Non-radical pathway dominated highly efficient degradation of norfloxacin using persulfate activation with iron-based biochar
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摘要:
近年来，环境中新污染物的去除备受关注。其中抗生素诺氟沙星作为一种典型的新污染物，能够大量富集于土壤中，威胁到人类健康。已有研究表明，众多去除手段中，铁基生物炭活化强氧化剂的方式是一种高效、廉价的原位去除手段。铁的含量、价态和负载情况是影响催化活性的关键因素。然而，如何将去除能力最大化还尚未探明。因此，针对土壤中的典型抗生素诺氟沙星，系统研究了铁基生物炭热解温度和生物质粒径对诺氟沙星的高效去除能力的影响。采用批实验获得了不同铁基生物炭对诺氟沙星的降解效率和能力；通过自由基淬灭实验结合多种表征探讨了诺氟沙星降解的关键机制。结果表明，热解温度900 °C、生物质粒径为75～150 μm时制备出的铁基生物炭能够在10 min内完全降解诺氟沙星，并且3次使用后仍能保持50%的降解能力。通过作用机制分析，说明诺氟沙星的降解机制是由单线态氧主导的非自由基途径，硫酸根自由基和羟基自由基起辅助作用。研究构建的催化氧化体系对诺氟沙星降解效率高，对环境pH适用性强，二次污染风险低，有望用于土壤中诺氟沙星类污染的修复。
Abstract:In recent years, the removal of new pollutants has been widely concerned. The antibiotic norfloxacin, a typical emerging contaminant, is capable of concentrating in large quantities in the soil and threatening human health. It has been shown that among many removal means, the activation of strong oxidants by iron-based biochar is an efficient and inexpensive in-situ removal method. The content, valence, and loading of iron are the key factors affecting the catalytic activity; however, how to maximize its removal capacity has not been explored yet. This study systematically investigated the effects of pyrolysis temperature and biomass particle size of iron-based biochar on the efficient removal of norfloxacin, a typical antibiotic in soil. The degradation efficiency and capacity of different iron-based biochar for norfloxacin were obtained using batch experiments; the key mechanisms of norfloxacin degradation were explored by free radical quenching experiments combined with multiple characterizations. The results show that the iron-based biochar prepared at 900 °C pyrolysis temperature and small biomass particle size (75～150 μm) exhibit the best removal efficiency and is able to degrade norfloxacin completely within 10 min. Furthermore, it can maintain a 50% degradation capacity after three times use. The mechanism analysis indicates that the non-radical pathway dominates this degradation process by singlet oxygen, while the sulfate and hydroxyl radicals play auxiliary roles. The catalytic oxidation system constructed in this study has high degradation efficiency of norfloxacin, high applicability to environmental pH, and low risk of secondary contamination. It is expected to be used for the remediation of norfloxacin-type contamination in the soil.
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Key words:
- iron-based biochar /
- persulfate /
- antibiotics /
- pyrolysis temperature /
- biomass particle size /
- non-radical pathway
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[1] 中华人民共和国国务院. 新污染物治理行动方案[R]. 北京,2022. [State Council of the People’s Republic of China. Action plan for new pollutants treatment[R]. Beijing,2022. (in Chinese)]
State Council of the People’s Republic of China. Action plan for new pollutants treatment[R]. Beijing, 2022. （in Chinese） [2] 中华人民共和国国务院. 重点管控新污染物清单(2023 年版)[R]. 北京,2022. [State Council of the People’s Republic of China. List of key controlled new pollutants (2023 edition)[R]. Beijing,2022. (in Chinese)]
State Council of the People’s Republic of China. List of key controlled new pollutants （2023 edition）[R]. Beijing, 2022. （in Chinese） [3] NISHA A. Antibiotic residues:A global health hazard[J]. Veterinary World,2008,2(2):375. doi: 10.5455/vetworld.2008.375-377
[4] ZHU Yongguan,ZHAO Yi,LI Bing,et al. Continental-scale pollution of estuaries with antibiotic resistance genes[J]. Nature Microbiology,2017,2:16270. doi: 10.1038/nmicrobiol.2016.270
