Article(id=1241116652398498523, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1241116641321350143, articleNumber=null, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1724601600000, receivedDateStr=2024-08-26, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773834868764, onlineDateStr=2026-03-18, pubDate=1742400000000, pubDateStr=2025-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773834868764, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773834868764, creator=13701087609, updateTime=1773834868764, updator=13701087609, issue=Issue{id=1241116641321350143, tenantId=1146029695717560320, journalId=1234093305789726721, year='2025', volume='45', issue='3', pageStart='1185', pageEnd='1776', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773834866123, creator=13701087609, updateTime=1773881366030, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241311676130193619, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1241116641321350143, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241311676130193620, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1241116641321350143, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1272, endPage=1279, ext={EN=ArticleExt(id=1241116654827000651, articleId=1241116652398498523, tenantId=1146029695717560320, journalId=1234093305789726721, language=EN, title=Degradation of oxytetracycline by Fe(III) combined with peracetic acid, columnId=1234106386360103680, journalTitle=China Environmental Science, columnName=Water Pollution Control, runingTitle=null, highlight=null, articleAbstract=

In this study, the degradation efficiency and mechanism of oxytetracycline(OTC)in the Fe(Ⅲ)/peracetic acid(PAA)system were investigated, and the effects of initial pH, reagents dosage and water components on OTC degradation were also explored. The results suggested that in the degradation of OTC by Fe(Ⅲ)/PAA system, Fe(Ⅲ)complexed with OTC to form Fe(Ⅲ)-OTC complex, which reduced Fe(Ⅲ)to Fe(II)through internal electron transfer. Subsequently, the generated Fe(II)catalyzed PAA to produce reactive species, thus accelerating the degradation of OTC. The results of chemical probe and radical quenching experiments showed that organic radicals(CH3C(O)O and CH3C(O)OO), HO and Fe(IV)played major roles for the degradation of OTC in Fe(III)/PAA system. Acidic conditions were beneficial to the degradation of OTC in this system, while the removal of OTC under neutral and weakly alkaline conditions was mainly due to the PAA oxidation. The removal efficiency of OTC increased gradually with the increase of PAA or Fe(Ⅲ)dosage, but their excess concentration would inhibit OTC degradation. The presence of Cl- and natural organic matter in Fe(Ⅲ)/PAA systeminhibited the degradation of OTC, while NO3-, SO42- and HCO3- had little effect on OTC removal. The Fe(Ⅲ)/PAA system also ha d a good treatment effect on the other tetracycline pollutants.

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考察了Fe(Ⅲ)/过氧乙酸(PAA)体系对土霉素(OTC)的降解效能与机理,以及初始pH值、药剂投加量、水体基质对OTC降解的影响.结果表明:Fe(Ⅲ)/PAA体系降解OTC过程中,Fe(Ⅲ)与OTC发生络合形成Fe(Ⅲ)-OTC络合物,该络合物通过内部电子转移使Fe(Ⅲ)还原为Fe(Ⅱ),生成的Fe(Ⅱ)催化PAA产生活性物种,从而加快了OTC的降解.化学探针和自由基淬灭实验结果表明,有机自由基(CH3C(O)O和CH3C(O)OO)、HO和Fe(Ⅳ)为该体系的主要活性物种.酸性条件有利于该体系对OTC的降解,在中性及弱碱性条件下,OTC在该体系中的去除主要是由于PAA氧化作用.随着PAA、Fe(Ⅲ)投加量的提高,OTC的去除效率逐渐增加,但是其过量则会抑制OTC降解.水中Cl-和天然有机物的存在会抑制OTC的降解,而NO3-、SO42-和HCO3-对OTC的降解几乎没有影响.Fe(Ⅲ)/PAA体系对其他四环素类污染物也有较好的处理效果.

, correspAuthors=刘义青, authorNote=null, correspAuthorsNote=
* 责任作者,副教授,
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胡虹(1996-),女,四川自贡人,西南交通大学硕士研究生,研究方向为水污染控制..

