碳球负载纳米零价铁活化过硫酸盐降解水中恩诺沙星的性能研究

doi:10.16258/j.cnki.1674-5906.2024.05.009

生态环境学报 ›› 2024, Vol. 33 ›› Issue (5): 757-770.DOI: 10.16258/j.cnki.1674-5906.2024.05.009

• 研究论文【环境科学】 • 上一篇下一篇

碳球负载纳米零价铁活化过硫酸盐降解水中恩诺沙星的性能研究

赵乐依¹(), 朱雪强¹^,^*(), 刘健¹^,², 路平¹

1.中国矿业大学环境与测绘学院，江苏徐州 221116
2.江苏云意电气股份有限公司，江苏徐州 221116

收稿日期:2023-12-20 出版日期:2024-05-18 发布日期:2024-06-27
通讯作者: * 朱雪强。E-mail: zhuxq0615@163.com
作者简介:赵乐依（1999年生），女，硕士研究生，研究方向为土壤与地下水修复。E-mail: zhaoleyi1999@163.com
基金资助:
国家重点研发计划项目(2020YFC1806502);徐州市创新引领示范专项项目(KC23382)

Study on the Performance of Carbon Sphere-Supported Nano Zero-Valent Iron Activated Persulfate for Degradation of Enrofloxacin in Water

ZHAO Leyi¹(), ZHU Xueqiang¹^,^*(), LIU Jian¹^,², LU Ping¹

1. School of Environment and Surveying, China University of Mining and Technology, Xuzhou 221116, P. R. China
2. Jiangsu Yunyi Electric Co., Ltd, Xuzhou 221116, P. R. China

Received:2023-12-20 Online:2024-05-18 Published:2024-06-27

摘要/Abstract

摘要：

恩诺沙星（ENR）属于氟喹诺酮类抗生素，具有稳定性强、难分解、易富集等特性，常用于水产养殖、畜禽养殖等，其在环境中总体浓度较低，但长期低剂量暴露可能对人体健康和生态环境带来极大风险。采用碳球（CS）负载纳米零价铁（nZVI）活化过硫酸盐（PS）去除水体中的ENR。应用两步碳热还原法制备了碳球负载纳米零价铁（Fe@C），采用单因素实验研究了Fe@C投加量、PS浓度、ENR初始浓度和pH值对ENR降解的影响及降解动力学，通过自由基及降解产物分析推测了Fe@C活化PS降解ENR的反应机制与降解路径。结果表明，ENR的降解符合准一级动力学，在温度为25 ℃、Fe@C投加量为0.3 g∙L⁻¹、PS浓度为1 mmol∙L⁻¹、ENR初始质量浓度为10 mg∙L⁻¹、pH值为3的条件下，ENR降解率最高达98.6%。ENR降解率随着腐植酸（HA）、氨氮（NH₃-N）、碳酸氢根离子（HCO₃⁻）浓度的升高而降低。氯离子（Cl⁻）在低浓度时对ENR的降解有微弱的促进作用，高浓度时有抑制作用。自由基淬灭实验表明SO₄⁻∙是ENR降解的主要自由基。根据ENR的降解产物，推测哌嗪环的裂解、喹诺酮环的分解及脱氟为ENR主要降解途径。碳球负载纳米零价铁活化PS高级氧化工艺可作为一种高效去除水中ENR的工艺。

关键词: 恩诺沙星, 碳球负载纳米零价铁, 过硫酸盐, 降解途径, 活化, 降解动力学

Abstract:

Enrofloxacin (ENR) belongs to the fluoroquinolone class of antibiotics, characterized by strong stability, difficult degradation, and easy accumulation. It is commonly used in aquaculture and livestock farming. Although its overall concentration in the environment is low, long-term exposure to low doses may pose significant risks to human health and the ecological environment. The removal of ENR from water is achieved by utilizing carbon spheres (CS) loaded with nano zero-valent iron (nZVI) to activate persulfate (PS). Carbon spheres loaded with nano zero-valent iron (Fe@C) were prepared using a two-step carbon thermal reduction method. Single-factor experiments were conducted to investigate the effects of Fe@C dosage, PS concentration, initial ENR concentration and pH on ENR degradation. The reaction mechanism and degradation pathway of ENR by Fe@C activated PS were speculated through the analysis of free radicals and degradation products. The results indicated that the degradation of ENR followed a pseudo-first-order kinetics. Under the conditions of 25 ℃, Fe@C dosage of 0.3 g∙L⁻¹, PS concentration of 1 mmol∙L⁻¹, initial ENR mass concentration of 10 mg∙L⁻¹, and pH of 3, the highest ENR degradation rate reached 98.6%. The degradation rate of ENR decreased with increasing concentrations of humic acid (HA), ammonia nitrogen (NH₃-N), and bicarbonate ions (HCO₃⁻). The chloride ions (Cl⁻) had a slight promoting effect on the degradation of ENR at low concentrations and an inhibitory effect at high concentrations. Free radical quenching experiments indicated that SO₄⁻∙ was the main free radical involved in ENR degradation. Based on the degradation products of ENR, it was speculated that the cleavage of the piperazine ring, decomposition of the quinolone ring, and defluorination were the main degradation pathways of ENR. The Fe@C activated persulfate advanced oxidation process can serve as an efficient technology for removing ENR from water.