[5] BAQUERO F,MARTÍNEZ J L,CANTÓN R. Antibiotics and antibiotic resistance in water environments[J]. Current Opinion in Biotechnology,2008,19(3):260 − 265. doi: 10.1016/j.copbio.2008.05.006
[6] 戴轩宇,蔡沐涵. 快速溶剂萃取-固相萃取-超高效液相色谱串联质谱法测定土壤中19种抗生素残留[J]. 环境科技,2023,36(5):66 − 72. [DAI Xuanyu,CAI Muhan. Determination of 19 antibiotics in soil by accelerated solvent extraction-solid phase extraction-ultra high performance liquid chromatography-triple quadrupole mass spectrometry[J]. Environmental Science and Technology,2023,36(5):66 − 72. (in Chinese with English abstract)]
DAI Xuanyu, CAI Muhan . Determination of 19 antibiotics in soil by accelerated solvent extraction-solid phase extraction-ultra high performance liquid chromatography-triple quadrupole mass spectrometry[J]. Environmental Science and Technology,2023 ,36 （5 ）:66 −72 . （in Chinese with English abstract）[7] 郭子宁,王旭升,向师正,等. 再生水入渗区典型抗生素分布特征与地下水微生物群落影响因素研究[J]. 岩矿测试,2022,41(3):451 − 462. [GUO Zining,WANG Xusheng,XIANG Shizheng,et al. Distribution characteristics of typical antibiotics in reclaimed water infiltration area and influencing factors of groundwater microbial community[J]. Rock and Mineral Analysis,2022,41(3):451 − 462. (in Chinese with English abstract)]
GUO Zining, WANG Xusheng, XIANG Shizheng, et al . Distribution characteristics of typical antibiotics in reclaimed water infiltration area and influencing factors of groundwater microbial community[J]. Rock and Mineral Analysis,2022 ,41 （3 ）:451 −462 . （in Chinese with English abstract）[8] LI Xuewen,XIE Yunfeng,LI Canglin,et al. Investigation of residual fluoroquinolones in a soil–vegetable system in an intensive vegetable cultivation area in Northern China[J]. Science of the Total Environment,2014,468/469:258 − 264. doi: 10.1016/j.scitotenv.2013.08.057
[9] MORALES MUÑOZ S,LUQUE GARCÍA J L,LUQUE DE CASTRO M D. Continuous microwave-assisted extraction coupled with derivatization and fluorimetric monitoring for the determination of fluoroquinolone antibacterial agents from soil samples[J]. Journal of Chromatography A,2004,1059(1/2):25 − 31.
[10] LINDBERG R H,OLOFSSON U,RENDAHL P,et al. Behavior of fluoroquinolones and trimethoprim during mechanical,chemical,and active sludge treatment of sewage water and digestion of sludge[J]. Environmental Science & Technology,2006,40(3):1042 − 1048.
[11] JIANG Canlan,JI Yuefei,SHI Yuanyuan,et al. Sulfate radical-based oxidation of fluoroquinolone antibiotics:Kinetics,mechanisms and effects of natural water matrices[J]. Water Research,2016,106:507 − 517.1 doi: 10.1016/j.watres.2016.10.025
[12] 陈凯,刘菲,杨梓涵,等. 原位化学氧化修复工程中氧化剂需求量的测算研究现状[J]. 岩矿测试,2023,42(2):271 − 281. [CHEN Kai,LIU Fei,YANG Zihan,et al. Review on the determination of oxidant demand for in-situ chemical oxidation application[J]. Rock and Mineral Analysis,2023,42(2):271 − 281. (in Chinesewith English abstract)]
CHEN Kai, LIU Fei, YANG Zihan, et al . Review on the determination of oxidant demand for in-situ chemical oxidation application[J]. Rock and Mineral Analysis,2023 ,42 （2 ）:271 −281 . （in Chinesewith English abstract）[13] TSITONAKI A,PETRI B,CRIMI M,et al. In situ chemical oxidation of contaminated soil and groundwater using persulfate:A review[J]. Critical Reviews in Environmental Science & Technology,2010,40(1):55 − 91.
[14] POULSON S R,NARAOKA H. Carbon isotope fractionation during permanganate oxidation of chlorinated ethylenes (cDCE,TCE,PCE)[J]. Environmental Science & Technology,2002,36(15):3270 − 3274.
