Enhanced norfloxacin oxidation with an Fe(VI)/peroxydisulfate-quinone process: iron species-driven multi-oxidation, quinone-based regulation, and density functional theory analysis

IF 12.4 1区环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL

Water Research Pub Date : 2025-10-22 DOI:10.1016/j.watres.2025.124850

Xiao Luo , Yihan Li , Xiaoke Ma , Tapas Sen , Lin Zhao , Yongkui Yang , Peizhe Sun

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引用次数: 0

Abstract

The individual Fe(VI) as FeO₄^2- or peroxydisulfate (PDS) oxidation process faces challenges of limited oxidation efficiency, excessive dosage consumption, and a narrow pH range. Fe is an important component in both Fe(VI) oxidation and PDS activation. We propose linking Fe in the combined Fe(VI)/PDS process to address the challenges of their individual processes. The contribution of Fe species to reactive oxygen species (ROS) production in the Fe(VI)/PDS process and the regulatory effects of quinones on Fe species in the Fe(VI)/PDS-benzoquinone (BQ) process were investigated. The reactive oxidation species generated by the Fe(VI)/PDS process included high-valency iron species such as Fe(VI), Fe(V), and Fe(IV); hydroxy radicals (∙OH), singlet oxygen (¹O₂), and SO₄˙ˉ contributed differently at varying pH levels. PDS accelerated the conversion of Fe(VI) to Fe(V) and Fe(IV), which are more reactive, and facilitated their regeneration from Fe(III) and Fe(II). The Fe(II) concentration in the Fe(VI)/PDS process increased by 35.0 % after BQ addition, which enhanced PDS activation and shifted the dominant oxidizer from high-valency iron to ROS. In the Fe(VI)/PDS-BQ process, norfloxacin underwent oxidative degradation via piperazinyl ring degradation, defluorination, and quinolone group degradation, as evidenced by degradation byproducts and further supported by density functional theory calculations. The Fe(VI)/PDS-BQ process significantly reduced the toxicity of norfloxacin. A novel Fe(VI)/PDS-BQ process was developed with the potential to eliminate antibiotics from water and to identify the Fe-involved oxidation mechanism regulated by BQ addition and pH.

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铁(VI)/过氧二磺酸盐-醌强化诺氟沙星氧化过程：铁驱动的多重氧化、醌调控和密度泛函数理论分析

单个Fe（VI）作为FeO42-或过氧硫酸氢盐（PDS）氧化过程面临氧化效率有限、用量消耗过大和pH范围窄的挑战。铁是Fe（VI）氧化和PDS活化的重要组分。我们建议在Fe(VI)/PDS联合工艺中连接Fe，以解决各自工艺的挑战。研究了Fe(VI)/PDS工艺中Fe(VI)/PDS-苯醌（BQ）工艺中Fe(VI)/PDS-苯醌（BQ）工艺中Fe(VI)/PDS-苯醌（BQ）工艺中Fe（VI）对活性氧（ROS）生成的贡献以及醌类对Fe(VI)/PDS-苯醌（BQ）工艺中Fe（VI）的调控作用。Fe(VI)/PDS工艺生成的活性氧化物质主要为Fe（VI）、Fe(V)和Fe（IV）等高价铁；在不同的pH水平下，羟基自由基（∙OH）、单线态氧（1O2）和SO4˙PDS加速了Fe（VI）向Fe(V)和Fe（IV）的转化，并促进了它们从Fe（III）和Fe（II）再生。添加BQ后，Fe(VI)/PDS过程中的Fe（II）浓度提高了35.0%，增强了PDS的活性，使优势氧化剂由高价铁转向活性氧。在Fe(VI)/PDS-BQ工艺中，诺氟沙星经过哌嗪基环降解、脱氟和喹诺酮基降解等氧化降解过程，得到了降解副产物的证实，并得到了密度泛函理论计算的支持。Fe(VI)/PDS-BQ工艺显著降低了诺氟沙星的毒性。开发了一种新的Fe(VI)/PDS-BQ工艺，该工艺具有去除水中抗生素的潜力，并确定了BQ添加量和pH调节铁参与氧化的机制。

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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.