Key words: enrofloxacin (ENR), carbon sphere-supported nano zero-valent iron, persulfate, degradation pathways, activation, degradation kinetics

中图分类号:

赵乐依, 朱雪强, 刘健, 路平. 碳球负载纳米零价铁活化过硫酸盐降解水中恩诺沙星的性能研究[J]. 生态环境学报, 2024, 33(5): 757-770.

ZHAO Leyi, ZHU Xueqiang, LIU Jian, LU Ping. Study on the Performance of Carbon Sphere-Supported Nano Zero-Valent Iron Activated Persulfate for Degradation of Enrofloxacin in Water[J]. Ecology and Environment, 2024, 33(5): 757-770.

图/表 18

图1 Fe@C的SEM谱图和EDS谱图

Figure 1 SEM image and EDS image of Fe@C

图2 Fe@C的N2吸附-解吸曲线及对应的孔径分布

Figure 2 N2 adsorption-desorption curve and desorption pore size distribution of Fe@C

图3 不同体系中ENR的降解效率

Figure 3 Degradation efficiency of ENR in different systems

图4 不同铁碳比对ENR降解效果的影响实验条件：[ENR]=10 mg?L?1，[PS]=0.5 mmol?L?1，[Fe@C]=0.2 g?L?1，θ=25 ℃，pH未调节

Figure 4 Effect of Fe@C with different CS ratio on the degradation of ENR

图5 Fe@C投加量对 ENR降解效果的影响实验条件：[ENR]=10 mg?L?1，[PS]=0.5 mmol?L?1，[Fe@C-5]=0.1、0.2、0.3、0.4和0.5 g?L?1，θ=25 ℃，pH未调节

Figure 5 Effect of Fe@C dosages on the degradation of ENR

图6 PS浓度对ENR降解效果的影响实验条件：[ENR]=10 mg?L?1；[PS]=0.2－5 mmol?L?1；[Fe@C]=0.3 g?L?1；θ=25 ℃；pH未调节

Figure 6 Effect of PS concentrations on the degradation of ENR

图7 ENR初始质量浓度对ENR降解效果的影响实验条件：[ENR]=10－50 mg?L?1，[PS]=1 mmol?L?1，[Fe@C]=0.3 g?L?1，θ=25 ℃，pH未调节

Figure 7 The impact of initial ENR mass concentration on the degradation effect of ENR

图8 pH值对ENR降解效果的影响实验条件：[ENR]=10 mg?L?1，[PS]=1 mmol?L?1，[Fe@C]=0.3 g?L?1，θ=25 ℃

Figure 8 Effect of pH value on the degradation of ENR

图9 吸附和氧化对ENR降解效果的影响实验条件：[ENR]=10 mg?L?1，[PS]=1 mmol?L?1，[Fe@C]=0.3 g?L?1，θ=25 ℃，pH=3

Figure 9 Effect of adsorption and oxidation on the degradation of ENR

图10 不同质量浓度腐植酸对ENR降解效果的影响实验条件：[ENR]=10 mg?L?1，[PS]=1 mmol?L?1，[Fe@C]=0.3 g?L?1，θ=25 ℃，pH=3

Figure 10 Effect of different mass concentrations of HA on the degradation of ENR

图11 不同质量浓度NH3-N对ENR降解效果的影响实验条件：[ENR]=10 mg?L?1，[PS]=1 mmol?L?1，[Fe@C]=0.3 g?L?1，θ=25 ℃，pH=3

Figure 11 Effect of different mass concentrations of NH3-N on the degradation of ENR

图12 不同无机阴离子对ENR降解效果的影响实验条件：[ENR]=10 mg?L?1，[PS]=1 mmol?L?1，[Fe@C]=0.3 g?L?1，θ=25 ℃，pH=3