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Fe(II/III)对四环素类抗生素降解的影响及机制研究 [D]. 北京:北京交通大学,2016., articleTitle=Fe(II/III)对四环素类抗生素降解的影响及机制研究, refAbstract=null), Reference(id=1241116677664985546, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, doi=null, pmid=null, pmcid=null, year=2016, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[31], rfOrder=35, authorNames=Wang H, journalName=Beijing: Beijing Jiaotong University, refType=null, unstructuredReference=Wang H. Effect of Fe(II/III) on the degradation of tetracycline antibiotics and its mechanism [J]. Beijing: Beijing Jiaotong University2016., articleTitle=Effect of Fe(II/III) on the degradation of tetracycline antibiotics and its mechanism, refAbstract=null)], funds=[Fund(id=1241116669666447439, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, awardId=2023YFB2390100, language=CN, fundingSource=国家重点研发计划(2023YFB2390100), fundOrder=null, country=null), Fund(id=1241116669762916443, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, awardId=2682024QZ007, language=CN, fundingSource=西南交通大学新型交叉学科培育基金项目(2682024QZ007), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241116663215608340, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, xref=null, ext=[AuthorCompanyExt(id=1241116663270134301, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, companyId=1241116663215608340, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=School of Environmental Science and Engineering, Southwest Jiaotong University, Chengdu 611756, China), AuthorCompanyExt(id=1241116663295300129, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, companyId=1241116663215608340, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=西南交通大学环境科学与工程学院,四川 成都 611756)])], figs=[ArticleFig(id=1241116667367969639, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=EN, label=Fig.1, caption=Degradation of OTC in different systems, and change of UV-vis spectrum of OTC in Fe(Ⅲ)/PAA system, figureFileSmall=hZTm41D3P5rI79QaytCEMA==, figureFileBig=hPrSbUDUe7Vzgt7V+EeXFQ==, tableContent=null), ArticleFig(id=1241116667493798774, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=CN, label=图1, caption=不同体系下OTC降解及Fe(Ⅲ)/PAA体系中OTC紫外-可见光谱变化

实验条件:[Fe(Ⅲ)]0 = 10µmol/L,[PAA]0 = 0.3mmol/L,[H2O2]0 =0.42mmol/L,[OTC]0 = 40µmol/L,pH0 = 4.0,T = 25℃

, figureFileSmall=hZTm41D3P5rI79QaytCEMA==, figureFileBig=hPrSbUDUe7Vzgt7V+EeXFQ==, tableContent=null), ArticleFig(id=1241116667724485522, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=EN, label=Fig.2, caption=Changes of Fe and PAA concentrations during OTC degradation in Fe(Ⅲ)/PAA system, and effects of different chelating agents on OTC degradation in Fe(Ⅲ)/PAA system, figureFileSmall=2ld2A92nZc7My4rdVm+mlg==, figureFileBig=iWQ7deXAcqHy5Q+pk2i7tQ==, tableContent=null), ArticleFig(id=1241116667997115297, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=CN, label=图2, caption=Fe(Ⅲ)/PAA降解OTC过程中铁和PAA浓度的变化及不同络合剂对Fe(Ⅲ)/PAA降解OTC的影响

实验条件:[Fe(Ⅲ)]0 = 10µmol/L,[PAA]0 = 0.3mmol/L,[OTC]0 = [EDTA]0 = [NTA]0 = 40µmol/L,pH0 = 4.0,T = 25℃

, figureFileSmall=2ld2A92nZc7My4rdVm+mlg==, figureFileBig=iWQ7deXAcqHy5Q+pk2i7tQ==, tableContent=null), ArticleFig(id=1241116668143915952, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=EN, label=Fig.3, caption=Changes of PMSO and PMSO2 concentrations in Fe(Ⅲ)/PAA system, and effects of different scavengers on OTC degradation in Fe(Ⅲ)/PAA system, figureFileSmall=MRvJQtwkNS5RqhriC6Y6mQ==, figureFileBig=WCpV5lwvYGHVNAdCAtFxMg==, tableContent=null), ArticleFig(id=1241116668244579258, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=CN, label=图3, caption=Fe(Ⅲ)/PAA体系中PMSO和PMSO2浓度变化及不同淬灭剂对Fe(Ⅲ)/PAA降解OTC的影响

