高级氧化技术降解抗生素及去除耐药性的研究进展

doi:10.16085/j.issn.1000-6613.2020-1993

摘要/Abstract

摘要：

近年来由于抗生素滥用而导致的水污染日益严重，抗生素残留及耐药性已成为当今社会面临的最严峻挑战之一。高级氧化工艺以其快速的反应速率和良好的处理效果，越来越多地被用于治理含抗生素的废水。本文首先阐述了抗生素的污染现状；其后根据起主导作用的自由基种类，分类对比了传统高级氧化和过硫酸盐高级氧化处理抗生素及耐药性的特征，深入分析了过硫酸盐高级氧化的反应机理，重点介绍了热活化、紫外活化、零价铁及其改性活化和电活化等不同活化过硫酸盐的方式，并研究总结了这些技术用于处理抗生素及其耐药性的降解效果和进展；综合分析了目前高级氧化降解抗生素及去除耐药性的环境影响因素和存在的问题；最后对高级氧化的未来发展进行了展望。

关键词: 高级氧化, 自由基, 过硫酸盐, 活化, 抗生素, 耐药性, 废水

Abstract:

In recent years, the water pollution caused by the abuse of antibiotics has become increasingly serious, so antibiotics residue and antibiotic resistance have become one of the most serious challenges today. With fast reaction rate and good treatment effect, advanced oxidation processes are increasingly used to treat wastewater containing antibiotics. This article firstly describes the current status of antibiotic pollution. Moreover, according to the classification of free radicals, the characteristics of antibiotics and antibiotic resistance bytraditional and persulfate advanced oxidation treatments were compared. Later, the basic characteristics and reaction mechanism of persulfate advanced oxidation were analyzed in depth. Meanwhile, the degradation effects and research progress of different activation methods for antibiotics and antibiotic resistance were reviewed and summarized, mainly focusing on thermal, ultraviolet, transition metal, and electrical activation, and the environmental impact factors and existing problems of advanced oxidation degradation of antibiotics and antibiotic resistance removal were comprehensively analyzed. Finally, the future development of advanced oxidation was prospected.

Key words: advanced oxidation, radical, persulfate, activation, antibiotics, antibiotic resistant bacteria, wastewater

中图分类号:

吴文瞳, 张玲玲, 李子富, 王晨希, 余春松, 王庆国. 高级氧化技术降解抗生素及去除耐药性的研究进展[J]. 化工进展, 2021, 40(8): 4551-4561.

WU Wentong, ZHANG Lingling, LI Zifu, WANG Chenxi, YU Chunsong, WANG Qingguo. Research progress of advanced oxidation technology in degradation of antibiotics and removal of antibiotic resistance[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4551-4561.

图/表 6

表1 抗生素、ARB及ARGs在各国水体中的分布

国家	水生系统	抗生素	ARB	ARGs	文献
中国	太湖流域地表水	四环素、土霉素等9种	耐药大肠杆菌	bla_CTX，sulⅠ，tet A，qnr S，aac-1b等39种	［3］
中国	北京市区7条河流	磺胺类和四环素	河流细菌（耐药率0.512～0.971）	sul1，sul2，tetA，tetB，tetE，tetW，tetM，tetZ	［4］
西班牙	河流，污水处理厂	甲氧苄啶、氧氟沙星等11种	—	qnrS，ermB，tetW，blaTEM，bla_NDM，bla_KPC，vanA	［5］
荷兰	62家污水处理厂	—	耐药革兰阳性细菌、大肠杆菌等	ermB，sul1，sul2，tetM，tetM，qnrS，blaCT_XM	［6］
日本	宫崎市城市河流	万古霉素	耐药肠球菌	vanA，vanB，vanC1，vanC2/C3	［7］
印度	医院废水，河流	—	耐药大肠杆菌、肠球菌属、假单胞菌	bla_TEM，bla_CTX-M，bla_SHV，bla_NDM，aadA	［8］
德国，澳大利亚	河流	四环素、氯霉素、磺酰胺等8种	—	Ampc，vanA，tetA，aac（3）-IIa，dfrA1，ermA 等24种	［9］
美国	河流	β-内酰胺类抗生素	耐药革兰阴性菌	—	［10］
法国	河流	四环素、阿莫西林等16种	耐药大肠杆菌	—	［11］