Figure 12 Effect of different inorganic anions on the degradation of ENR

图13 pH=7各淬灭剂对ENR降解效果的影响

Figure 13 Effect of each quencher on the degradation of ENR at pH=7

图14 EPR检测谱图

Figure 14 EPR detection spectrum

图15 反应前(a)后(b)Fe@C的XRD衍射谱图

Figure 15 XRD diffraction spectra of Fe@C before (a) and after (b) the reaction

图16 ENR降解产物质谱图

Figure 16 Mass spectrum of ENR degradation products

表1 ENR降解产物

Table 1 Products of ENR degradation

名称	化学式	LCMS质荷比	m/z	保留时间/min
1	C₁₉H₂₃FN₃O₄	376.16562	376.16	8.06
2	C₁₉H₂₁FN₃O₄	374.00037	374.15	9.07
3	C₁₇H₁₉FN₃O₄	348.12372	348.14	9.18
4	C₁₇H₁₉FN₃O₃	331.99915	332.14	4.71
5	C₁₃H₁₂FN₂O₃	263.00095	263.08	5.98
6	C₁₉H₂₃FN₃O₄	376.16696	376.17	10.14
7	C₁₉H₂₅FN₃O₄	378.18158	378.18	10.42
8	C₁₇H₂₅FN₃O₃	338.18842	338.18	11.70
9	C₁₇H₁₈N₃O₄	328.12994	328.13	3.25
10	C₁₄H₁₀N₂O₅	286.05911	286.06	8.33
11	C₁₃H₁₁N₂O₄	258.82837	259.07	9.72

