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磁性市政污泥生物炭活化过硫酸盐降解水中四环素的性能和机制
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Abstract:
四环素(TC)本身特定的结构导致其在生物体内不易被代谢，且容易在水中积累，逐渐对环境和人类健康造成威胁。本研究以含铁市政污泥为原料制备磁性污泥生物炭(MSB)，用于水体中TC的降解性能和机制研究。应用傅里叶红外光谱(FTIR)，X射线光电子能谱(XPS)等探究反应前后MSB的理化性质；并探究了炭化温度，MSB900投加量，过硫酸盐初始浓度、共存离子等因素对MSB900活化过硫酸盐降解水中TC的影响。表征结果表明MSB900表面含有多种含氧官能团以及铁元素，且反应后含氧官能团和铁元素的含量均有明显下降。研究结果表明MSB在最佳实验条件下(炭化温度为900℃、1.33 g/L投加量、10 mmol/L过硫酸盐浓度、pH 3)对TC的降解效果最好，此时最大去除率为94.07%。此外，阴离子Cl？、HCO3？、SO？2？对TC去除率影响不显著，而金属阳离子Ca2+、K+、Mg2+、Na+有一定的抑制作用；Ca2+的抑制作用最强，Na？的抑制作用最弱。MSB900活化过硫酸盐降解水中TC的机制主要为发生了Fe2+/Fe3+循环促成了硫酸根自由基(SO？？？)与羟基自由基(？OH)的生成。本研究表明以含铁污泥为原料制备的磁性污泥生物炭可以作为一种有效的活化过硫酸盐降解TC的环保功能材料。
The unique structural characteristics of tetracycline render it resistant to metabolic degradation in organisms, leading to its accumulation in aquatic environments and posing a growing threat to both ecosystems and human health. In this study, magnetic sludge biochar (MSB) was synthesized from iron-rich sewage sludge to investigate its efficacy and mechanism in degrading tetracycline (TC) in aqueous solutions. The physicochemical properties of MSB were characterized using Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The effects of key parameters—including pyrolysis temperature, MSB dosage, persulfate concentration, solution pH, and coexisting ions—on tetracycline degradation were systematically evaluated. Characterization revealed that MSB900 (pyrolyzed at 900？C) exhibited abundant oxygen-containing functional groups and iron species, although their concentrations decreased significantly after pyrolysis. Under optimal conditions (pyrolysis temperature: 900？C, MSB dosage: 1.33 g/L, persulfate concentration: 10 mmol/L, pH 3), the degradation efficiency of TC reached 94.07%. Furthermore, common anions (Cl？, HCO？？, SO？2？) exhibited negligible effects on degradation, whereas cationic species (Ca2？, K？, Mg2？, Na？) slightly inhibited the process. Mechanistic studies indicated that TC degradation involved the redox cycling of Fe2？/Fe3？ and the synergistic action of sulfate radical (SO？？？) and hydroxyl radicals (？OH). These findings demonstrate that iron-laden sludge-derived magnetic biochar serves as an efficient and sustainable persulfate activator for the remediation of TC-contaminated
| [1] | 张韶珂, 王梦丽, 张杰, 等. 改性玉米秸秆在污水处理中的应用[J]. 应用化工, 2023, 52(3): 815-819+826. |
| [2] | Ahmadi, M., Motlagh, H.R., Jaafarzadeh, N., et al. (2017) Enhanced Photocatalytic Degradation of Tetracycline and Real Pharmaceutical Waste Water Using MWCNT/TiO2 Nanocomposite. Journal of Environmental Management, 186, 55-63. |
| [3] | 胡佳南. 莱茵衣藻对水环境中盐酸四环素的去除研究[D]: [硕士学位论文]. 泰安: 山东农业大学, 2018. |
| [4] | 廖权, 骆华勇, 荣宏伟, 等. 纳米氧化铝改性凝胶球对四环素吸附性能分析[J]. 环境工程, 2020, 38(9): 36-42. |
| [5] | 张修宇. 牛粪生物炭对水中四环素的吸附特性研究[D]: [硕士学位论文]. 哈尔滨: 东北农业大学, 2020. |
| [6] | 赵怀燕, 张广瑶, 涂佳艺, 等. 四环素在环境中的污染现状及锰氧化物对其降解的研究进展[J]. 安徽农业大学学报, 2022, 49(5): 809-814. |
| [7] | 张爱佳, 单凤君, 张震斌, 等. 金属有机骨架材料去除水中四环素研究进展[J]. 辽宁工业大学学报(自然科学版), 2022, 42(6): 399-407. |
| [8] | 张浩, 罗义, 周启星. 四环素类抗生素生态毒性研究进展[J]. 农业环境科学学报, 2008, 27(2): 407-413. |