实验条件:[Fe(Ⅲ)]0 = 10µmol/L,[PAA]0 = 0.3mmol/L,[OTC]0 =[PMSO]0 = 40µmol/L,[MeOH]0 = [TBA]0 = 100mmol/L,NB =1mmol/L,pH0 = 4.0,T = 25℃

, figureFileSmall=MRvJQtwkNS5RqhriC6Y6mQ==, figureFileBig=WCpV5lwvYGHVNAdCAtFxMg==, tableContent=null), ArticleFig(id=1241116668370408388, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=EN, label=Fig.4, caption=Degradation mechanism of OTC in Fe(Ⅲ)/PAA system, figureFileSmall=vmIbGoeU3Gs8osJ6uZt8bg==, figureFileBig=hCN+hFqZLdkkHRtSHP4LBw==, tableContent=null), ArticleFig(id=1241116668504626133, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=CN, label=图4, caption=Fe(Ⅲ)/PAA体系降解OTC的机理, figureFileSmall=vmIbGoeU3Gs8osJ6uZt8bg==, figureFileBig=hCN+hFqZLdkkHRtSHP4LBw==, tableContent=null), ArticleFig(id=1241116668634649568, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=EN, label=Fig.5, caption=Effect of initial pH on OTC degradation in Fe(Ⅲ)/PAA and PAA alone systems, figureFileSmall=zQgawAp8wTdu/r/kpQl5xw==, figureFileBig=5V7HGjp05RXi4ZLIYw+y2A==, tableContent=null), ArticleFig(id=1241116668756284399, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=CN, label=图5, caption=初始pH值对Fe(Ⅲ)/PAA与单独PAA降解OTC的影响

实验条件:[Fe(Ⅲ)]0 = 10µmol/L,[PAA]0 = 0.3mmol/L,[OTC]0 = 40µmol/L,T = 25℃

, figureFileSmall=zQgawAp8wTdu/r/kpQl5xw==, figureFileBig=5V7HGjp05RXi4ZLIYw+y2A==, tableContent=null), ArticleFig(id=1241116668882113532, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=EN, label=Fig.6, caption=Effects of PAA, Fe(Ⅲ)and OTC dosages on OTC degradation in Fe(Ⅲ)/PAA sytem, figureFileSmall=cS/yKvZeFCp0CarxvQariQ==, figureFileBig=WP7fqunpnoxjLYwoFSrQKA==, tableContent=null), ArticleFig(id=1241116668995358726, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=CN, label=图6, caption=不同浓度的PAA, Fe(Ⅲ)和OTC对Fe(Ⅲ)/PAA降解OTC的影响

实验条件:[Fe(Ⅲ)]0 = 10µmol/L(图b除外),[PAA]0 = 0.3mmol/L(图a除外),[OTC]0 = 40µmol/L(图c除外),pH0 = 4.0,T = 25℃

, figureFileSmall=cS/yKvZeFCp0CarxvQariQ==, figureFileBig=WP7fqunpnoxjLYwoFSrQKA==, tableContent=null), ArticleFig(id=1241116669137965074, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=EN, label=Fig.7, caption=Effect of water matrix on OTC degradation in Fe(Ⅲ)/PAA system, figureFileSmall=y+mcqttlVoWQNEx8l/agSw==, figureFileBig=u0cq1DVSYOCY7EdKVwYbJA==, tableContent=null), ArticleFig(id=1241116669255405603, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=CN, label=图7, caption=水体成分对Fe(Ⅲ)/PAA体系降解OTC的影响

实验条件:[Fe(Ⅲ)]0 = 10µmol/L,[PAA]0 = 0.3mmol/L,[OTC]0 = 40µmol/L,pH0 = 4.0,T = 25℃

, figureFileSmall=y+mcqttlVoWQNEx8l/agSw==, figureFileBig=u0cq1DVSYOCY7EdKVwYbJA==, tableContent=null), ArticleFig(id=1241116669381234738, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=EN, label=Fig.8, caption=Degradation of other tetracycline antibiotics by Fe(Ⅲ)/PAA system, figureFileSmall=pTGxWSb7uhwlIOJJZaWIxg==, figureFileBig=agD6F5M9NfdGpAMvWqnJrw==, tableContent=null), ArticleFig(id=1241116669519646786, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652398498523, language=CN, label=图8, caption=Fe(Ⅲ)/PAA体系对其他四环素类抗生素的降解