[15] BOKARE A D,CHOI W. Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes[J]. Journal of Hazardous Materials,2014,275:121 − 135. doi: 10.1016/j.jhazmat.2014.04.054
[16] ZHANG Xiangmin,DAMACHARLA D,MA D,et al. Quantitative proteomics reveals novel protein interaction partners of PP2A catalytic subunit in pancreatic β-cells[J]. Molecular and Cellular Endocrinology,2016,424:1 − 11. doi: 10.1016/j.mce.2016.01.008
[17] LUO Jiayi,YI Yuanqiang,YING Guangguo,et al. Activation of persulfate for highly efficient degradation of metronidazole using Fe(II)-rich potassium doped magnetic biochar[J]. Science of the Total Environment,2021,819:152089.
[18] YAO Shuhua,CHEN Xuejing,GOMEZ MA,et al. One-step synthesis of zerovalent-iron-biochar composites to activate persulfate for phenol degradation[J]. Water science and technology,2019,80(10):1851 − 1860. doi: 10.2166/wst.2020.001
[19] MAGIOGLOU E,FRONTISTIS Z,VAKROS J,et al. Activation of persulfate by biochars from valorized olive stones for the degradation of sulfamethoxazole[J]. Catalysts,2019,9(5):419. doi: 10.3390/catal9050419
[20] HUONG P T,JITAE K,ALTAHTAMOUNI T M,et al. Novel activation of peroxymonosulfate by biochar derived from rice husk toward oxidation of organic contaminants in wastewater[J]. Journal of Water Process Engineering,2020,33:101037. doi: 10.1016/j.jwpe.2019.101037
[21] SONG Haocheng,LI Qiang,YE Yuxuan,et al. Degradation of cephalexin by persulfate activated with magnetic loofah biochar:Performance and mechanism[J]. Separation and Purification Technology,2021,272:118971. doi: 10.1016/j.seppur.2021.118971
[22] HONGH Qiaofeng,LIU Chao,WANG Zhengbei,et al. Electron transfer enhancing Fe(II)/Fe(III) cycle by sulfur and biochar in magnetic FeS@biochar to active peroxymonosulfate for 2,4-dichlorophenoxyacetic acid degradation[J]. Chemical Engineering Journal,2021,417(2):129238.
[23] LI Xiaodong,CAO Huizhen,CAO Yuan,et al. Insights into the mechanism of persulfate activation with biochar composite loaded with Fe for 2,4-dinitrotoluene degradation[J]. Journal of Environmental Management,2023,341:117955. doi: 10.1016/j.jenvman.2023.117955
[24] XU Zibo,WAN Zhonghao,SUN Yuqing,et al. Unraveling iron speciation on Fe-biochar with distinct arsenic removal mechanisms and depth distributions of As and Fe[J]. Chemical Engineering Journal,2021,425:131489. doi: 10.1016/j.cej.2021.131489
[25] LI Shasha,SHAO Liming,ZHANG Hua,et al. Quantifying the contributions of surface area and redox-active moieties to electron exchange capacities of biochar[J]. Journal of Hazardous Materials,2020,394:122541. doi: 10.1016/j.jhazmat.2020.122541
[26] XU Zibo,WAN Zhonghao,SUN Yuqing,et al. Electroactive Fe-biochar for redox-related remediation of arsenic and chromium:Distinct redox nature with varying iron/carbon speciation[J]. Journal of Hazardous Materials,2020,430:128479.
[27] LUO Jiayi,YI Yunqiang,YING Guangguo,et al. Activation of persulfate for highly efficient degradation of metronidazole using Fe(II)-rich potassium doped magnetic biochar[J]. Science of the Total Environment,2022,819:152089. doi: 10.1016/j.scitotenv.2021.152089
[28] WANG Kun,SUN Yuebing,TANG Jingchun,et al. Aqueous Cr(VI) removal by a novel ball milled Fe0-biochar composite:Role of biochar electron transfer capacity under high pyrolysis temperature[J]. Chemosphere,2020,241:125044. doi: 10.1016/j.chemosphere.2019.125044
[29] CHEN Yidi,BAI Shunwen,LI Ruixiang,et al. Magnetic biochar catalysts from anaerobic digested sludge:Production,application and environment impact[J]. Environment International,2019,126:302 − 308. doi: 10.1016/j.envint.2019.02.032
[30] GUO Lijun,ZHAO Liming,TANG Yuling,et al. An iron–based biochar for persulfate activation with highly efficient and durable removal of refractory dyes[J]. Journal of Environmental Chemical Engineering,2022,10(1):106979. doi: 10.1016/j.jece.2021.106979
[31] JIN Zilan,XIAO Shuangjie,DONG Haoran,et al. Adsorption and catalytic degradation of organic contaminants by biochar:Overlooked role of biochar’s particle size[J]. Journal of Hazardous Materials,2022,422:126928. doi: 10.1016/j.jhazmat.2021.126928
[32] MA Shaoqiang,JING Fanqi,Sohi S P ,et al. New insights into contrasting mechanisms for PAE adsorption on millimeter,micron- and nano-scale biochar[J]. Environmental Science and Pollution Research,2019,26(18):18636-18650.