图17 ENR可能的降解途径

Figure 17 The possible pathway of ENR degradation

参考文献 39

[1]	AZHAR M R, ABID H R, SUN H Q, et al., 2016. Excellent performance of copper based metal organic framework in adsorptive removal of toxic sulfonamide antibiotics from wastewater[J]. Journal of Colloid and Interface Science, 478: 344-352. DOI PMID
[2]	CERQUEIRA F, MATAMOROS V, BAYONA J, et al., 2019. Distribution of antibiotic resistance genes in soils and crops. A field study in legume plants (Vicia faba L.) grown under different watering regimes[J]. Environmental Research, 170: 16-25.
[3]	CHEN L W, ZUO X, YANG S J, et al., 2019. Rational design and synthesis of hollow Co₃O₄@Fe₂O₃ core-shell nanostructure for the catalytic degradation of norfloxacin by coupling with peroxymonosulfate[J]. Chemical Engineering Journal, 359: 373-384.
[4]	CHENG D L, NGO H H, GUO W S, et al., 2018a. Anaerobic membrane bioreactors for antibiotic wastewater treatment: Performance and membrane fouling issues[J]. Bioresource Technology, 267: 714-724.
[5]	CHENG D L, NGO H H, GUO W S, et al., 2018b. Bioprocessing for elimination antibiotics and hormones from swine wastewater[J]. Science of the Total Environment, 621: 1664-1682.
[6]	DANNER M C, ROBERTSON A, BEHRENDS V, et al., 2019. Antibiotic pollution in surface fresh waters: Occurrence and effects[J]. Science of the Total Environment, 664: 793-804.
[7]	GUO H G, GAO N Y, YANG Y, et al., 2016. Kinetics and transformation pathways on oxidation of fluoroquinolones with thermally activated persulfate[J]. Chemical Engineering Journal, 292: 82-91.
[8]	GUO W Q, ZHAO Q, DU J S, et al., 2020. Enhanced removal of sulfadiazine by sulfidated ZVI activated persulfate process: Performance, mechanisms and degradation pathways[J]. Chemical Engineering Journal, 388: 124303.
[9]	KOVALAKOVA P, CIZMAS L, MCDONALD T J, et al., 2020. Occurrence and toxicity of antibiotics in the aquatic environment: A review[J]. Chemosphere, 251: 126351.
[10]	LI S, TANG J C, LIU Q L, et al., 2020. A novel stabilized carbon-coated nZVI as heterogeneous persulfate catalyst for enhanced degradation of 4-chlorophenol[J]. Environment International, 138: 105639.
[11]	LI S, TANG J C, YU C, et al., 2022. Efficient degradation of anthracene in soil by carbon-coated nZVI activated persulfate[J]. Journal of Hazardous Materials, 431: 128581.
[12]	MARTINEZ J L, 2009. Environmental pollution by antibiotics and by antibiotic resistance determinants[J]. Environmental Pollution, 157(11): 2893-2902. DOI PMID
[13]	RASHEED A, HOWE J Y, DADMUN M D, et al., 2007. The efficiency of the oxidation of carbon nanofibers with various oxidizing agents[J]. Carbon, 45(5): 1072-1080.
[14]	SUN C J, QU L L, WU L, et al., 2020. Advances in analysis of nitrated polycyclic aromatic hydrocarbons in various matrices[J]. Trac-trends in Analytical Chemistry, 127: 115878.
[15]	SZEKERES E, CHIRIAC C M, BARICZ A, et al., 2018. Investigating antibiotics, antibiotic resistance genes, and microbial contaminants in groundwater in relation to the proximity of urban areas[J]. Environmental Pollution, 236: 734-744. DOI PMID
[16]	WANG J L, ZHUAN R, 2020. Degradation of antibiotics by advanced oxidation processes: An overview[J]. Science of the Total Environment, 701: 135023.
[17]	WANG S Z, WANG J L, 2019. Oxidative removal of carbamazepine by peroxymonosulfate (PMS) combined to ionizing radiation: Degradation, mineralization and biological toxicity[J]. Science of the Total Environment, 658: 1367-1374.
[18]	WANG X Y, DU Y, MA J, 2016. Novel synthesis of carbon spheres supported nanoscale zero-valent iron for removal of metronidazole[J]. Applied Surface Science, 390: 50-59.
[19]	WANG Y F, WANG L F, LIU R M, et al., 2022. Source-specific risk apportionment and critical risk source identification of antibiotic resistance in Fenhe River basin, China[J]. Chemosphere, 287(Part 1): 131997.
[20]	XU J, ZHANG X L, SUN C, et al., 2018. Catalytic degradation of diatrizoate by persulfate activation with peanut shell biochar-supported nano zero-valent iron in aqueous solution[J]. International Journal of Environment Research and Public Health, 15(9): 1937.
[21]	YU F, LI Y, HAN S, et al., 2016. Adsorptive removal of antibiotics from aqueous solution using carbon materials[J]. Chemosphere, 153: 365-385. DOI PMID
[22]	ZHANG J K, CHEN L, ZHANG X Y, 2022. Removal of p-nitrophenol by nano zero valent iron-cobalt and activated persulfate supported onto activated carbon[J]. Water, 14(9): 1387.