实验条件:[Fe(Ⅲ)]0 = 10µmol/L,[PAA]0 = 0.3mmol/L,[TC]0 = [OTC]0 =[CTC]0 = 40µmol/L,pH0 = 4.0,T = 25℃

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Fe(Ⅲ)联合过氧乙酸降解水中土霉素
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胡虹 , 潘承欢 , 刘义青 *
中国环境科学 | 水污染与控制 2025,45(3): 1272-1279
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中国环境科学 | 水污染与控制 2025, 45(3): 1272-1279
Fe(Ⅲ)联合过氧乙酸降解水中土霉素
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胡虹 , 潘承欢, 刘义青*
作者信息
  • 西南交通大学环境科学与工程学院,四川 成都 611756
  • 胡虹(1996-),女,四川自贡人,西南交通大学硕士研究生,研究方向为水污染控制..

通讯作者:

* 责任作者,副教授,
Degradation of oxytetracycline by Fe(III) combined with peracetic acid
Hong HU , Cheng-huan PAN, Yi-qing LIU*
Affiliations
  • School of Environmental Science and Engineering, Southwest Jiaotong University, Chengdu 611756, China
出版时间: 2025-03-20
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考察了Fe(Ⅲ)/过氧乙酸(PAA)体系对土霉素(OTC)的降解效能与机理,以及初始pH值、药剂投加量、水体基质对OTC降解的影响.结果表明:Fe(Ⅲ)/PAA体系降解OTC过程中,Fe(Ⅲ)与OTC发生络合形成Fe(Ⅲ)-OTC络合物,该络合物通过内部电子转移使Fe(Ⅲ)还原为Fe(Ⅱ),生成的Fe(Ⅱ)催化PAA产生活性物种,从而加快了OTC的降解.化学探针和自由基淬灭实验结果表明,有机自由基(CH3C(O)O和CH3C(O)OO)、HO和Fe(Ⅳ)为该体系的主要活性物种.酸性条件有利于该体系对OTC的降解,在中性及弱碱性条件下,OTC在该体系中的去除主要是由于PAA氧化作用.随着PAA、Fe(Ⅲ)投加量的提高,OTC的去除效率逐渐增加,但是其过量则会抑制OTC降解.水中Cl-和天然有机物的存在会抑制OTC的降解,而NO3-、SO42-和HCO3-对OTC的降解几乎没有影响.Fe(Ⅲ)/PAA体系对其他四环素类污染物也有较好的处理效果.

土霉素  /  过氧乙酸  /  Fe(Ⅲ)  /  高级氧化

In this study, the degradation efficiency and mechanism of oxytetracycline(OTC)in the Fe(Ⅲ)/peracetic acid(PAA)system were investigated, and the effects of initial pH, reagents dosage and water components on OTC degradation were also explored. The results suggested that in the degradation of OTC by Fe(Ⅲ)/PAA system, Fe(Ⅲ)complexed with OTC to form Fe(Ⅲ)-OTC complex, which reduced Fe(Ⅲ)to Fe(II)through internal electron transfer. Subsequently, the generated Fe(II)catalyzed PAA to produce reactive species, thus accelerating the degradation of OTC. The results of chemical probe and radical quenching experiments showed that organic radicals(CH3C(O)O and CH3C(O)OO), HO and Fe(IV)played major roles for the degradation of OTC in Fe(III)/PAA system. Acidic conditions were beneficial to the degradation of OTC in this system, while the removal of OTC under neutral and weakly alkaline conditions was mainly due to the PAA oxidation. The removal efficiency of OTC increased gradually with the increase of PAA or Fe(Ⅲ)dosage, but their excess concentration would inhibit OTC degradation. The presence of Cl- and natural organic matter in Fe(Ⅲ)/PAA systeminhibited the degradation of OTC, while NO3-, SO42- and HCO3- had little effect on OTC removal. The Fe(Ⅲ)/PAA system also ha d a good treatment effect on the other tetracycline pollutants.

