Exploration of low-dose ozone-activated periodate (O₃/IO₄⁻) for rapid degradation of the β-Blocker pindolol: efficiency and radical mechanism

IF 11.4 1区环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL

Water Research Pub Date : 2025-06-26 DOI:10.1016/j.watres.2025.124116

Mengya Zhang , Tao Lin , Han Chen

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Abstract

The emergence of recalcitrant organic pollutants poses a significant threat to aquatic environments. PI-based AOPs have been widely used in water treatment and show great potential in degrading these pollutants. This study pioneers the application of low-dose ozone-activated periodate (O₃/IO₄⁻), a novel advanced oxidation process (AOP), for rapid degradation of β-blocker contaminants exemplified by pindolol (PIN). The O₃/PI system exhibits broad pH applicability. Under optimal conditions of 0.175 mg/L O₃, 0.1 mM IO₄⁻, and pH 7.0, the system achieved 99.2 % PIN degradation within 20 s (k_obs = 0.254 s⁻¹) when treating an initial PIN concentration of 1 µM, indicating a strong synergistic effect between low-dose O₃ and PI activation. Radical quenching experiments coupled with electron paramagnetic resonance (EPR) spectroscopy revealed a multi-radical mechanism involving iodine species (IO₃•) and reactive oxygen species (ROS) (•OH, •O₂⁻, ¹O₂), with density functional theory (DFT) calculations confirming ozone-periodate adduct formation (OOOIO₄⁻) as the initiation step for radical chain propagation. The degradation of PIN by the O₃/PI system was minimally affected by coexisting substances in the aqueous matrix, with only high concentrations of HCO₃⁻ and humic acid (HA) showing some influence, while Cl⁻ had negligible effects. This highlights the stability of the O₃/PI system and its potential for practical water treatment applications. The identification of transformation products (TPs) and theoretical calculations elucidated the key ROS (IO₃• and •OH) in the PIN degradation process and their attack pathways (HAA, RAF, and SET). Potential degradation pathways for PIN are proposed. Zebrafish toxicity experiments showed that the O₃/PI system effectively detoxifies PIN, though the toxicity of intermediates warrants attention. In conclusion, the developed O₃/PI system offers an efficient and environmentally friendly strategy for PI activation and the treatment of emerging organic pollutants such as PIN.

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低剂量臭氧活化高碘酸盐（O₃/IO₄）对β-阻滞剂品多洛尔的快速降解的探索：效率和自由基机制

顽固性有机污染物的出现对水生环境构成了重大威胁。基于pi的AOPs在水处理中得到了广泛的应用，在降解这些污染物方面显示出巨大的潜力。这项研究开创了低剂量臭氧活化高碘酸盐（O₃/IO₄⁻）的应用，这是一种新的高级氧化工艺（AOP），用于快速降解以pindolol （PIN）为例的β阻断剂污染物。O₃/PI体系具有广泛的pH适用性。在0.175 mg/L O₃，0.1 mM IO₄⁻，pH 7.0的最佳条件下，当初始PIN浓度为1 μ M时，该系统在20秒内实现了99.2%的PIN降解（kobs = 0.254 s⁻），这表明低剂量O₃和PI活化之间有很强的协同作用。自由基猝灭实验结合电子顺磁共振（EPR）光谱揭示了一个涉及碘种（IO₃•）和活性氧（ROS）（•OH，•O₂⁻，¹O₂）的多自由基机制，密度泛函数理论（DFT）计算证实臭氧-高酸盐加合物（OOOIO₄⁻）的形成是自由基链传播的起始步骤。O₃/PI体系对PIN的降解受水基质中共存物质的影响最小，只有高浓度的HCO₃⁻和腐殖酸（HA）有一定的影响，而Cl⁻的影响可以忽略。这突出了O₃/PI系统的稳定性及其在实际水处理应用中的潜力。转化产物（TPs）的鉴定和理论计算阐明了PIN降解过程中的关键ROS （IO₃•和•OH）及其攻击途径（HAA、RAF和SET）。提出了PIN的潜在降解途径。斑马鱼毒性实验表明，O₃/PI系统有效地解毒PIN，尽管中间体的毒性值得注意。总之，开发的O₃/PI系统为PI活化和处理新出现的有机污染物（如PIN）提供了一种有效和环保的策略。

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来源期刊

Water Research 环境科学-工程：环境

CiteScore

20.80

自引率

9.40%

发文量

1307

审稿时长

38 days

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.