[23]	ZHANG R H, CHEN Y D, LI S D, et al., 2022. Remediation and optimisation of petroleum hydrocarbon degradation in contaminated water by persulfate activated with bagasse biochar-supported nanoscale zerovalent iron[J]. Sustainability, 14(15): 9324.
[24]	ZHI S L, SHEN S Z, ZHOU J, et al., 2020. Systematic analysis of occurrence, density and ecological risks of 45 veterinary antibiotics: Focused on family livestock farms in Erhai Lake basin, Yunnan, China[J]. Environmental Pollution, 267(Part 1): 115539.
[25]	ZHOU M D, LI C X, ZHAO L X, et al., 2021. Synergetic effect of nano zero-valent iron and activated carbon on high-level ciprofloxacin removal in hydrolysis-acidogenesis of anaerobic digestion[J]. Science of the Total Environment, 752: 142261.
[26]	ZHOU Y Z, WANG T, ZHI D, et al., 2019. Applications of nanoscale zero-valent iron and its composites to the removal of antibiotics: A review[J]. Journal of Materials Science, 54(19): 12171-12188.
[27]	ZHU T T, SU Z X, LAI W X, et al., 2021. Insights into the fate and removal of antibiotics and antibiotic resistance genes using biological wastewater treatment technology[J]. Science of the Total Environment, 776: 145906.
[28]	ZOU J, MA J, CHEN L W, et al., 2013. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine[J]. Environmental Science & Technology, 47(20): 11685-11691.
[29]	陈涛, 沈梦楠, 蔡航, 等, 2024. 环境中抗生素修复技术研究进展[J]. 化工设计通讯, 50(1): 141-143.
	CHEN T, SHEN M N, CAI H, et al., 2024. Research progress in antibiotic remediation technology in the environment[J]. Chemical Engineering Design Communications, 50(1): 141-143.
[30]	仇思, 李小明, 罗琨, 等, 2022. g-C₃N₄/Ag₃PO₄/CNT对亚甲基蓝和四环素光催化的降解[J]. 环境化学, 41(7): 2414-2424.
	CHOU S, LI X M, LUO K, et al., 2022. Study on the photocatalytic degradation performance of g-C₃N₄/Ag₃PO₄/CNT on methylene blue and tetracycline[J]. Environmental Chemistry, 41(7): 2414-2424.
[31]	杜毅, 2018. 新型碳球负载纳米铁的制备及其去除水中抗生素研究[D]. 昆明: 昆明理工大学.
	DU Y, 2018. Novel synthesis of carbon spheres-supported nanoscale zero-valent iron for removal of metronidazole[D]. Kunming: Kunming University of Science and Technology.
[32]	胡锋平, 龙兰兰, 占鹏, 等, 2023. 过渡金属负载碳基复合材料活化过硫酸盐降解有机废水研究进展[J]. 应用化工, 52(3): 885-891.
	HU F P, LONG L L, ZHAN P, et al., 2023. Research progress of activated persulfate degradation of organic wastewater by transition metal supported carbon matrix composites[J]. Applied Chemical Industry, 52(3): 885-891.
[33]	廖晓数, 朱成煜, 仇玥, 等, 2022. 纳米零价铁基生物炭活化过硫酸盐降解土霉素[J]. 环境工程, 40(8): 118-124, 195.
	LIAO X S, ZHU C Y, QIU Y, et al., 2022. Persulfate activation via nanoscale zero-valent iron based biochar for oxytetracycline degradation[J]. Environmental Engineering, 40(8): 118-124, 195.
[34]	鲁涛涛, 2023. 炭载纳米零价铁的制备及其在污染场地原位修复中的应用研究[D]. 北京: 北京石油化工学院.
	LU T T, 2023. Preparation of carbon-supported nano zero-valent iron and its application in in-situ remediation of contaminated sites[D]. Beijing: Beijing Institute of Petrochemical Technology.
[35]	唐亚鑫, 黄雯, 张建强, 等, 2022. Fe⁰/Fe₃C羊粪生物炭复合材料的制备及其活化过一硫酸盐降解磺胺嘧啶[J]. 环境化学, 41(12): 3991-4005.
	TANG Y X, HUANG W, ZHANG J Q, et al., 2022. Preparation of Fe⁰/ Fe₃C sheep manure biochar composites foractivating peroxymonosulfate to degrade sulfadiazine[J]. Environmental Chemistry, 41(12): 3991-4005.
[36]	杨颖, 郭洪光, 邓钦祖, 等, 2016. Fe²⁺激活过氧单硫酸盐去除水中氨氮分析[J]. 中南大学学报(自然科学版), 47(8): 2900-2906.
	YANG Y, GUO H G, DENG Q Z, et al., 2016. Analysis on removal of ammonia nitrogen using peroxymonosulfate activated by Fe²⁺[J]. Journal of Central South University(Science and Technology), 47(8): 2900-2906.
[37]	殷凯, 2019. Mn(Ⅶ)及基于UV的氧化降解水中新兴微污染物的研究[D]. 长沙: 湖南大学.
	YIN K, 2019. Degradation of emerging micropollutants in water by permanganate and UV-based oxidations[D]. Changsha: Hunan University.
[38]	于江波, 于婧, 刘杰, 等, 2024. 光催化去除水体中的抗生素[J]. 化学进展, 36(1): 95-105. DOI
	YU J B, YU J, LIU J, et al., 2024. Photocatalytic removal of antibiotics from water[J]. Progress in Chemistry, 36(1): 95-105. DOI
[39]	张宏玲, 李森, 张杨, 等, 2016. 过渡金属离子活化过硫酸盐去除土壤中的芘[J]. 环境工程学报, 10(10): 6009-6014.
	ZHANG H L, LI S, ZHANG Y, et al., 2016. Removal of pyrene in contaminated soil by transition metal ions activated persulfate[J]. Chinese Journal of Environmental Engineering, 10(10): 6009-6014.

碳球负载纳米零价铁活化过硫酸盐降解水中恩诺沙星的性能研究

Study on the Performance of Carbon Sphere-Supported Nano Zero-Valent Iron Activated Persulfate for Degradation of Enrofloxacin in Water

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 18

参考文献 39

相关文章 2

编辑推荐

Metrics

本文评价

[1]	丛鑫, 曹平, 王晓博. 生物炭负载纳米铁活化过硫酸盐去除土壤中的五氯联苯[J]. 生态环境学报, 2024, 33(2): 282-290.
[2]	周椿富, 于锐, 王翔, 闯绍闯, 杨洪杏, 谢越. 抗生素对不同土壤中酶活性的影响[J]. 生态环境学报, 2022, 31(11): 2234-2241.