基-1- h -吡唑(DMPZ)在模拟阳光照射下可以检测含有溶解有机物(DOM)和卤化物离子的水溶液中的Br2•−。通过DMPZ与Br2•−反应生成Br-DMPZ可作为Br2•−存在的可靠指标。DMPZ与Br2•−的二次反应速率常数为1.68 × 107 M−1 s−1。以DMPZ为探针,测定了卤化物浓度为540 mM Cl− + 0.8 mM Br−的海水中DOM产生的Br2•−([Br2•−]ss)在模拟阳光照射下的稳态浓度为10−18 M。同时,在天然海水中测得的[Br2•−]ss在10 ~ 20 m的水平。此外,利用DOM模型化合物对Br2•−生成的初步探索表明,芳香酮和富电子发色团可能有助于Br2•−的形成。这些发现证实了在光照条件下使用DMPZ作为海水中Br2•−的定量探针的可行性,从而增强了我们对水中溴自由基形成及其所涉及的复杂环境过程的理解。
Quantitative probe detection of photosensitized dibromide radical anions generated from dissolved organic matter in aquatic systems
Dibromide radical anions (Br2•−) are prevalent in marine and estuarine waters, significantly influencing the photochemical transformation of pollutants. Despite their importance, the lack of probes to quantitatively detect Br2•− greatly hampers the understanding of their environmental behavior. In this study, we demonstrated that 3,5-dimethyl-1-H-pyrazole (DMPZ) can detect Br2•− in aqueous solutions containing dissolved organic matter (DOM) and halide ions under simulated sunlight irradiation. The formation of Br-DMPZ through the reaction of DMPZ with Br2•− serves as a reliable indicator of Br2•− presence. The secondary reaction rate constant of DMPZ with Br2•− was determined to be 1.68 × 107 M−1 s−1. The steady-state concentration of Br2•− ([Br2•−]ss) produced by DOM in water with seawater-level concentrations of halides (540 mM Cl− + 0.8 mM Br−) under simulated sunlight irradiation was determined to be at the level of 10−18 M using DMPZ as a probe. Meanwhile, the [Br2•−]ss in natural seawater was measured to be at the level of 10−20 M. Furthermore, preliminary exploration of Br2•− generation using DOM model compounds suggested that aromatic ketones and electron-rich chromophores may contribute to Br2•− formation. These findings confirm the feasibility of using DMPZ as a quantitative probe for Br2•− in seawater under light conditions, thereby enhancing our understanding of bromine radical formation in water and the complex environmental processes involved.
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.