| [9] | 朱鋆珊, 郭丽, 李平. 高级氧化技术在四环素废水处理中的应用进展[J]. 化工科技, 2019, 27(4): 65-68. |
| [10] | 张婷婷, 许贺, 蔡冬清, 等. 香榧壳生物炭/g-C3N4活化过硫酸盐的光催化性能[J]. 中国环境科学, 2022, 42(3): 1146-1156. |
| [11] | 朱睿, 谭烨, 李春全, 等. 基于过渡金属活化的过硫酸盐高级氧化技术研究进展[J]. 化工矿物与加工, 2022, 51(1): 49-55. |
| [12] | An, L. and Xiao, P. (2020) Zero-Valent Iron/Activated Carbon Microelectrolysis to Activate Peroxydisulfate for Efficient Degradation of Chlortetracycline in Aqueous Solution. RSC Advances, 10, 19401-19409. https://doi.org/10.1039/d0ra03639k |
| [13] | 吴彦霖. 基于羟基自由基和硫酸根自由基的高级氧化技术的研究[D]: [博士学位论文]. 上海: 复旦大学, 2014. |
| [14] | 陈一萍, 夏管商, 郑朝洪, 等. CNTs/PMS高级氧化体系去除水中的环丙沙星[J]. 化工进展, 2019, 38(4): 2037-2045. |
| [15] | Zhu, Y., Guan, Z., Li, X., et al. (2023) Ultrafast Short-Range Catalytic Pathway Modified Peroxymonosulfate Activation over CuO with Surface Oxygen Defects for Tetracycline Hydrochloride Degradation. Environmental Research, 222, Article 115322. |
| [16] | 秦航道, 肖榕, 成昊, 等. 生物炭活化过一硫酸盐降解水中四环素的研究: 表征、催化活性、反应条件优化和机理[J]. 环境科学学报, 2023, 43(4): 243-253. |
| [17] | 董康妮. 利用改性苎麻秸秆生物炭活化过硫酸盐去除盐酸四环素的研究[D]: [硕士学位论文]. 重庆: 重庆大学, 2022. |
| [18] | Fu, D., Kurniawan, T.A., Wang, Y., Zhou, Z., Wei, Q., Hu, Y., et al. (2023) Applicability of Magnetic Biochar Derived from Fe-Enriched Sewage Sludge for Chromate Removal from Aqueous Solution. Chemical Engineering Science, 281, Article 119145. https://doi.org/10.1016/j.ces.2023.119145 |
| [19] | Wang, B., Deng, C., Ma, W. and Sun, Y. (2021) Modified Nanoscale Zero-Valent Iron in Persulfate Activation for Organic Pollution Remediation: A Review. Environmental Science and Pollution Research, 28, 34229-34247. https://doi.org/10.1007/s11356-021-13972-w |
| [20] | Cao, B., Qu, J., Bian, W., et al. (2024) Porous Hydrochar Loaded nZVI as an Efficient Catalyst to Activate Persulfate for Phenol Degradation: Performance and Mechanism. Journal of Cleaner Production, 444, Article 141221. |
| [21] | Yan, J., Han, L., Gao, W., Xue, S. and Chen, M. (2015) Biochar Supported Nanoscale Zerovalent Iron Composite Used as Persulfate Activator for Removing Trichloroethylene. Bioresource Technology, 175, 269-274. https://doi.org/10.1016/j.biortech.2014.10.103 |
| [22] | Li, Z., Schulz, L., Ackley, C. and Fenske, N. (2010) Adsorption of Tetracycline on Kaolinite with Ph-Dependent Surface Charges. Journal of Colloid and Interface Science, 351, 254-260. https://doi.org/10.1016/j.jcis.2010.07.034 |
| [23] | Wang, X., Tong, J. and Ma, J. (2023) Design of Sisal Fibre Biochar/Poly(Dopamine)/nzvi@pan Membrane for Efficient Degradation of Tetracycline. Reactive and Functional Polymers, 192, Article 105704. https://doi.org/10.1016/j.reactfunctpolym.2023.105704 |
| [24] | 许红. 磁性改性生物炭活化过硫酸氢盐降解四环素的效能及机制研究[D]: [硕士学位论文]. 贵阳: 贵州大学, 2023. |
| [25] | Yu, J., Feng, H., Tang, L., Pang, Y., Zeng, G., Lu, Y., et al. (2020) Metal-Free Carbon Materials for Persulfate-Based Advanced Oxidation Process: Microstructure, Property and Tailoring. Progress in Materials Science, 111, Article 100654. https://doi.org/10.1016/j.pmatsci.2020.100654 |