oxytetracycline  /  peracetic acid  /  Fe(Ⅲ)  /  advanced oxidation
胡虹, 潘承欢, 刘义青. Fe(Ⅲ)联合过氧乙酸降解水中土霉素. 中国环境科学, 2025 , 45 (3) : 1272 -1279 .
Hong HU, Cheng-huan PAN, Yi-qing LIU. Degradation of oxytetracycline by Fe(III) combined with peracetic acid[J]. China Environmental Science, 2025 , 45 (3) : 1272 -1279 .
地表水、地下水、饮用水和土壤等环境中频频检测出土霉素(OTC),这是由于传统污水处理厂对抗生素去除效果不理想以及抗生素的过度使用引起的;OTC在水环境中的长期暴露可能会诱发抗药性细菌的出现,从而对人类健康和水生态系统造成不利影响[1-3].目前,高级氧化技术(AOPs)已广泛用于此类污染物的降解研究.相比于其他氧化剂(如过氧化氢、过硫酸盐等),过氧乙酸(PAA)具有较高的氧化还原电位以及较低的过氧键(O-O)键能,其在AOPs中逐渐得到关注和应用[4-6].
通常,PAA能够被紫外光(UV)、热、超声、过渡金属、碳基材料等活化产生高活性物种[7-16].不管是UV、热还是超声活化都需要消耗大量能量,运行成本偏高;碳基材料通常催化效率较低;过渡金属由于其高催化活性且不需消耗能量,成为一类较优的PAA活化剂.其中Co和Fe是PAA活化效率较高的两种过渡金属,但由于Co可能会引发二次污染,故铁基催化剂成为首选.在铁基催化剂中,Fe(II)通常能够有效活化PAA,但Fe(Ⅲ)催化效率较差,可能是由于其较慢的Fe(II)转化效率.为了提高Fe(Ⅲ)活化效率,现有研究发现添加络合剂或还原剂能够提高Fe(Ⅲ)对PAA的活化.例如,通过在Fe(Ⅲ)/PAA体系中加入天然还原剂抗坏血酸(AA)可加速Fe(Ⅲ)/Fe(II)的氧化还原循环,强化Fe(Ⅲ)/PAA工艺对双氯芬酸的降解[17].Kim等[18]利用螯合剂吡啶甲酸(PICA),不仅拓宽Fe(Ⅲ)/PAA体系的初始pH值应用范围,还促进Fe(II)的生成,从而增强随后的PAA活化,提高该体系对微污染物的降解率.Liu等[19]发现向Fe(Ⅲ)/PAA体系中加入柠檬酸(CA)不仅可以增加Fe(Ⅲ)/Fe(II)在中碱性条件下的溶解度,拓宽该体系的反应pH值,还加速Fe(Ⅲ)/Fe(II)循环,显著提高其对污染物的去除率.
基于现有报道,Fe(Ⅲ)/PAA体系不能有效处理有机污染物,但实验发现,该体系能够高效降解OTC,无需辅助Fe(Ⅲ)转化,具体原因未见相关报道.为此,本文在文献阅读分析的基础上,辅以实验证实,分析探讨Fe(Ⅲ)/PAA体系对OTC的降解动力学及反应机理,揭示OTC的去除机制,以期为废水中OTC的去除提供技术支撑.
盐酸土霉素、金霉素、盐酸四环素、腐殖酸、苯甲砜、甲基苯基亚砜均购自上海阿拉丁生化科技股份有限公司.九水合硝酸铁、过氧乙酸、氯化钠、硝酸钾、硫酸钠、碳酸氢钠、五水硫酸铜、硝酸镁、硝酸钙、甲醇、叔丁醇、硝基苯、硫代硫酸钠、乙腈、冰乙酸、氢氧化钠、硫酸、邻菲罗啉盐酸盐一水合物均购自成都市科龙化工试剂厂.