[33] YU Jiangfang,TANG Lin,PANG Ya,et al. Magnetic nitrogen-doped sludge-derived biochar catalysts for persulfate activation:Internal electron transfer mechanism[J]. Chemical Engineering Journal,2019,364:146 − 159. doi: 10.1016/j.cej.2019.01.163
[34] ZHU Fang,WU Yuanyuan,LIANG Yukun,et al. Degradation mechanism of norfloxacin in water using persulfate activated by BC@nZVI/Ni[J]. Chemical Engineering Journal,2020,389:124276. doi: 10.1016/j.cej.2020.124276
[35] HU Xiaohong,XU Jianying,WU Mingshan,et al. Effects of biomass pre-pyrolysis and pyrolysis temperature on magnetic biochar properties[J]. Journal of Analytical and Applied Pyrolysis,2017,127:196 − 202. doi: 10.1016/j.jaap.2017.08.006
[36] LI Wei,LIU Baoxia,WANG Zeming,et al. Efficient activation of peroxydisulfate (PDS) by rice straw biochar modified by copper oxide (RSBC-CuO) for the degradation of phenacetin (PNT)[J]. Chemical Engineering Journal,2020,395:125094. doi: 10.1016/j.cej.2020.125094
[37] WANG Bingyu,LI Qiaoqiao,LV Ying,et al. Insights into the mechanism of peroxydisulfate activated by magnetic spinel CuFe2O4/SBC as a heterogeneous catalyst for bisphenol S degradation[J]. Chemical Engineering Journal,2021,416:129162. doi: 10.1016/j.cej.2021.129162
[38] YANG Shiying,WAHG Pin,YANG Xin,et al. Degradation efficiencies of azo dye Acid Orange 7 by the interaction of heat UV and anions with common oxidants:Persulfate,peroxymonosulfate and hydrogen peroxide[J]. Journal of Hazardous Materials,2010,179(1/2/3):552 − 558.
[39] LI Ke,STEFAN M I,CRITTENDEN J C,et al. Trichloroethene degradation by UV/H2O2 advanced oxidation process:Product study and kinetic modeling[J]. Environmental Science & Technology,2007,41(5):1696 − 1703.
[40] ANIPSITAKIS G P,DIONYSIOU D D. Radical generation by the interaction of transition metals with common oxidants[J]. Environmental Science & Technology,2004,38(13):3705 − 3712.
[41] PHAM H T,SUTO K,INOUE C. Trichloroethylene transformation in aerobic pyrite suspension:Pathways and kinetic modeling[J]. Environmental Science & Technology,2009,43(17):6744 − 6749.
[42] ZHU Shishu,LI Xiaojie,KANG Jian,et al. Persulfate activation on crystallographic manganese oxides:Mechanism of singlet oxygen evolution for nonradical selective degradation of aqueous contaminants[J]. Environmental Science & Technology,2019,53(1):307 − 315.
[43] XU Xiangjian,YANG Yu,JIA Yongfong,et al. Heterogeneous catalytic degradation of 2,4-dinitrotoluene by the combined persulfate and hydrogen peroxide activated by the as-synthesized Fe-Mn binary oxides[J]. Chemical Engineering Journal,2019,374:776 − 786. doi: 10.1016/j.cej.2019.05.138
[44] CAI Song,WANG Tongshuai,WU Congyi,et al. Efficient degradation of norfloxacin using a novel biochar-supported CuO/Fe3O4 combined with peroxydisulfate:Insights into enhanced contribution of nonradical pathway[J]. Chemosphere,2023,329:138589. doi: 10.1016/j.chemosphere.2023.138589
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