图1 过硫酸盐结构

表2 SO4-·与·OH的化学性质

自由基	半衰期/μs	氧化电位/V	pH适用范围
SO $4 -$ ·	30～40	2.50～3.10	2～10
·OH	10^-3	2.80	2～9

表2 SO4-·与·OH的化学性质

自由基	半衰期/μs	氧化电位/V	pH适用范围
SO $4 -$ ·	30～40	2.50～3.10	2～10
·OH	10^-3	2.80	2～9

图2 过硫酸盐对ARB的灭活

表3 改性Fe0对过硫酸盐的氧化

改性方式	改性材料	抗生素	降解率	主要自由基	文献
纳米改性	纳米Fe⁰	磺胺甲唑	87.6%	·OH（pH>8.5）	［61］
纳米改性	纳米Fe⁰	磺胺嘧啶	93%	—	［62］
双金属体系	Fe⁰/Ag	左氧氟沙星氯霉素	60% 91%	SO $4 -$ ·、·OH、O $2 -$ ·	［63］
双金属体系	纳米Fe⁰/Cu	盐酸四环素	89%	SO $4 -$ ·	［64］
预处理	超声	磺胺嘧啶	95.7%	SO $4 -$ ·	［65］
	预磁化	磺胺嘧啶	49.3%	SO $4 -$ ·、·OH	［66］
	水热	氯霉素	70.89％	—	［67］
材料负载	介孔炭负载纳米Fe⁰	四环素	92.1%	SO $4 -$ ·、·OH	［68］
材料负载	生物炭负载Fe⁰/Ni	诺氟沙星	90%以上	SO $4 -$ ·	［69］
硫化改性	硫化纳米Fe⁰	磺胺嘧啶	100%	—	［70］
硫化改性	硫化纳米Fe⁰/生物炭	环丙沙星	99.01%±0.15%	SO $4 -$ ·、·OH	［71］

表3 改性Fe0对过硫酸盐的氧化

改性方式	改性材料	抗生素	降解率	主要自由基	文献
纳米改性	纳米Fe⁰	磺胺甲唑	87.6%	·OH（pH>8.5）	［61］
纳米改性	纳米Fe⁰	磺胺嘧啶	93%	—	［62］
双金属体系	Fe⁰/Ag	左氧氟沙星氯霉素	60% 91%	SO $4 -$ ·、·OH、O $2 -$ ·	［63］
双金属体系	纳米Fe⁰/Cu	盐酸四环素	89%	SO $4 -$ ·	［64］
预处理	超声	磺胺嘧啶	95.7%	SO $4 -$ ·	［65］
	预磁化	磺胺嘧啶	49.3%	SO $4 -$ ·、·OH	［66］
	水热	氯霉素	70.89％	—	［67］
材料负载	介孔炭负载纳米Fe⁰	四环素	92.1%	SO $4 -$ ·、·OH	［68］
材料负载	生物炭负载Fe⁰/Ni	诺氟沙星	90%以上	SO $4 -$ ·	［69］
硫化改性	硫化纳米Fe⁰	磺胺嘧啶	100%	—	［70］
硫化改性	硫化纳米Fe⁰/生物炭	环丙沙星	99.01%±0.15%	SO $4 -$ ·、·OH	［71］

表4 不同阴离子对降解抗生素废水的影响

不同离子	降解率	参考文献
Cl^-	降解速率下降	［3，88］
Cl^-	0.03mol/L Cl^-使降解速率略有提高，浓度的进一步增加使降解率下降	［89］
Br^-	降解速率下降	［89］
Br^-	无显著影响	［88］
NO $3 -$	降解速率下降	［3］
NO $3 -$	较弱抑制作用	［90］
HCO $3 -$	降解速率下降	［3， 88］
	降解速率上升	［91］
	无显著影响	［92］
SO $4 2 -$	降解速率下降	［3］
SO $4 2 -$	降解率上升	［90］

表4 不同阴离子对降解抗生素废水的影响

不同离子	降解率	参考文献
Cl^-	降解速率下降	［3，88］
Cl^-	0.03mol/L Cl^-使降解速率略有提高，浓度的进一步增加使降解率下降	［89］
Br^-	降解速率下降	［89］
Br^-	无显著影响	［88］
NO $3 -$	降解速率下降	［3］
NO $3 -$	较弱抑制作用	［90］
HCO $3 -$	降解速率下降	［3， 88］
	降解速率上升	［91］
	无显著影响	［92］
SO $4 2 -$	降解速率下降	［3］
SO $4 2 -$	降解率上升	［90］

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