所有实验均在250mL烧杯中进行,在其中分别加入一定浓度的有机污染物和PAA溶液,使用0.5mol/L氢氧化钠和0.5mol/L硫酸调节溶液pH值,再加入0.1mL 10mmol/L Fe(Ⅲ)开启反应,反应溶液总体积为100mL.在实验过程中,用恒温水浴磁力搅拌器将反应温度控制在25℃,转速控制在400r/min,以确保溶液充分混合反应.在0,1,3,5,10和20min时分别取3.5mL样品放入装有0.5mL 0.1mol/L硫代硫酸钠的离心管中,以去除多余的氧化剂.所有实验至少重复两次,取平均值作图.
OTC、金霉素(CTC)、四环素(TC)的浓度采用紫外可见分光光度计(UV-4802,Unico)测定,测试波长分别为354,357和358nm.甲基苯基亚砜(PMSO)与苯甲砜(PMSO2)的浓度选用岛津LC-2030高效液相色谱仪测定,固定相选用Waters BEH C18色谱柱(2.1×50mm,1.7µm),流动相为乙腈和水,体积比为20:80,流速1mL/min,进样体积20µL,柱温40℃,波长分别为230和215nm.采用邻菲罗啉分光光度法测定体系中的总铁和Fe(Ⅱ)浓度,浓度差则为Fe(Ⅲ)浓度.Fe(Ⅲ)/PAA体系中OTC的降解效果采用Ct/C0来表示,CtC0分别表示t时刻和初始时刻对应OTC的物质的量浓度(µmol/L).
图1(a)所示,pH=4.0时,OTC在单独Fe(Ⅲ)体系中基本不发生降解;单独PAA体系20min内也仅氧化15%的OTC;但在PAA中引入Fe(Ⅲ)后,10min内对OTC的去除率达到80%左右,说明Fe(Ⅲ)/PAA体系可能产生了大量活性物种,迅速分解OTC.此外,OTC在Fe(Ⅲ)/PAA体系中紫外可见光谱的变化也证明了这一点,如图1(b)所示,OTC的特征吸收峰(354nm)随反应时间的推移而逐步降低.由于实验所用PAA溶液是H2O2和PAA的混合物,为了辨别H2O2的作用,设置了Fe(Ⅲ)/H2O2对照组.由图1(a)可知,Fe(Ⅲ)/H2O2体系降解OTC的速率很低,前20min内仅有30%左右降解,效率远低于Fe(Ⅲ)/PAA体系,说明H2O2在Fe(Ⅲ)/PAA体系降解OTC的过程中作用较小.如前言所述,PAA比H2O2具有更低的O-O键能,因此相同条件下,前者更易被活化.据此初步判定,Fe(Ⅲ)/PAA体系中导致OTC快速降解的原因主要是PAA的有效活化,而H2O2贡献度较小.
OTC是一种四环素类抗生素,其分子结构包含伯胺、叔胺等官能团,能够与Fe(Ⅲ)配位形成络合物[19-22].因此,在Fe(Ⅲ)/PAA体系中,OTC结构中C2上的酰胺和C3上的羟基官能团(图2(a))可能与Fe(III)结合形成Fe(III)-OTC络合物,结合点位为N和O原子[21].该络合物通过内部电子转移(即OTC作为电子供体,Fe(III)作为电子受体),使Fe(Ⅲ)还原为Fe(Ⅱ)[21-22].为了验证上述推测,本文监测了反应溶液中Fe(Ⅱ)的浓度变化.由图2(b)可知,在Fe(Ⅲ)/PAA体系降解OTC过程中,Fe(Ⅱ)迅速生成,在反应1min后其浓度超过4µmol/L,随后其浓度缓慢上升,到20min Fe(Ⅱ)浓度达到5µmol/L.该结果较好地证明了上述的猜想,即OTC与Fe(Ⅲ)结合形成了Fe(Ⅲ)-OTC络合物,加速了Fe(Ⅲ)还原为Fe(Ⅱ).此外,本文对比了单独PAA和Fe(Ⅲ)/PAA两个体系中PAA浓度的变化.如图2(c)所示,单独PAA体系中,PAA浓度仅轻微波动;而在Fe(Ⅲ)/PAA体系中,其浓度不断下降,20min后基本消耗近零,这主要是由于该体系中生成的Fe(Ⅱ)加速了PAA分解.
