第一作者：Hairui Lv
通讯作者：于雯超 讲师/王辉 教授
通讯单位：北京林业大学环境科学与工程学院
DOI:10.1016/j.cej.2025.159656
nZVI 的快速钝化限制了其对过一硫酸盐（PMS）的持续活化，阻碍了其在环境污染物降解中的应用。本研究合成了一种核壳结构的环糊精负载硫修饰纳米零价铁（S-nZVI@CD），它在活化 PMS 以同时降解诺氟沙星（NOR）和抗生素耐药基因（ARGs）方面表现出了高效性和持久性。硫通过促进亚铁离子循环增强了 PMS 的活化，而环糊精（CD）则改善了硫的分散性，防止了活性物质的快速消耗，创造了一个高效的反应环境。动力学研究表明，S-nZVI@CD/PMS 系统按照伪一阶动力学降解 NOR（kobs = 0.0313 min-1）和 DNA（kobs = 0.224 min-1），而 nZVI/PMS 和 S-nZVI/PMS 系统更倾向于表现出两阶段动力学。空气暴露测试表明，在空气中暴露 60 天后，S-nZVI@CD 仍能有效降解 NOR（99.5%）和 DNA（99.2%）。此外，S-nZVI@CD 还在实际再生水中表现出稳定的 PMS 活化性能，对 NOR 的去除率达到 100%，对总 ARGs 的去除率达到 97.4%，对 1 级整合子 (IntI1) 的去除率达到 98.2%。淬火实验、定量分析和 EPR 测试证实，硫酸根自由基 (SO4--) 和羟基自由基 (-OH) 是 S-nZVI@CD/PMS 系统中的主要活性物种。理论计算确定了 NOR（喹诺酮环）和 DNA（C10、C16、N17 和 N18）上易受自由基攻击的位点，这是它们有效降解的主要机制。这种利用两亲空腔结构的 CD 改性方法为持续活化 PMS 和提高污染物去除率提供了一种策略。
Fig. 1. SEM images for (a) nZVI, (b) S-nZVI@CD. (c) TEM element mapping of the S-nZVI@CD. (d) TEM images of the S-nZVI@CD. (e) XRD spectra of the, nZVI, S-nZVI, and S-nZVI@CD catalysts. (f) Fe2p XPS spectra of the nZVI and S-nZVI@CD.
Fig. 2. (a) NOR degradation by PMS without catalyst, nZVI/PMS, S-nZVI/PMS, and S-nZVI@CD/PMS, respectively. NOR degradation by S-nZVI@CD with different (b) β-CD loading ratio, (c) catalyst dosage, (d) PMS concentration, (e) NOR dosage, and (f) temperature. (Conditions: [NOR]0 = 1.6 μM, [PMS]0 = 16 μM, [S-nZVI@CD]0 = 0.05 g·L−1, initial pH = 7.0 ± 0.1, temperature at 25 ℃).
Fig. 3. (a) Degradation of free DNA by various systems. Degradation of free DNA at various (b) catalyst dosage, (c) pH, (d) PMS dosage, (e) free DNA dosage, (f) Temperature. (Conditions: [DNA]0 = 2 ng·μL−1, [PMS]0 = 16 μM, [S-nZVI@CD]0 = 0.05 g·L−1, initial pH = 7.0 ± 0.1, temperature at 25 ℃).
Fig. 4. (a) Removal efficiency of ARGs, MGEs, and NOR by nZVI/PMS, S-nZVI/PMS and S-nZVI@CD/PMS (The right red axis indicates the removal rate of NOR and ARGs). (b) Natural Water, nZVI, S-nZVI and S-nZVI@CD Column chart of community structure at the phylum level after processing. (c) Horizontal community structure heatmap. (d) The co-occurrence of ARGs, intI1, NOR, and bacterial communities based on network analysis. The nodes with different colors represent different phyla and ARGs. The nodes represent the bacteria at the genus level. The edges indicate strong significant (P < 0.05) correlations between unique ARGs and bacterial genera. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 5. (a) Effect of nZVI/PMS, S-nZVI/PMS, and S-nZVI@CD/PMS system scavengers on the removal of total ARGs and NOR in control. (b) EPR spectra for radicals detection •OH and SO4•−. (c) ATR-FTIR spectra of S-nZVI@CD before and after reaction. (d) Raman spectra of PMS solution, S-nZVI@CD /H2O, and S-nZVI@CD /PMS. (e) Scheme of the reactive species generation from PMS activated by S-nZVI@CD. (Conditions: [NOR]0 = 1.6 μM, [DNA]0 = 2 ng·μL−1, [PMS]0 = 16 μM, [S-nZVI@CD]0 = 0.05 g·L−1, initial pH = 7.0 ± 0.1, temperature at 25 ℃, [MeOH] = 50 mM, [FFA] = 50 mM, [p-BQ] = 2.0 mM, [DMSO] = 0.1 mM).
Fig. 6. (a) Optimized structure, (b) HOMO, (c) LUMO, (d) ESP of NOR. (e) Optimized structure, (f) HOMO, (g) LUMO, (h) ESP of dG. (h) Identified products and proposed pathways of NOR degradation in S-nZVI@CD /PMS system. (Conditions: [NOR]0 = 16 μM, [PMS]0 = 16 μM, [S-nZVI@CD]0 = 0.05 g·L−1, initial pH = 7.0 ± 0.1).
Hairui Lv, Wenchao Yu, Yuyang Li, Xue Sun, Xiangting Hou, Zhaoyong Bian, Hui Wang, Yuansong Wei, Cyclodextrin-supported sulfide zero-valent iron as PMS activator for simultaneous removing norfloxacin and ARGs in reclaimed water: Activation and controlled release of active components, Chemical Engineering Journal, 2025, https://doi.org/10.1016/j.cej.2025.159656
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