为了进一步验证OTC与Fe(Ⅲ)的络合作用,本文在Fe(Ⅲ)/PAA体系中分别投加了另外两种常用的金属络合剂EDTA和NTA,结果如图2(d)所示.EDTA或NTA的投加显著抑制了OTC的降解,这是由于两者会与OTC竞争络合体系中的Fe(Ⅲ),减少Fe(Ⅲ)-OTC络合物的形成[23-24].由此可见,在Fe(Ⅲ)/PAA降解OTC过程中,Fe(Ⅲ)-OTC络合物的形成至关重要,其能加速Fe(Ⅲ)的还原,促进Fe(Ⅱ)的生成和PAA的活化分解.
Fe(Ⅱ)活化PAA可产生多种活性物种,包括HO、CH3C(O)O、CH3C(O)OO、CH3、CH3OO等自由基以及Fe(Ⅳ).其中,CH3和CH3OO的氧化性较低,可忽略不计,故在该体系起作用的活性物种可能有HO、CH3C(O)O、CH3C(O)OO和Fe(Ⅳ).为了鉴定Fe(Ⅳ)的作用,本文通过化学探针实验,即在Fe(Ⅲ)/PAA体系中投加PMSO,因为PMSO能够被高价金属氧化为PMSO2[25].如图3(a)所示,PMSO浓度逐渐下降,而PMSO2浓度逐渐增加,表明该体系中Fe(IV)的生成.为了进一步识别活性自由基,分别在Fe(Ⅲ)/PAA体系中投加了甲醇(MeOH)、叔丁醇(TBA)和硝基苯(NB).TBA和NB是HO的淬灭剂,MeOH不仅可以淬灭HO还可以与有机自由基(RO,CH3C(O)O和CH3C(O)OO)反应[26].如图3(b)所示,NB和TBA轻微抑制OTC的去除,而MeOH则使OTC降解率大幅下降,该结果表明HO和RO均参与了OTC降解反应,但RO是主要活性物种.综上所述,在Fe(Ⅲ)/ PAA体系中,HO、CH3C(O)O、CH3C(O)OO和Fe(Ⅳ)均为反应物种,其中RO和Fe(Ⅳ)对OTC去除的贡献较大.
酸性条件下,Fe(Ⅲ)/PAA体系降解OTC的反应机理见图4所示.首先,Fe(Ⅲ)与OTC通过络合作用形成Fe(Ⅲ)-OTC络合物,其内的OTC通过内部电子转移使Fe(Ⅲ)还原成Fe(Ⅱ),如式(1)和(2)所示.接着,生成的Fe(Ⅱ)活化PAA产生HO、CH3C(O)O、CH3C(O)OO和Fe(Ⅳ)等活性物种,见式(3)~(9)[19].最后,这些活性物种与OTC反应,导致OTC的去除.
图5(a)可知,Fe (Ⅲ)/PAA体系降解OTC过程中,pH值从3.0升至4.0,OTC降解率随之提高,于pH 4.0时达到最佳;继续增高pH值,OTC降解率大幅下降.这可能是由于体系在中性及碱性条件下,Fe(Ⅲ)-OTC络合物较难形成,导致Fe(II)生成量减少,进而阻碍了活性物种的形成和OTC的降解.但研究发现,即使pH值提高至9.0,该体系对OTC的降解率仍能保持50%左右,与pH值在5.0和7.0下的OTC去除率类似.在pH 9.0时,OTC主要以去质子化形态存在,故其更易被氧化分解[26].在该pH值下,OTC有可能能够直接被PAA氧化分解.为此,本文研究了不同pH值条件下PAA对OTC的氧化降解,结果如图5(b)所示,酸性条件下PAA几乎无法氧化分解OTC,但中性及碱性条件下,PAA可以显著氧化降解OTC.综上所述,在Fe(Ⅲ)/PAA体系中,酸性条件下OTC主要是通过产生的Fe(Ⅱ)活化PAA生成的活性物种氧化去除,中性和碱性条件下OTC主要依赖于PAA氧化分解.
PAA作为Fe(Ⅲ)/PAA体系中活性物种的前驱体,其浓度高低直接影响到活性物种的生成量,因此有必要研究PAA浓度对该体系降解OTC的影响.如图6(a)所示,PAA浓度由0.1mmol/L升至0.3mmol/L,OTC的降解率随之提高;但继续升高其浓度时却抑制了OTC的降解.这是由于初始PAA投加量的增加可以导致Fe(Ⅲ)/PAA体系中形成更多的活性物种,从而加速OTC的去除.抑制现象可能是由于过量的PAA与OTC竞争体系中的活性物种导致.类似的现象在之前的研究中也有报道,如Lai等[27]在UV/PAA降解苯并三唑和苯并噻唑的过程中发现了过量PAA的抑制作用.
Fe(Ⅲ)作为络合物的形成基础,以及Fe(II)的重要来源,其浓度的高低十分重要.为此,采用不同Fe(Ⅲ)剂量研究Fe(Ⅲ)/PAA体系对OTC降解的影响.如图6(b)所示,Fe(Ⅲ)浓度从2µmol/L升至10µmol/L,OTC降解率持续升高;继续增加其浓度,反而出现了抑制作用.随着Fe(Ⅲ)浓度的增加,体系中生成的Fe(Ⅱ)浓度也会逐渐提高,但是过量的Fe(Ⅱ)则会与OTC竞争活性物种,故导致Fe(Ⅲ)浓度过高时OTC降解反而受到抑制.因此,在当前反应条件下,Fe(Ⅲ)/PAA体系中Fe(Ⅲ)的最佳浓度为10µmol/L.
图6(c)可知,OTC初始浓度在20~40µmol/L,其去除效率基本相同,约80%的OTC能在20min内降解;继续提高OTC浓度,其降解率有所降低.这主要是因为在该反应条件下,Fe(Ⅲ)浓度固定为10µmol/L,受限于其浓度,生成的Fe(Ⅲ)-OTC络合物有限,故产生的活性物种数量有限,从而OTC降解情况相差不大.该结果表明,Fe(Ⅲ)/PAA体系能够有效去除较宽浓度范围的OTC,适用性较强,易于推广应用.
考察了Fe(Ⅲ)/PAA体系降解OTC过程中,不同浓度Cl-、NO3-、SO42-、HCO3-和腐殖酸(HA)的影响.如图7(a)所示,所有浓度的Cl-均表现出抑制作用,因为Cl-可以消耗体系中的活性物种,见式(10)和(11)[28].由于NO3-和SO42-几乎很难与反应活性物种发生反应,所以它们对OTC的降解没有影响,如图7(b)和7(c)所示.虽然HCO3-能够与OTC竞争体系中的活性自由基(式(12)),但是生成的碳酸根自由基(CO3•-)也能够氧化降解OTC[26,29],故抑制作用和促进作用相互抵消,表现出无影响,见图7(d).HA对Fe(Ⅲ)/PAA降解OTC表现出抑制作用,其浓度越高抑制作用越强,如图7(e)所示.HA分子结构通常由芳环和脂环组成,环上连着多种活性官能团,如羟基、羧基、胺基、醌基等,其可能也会与Fe(Ⅲ)发生络合[30],进而导致Fe(Ⅲ)-OTC络合物和随后活性物种生成量的减少.此外,HA能够与OTC竞争体系中的活性物种,从而进一步抑制了OTC的去除.
选用了另外两种常见的四环素类抗生素(TC和CTC)作为代表,研究其在Fe(Ⅲ)/PAA体系中的去除情况.由图8可知,反应20min后,TC和CTC的去除率分别为84.6%和57.9%,表明在该体系中,Fe(Ⅲ)能够与TC和CTC分别形成络合物[31],该络合物通过内部电子转移使Fe(Ⅲ)还原为Fe(II),生成的Fe(II)活化PAA产生了多种活性物种,进而导致TC和CTC氧化分解.上述结果说明Fe(Ⅲ)/PAA体系适用于去除水环境中的四环素类污染物.
3.1 pH 4.0时,Fe(Ⅲ)/PAA体系能够有效降解OTC,因为Fe(Ⅲ)和OTC之间发生络合形成Fe(Ⅲ)-OTC络合物,其通过内部电子转移促进Fe(Ⅲ)还原为Fe(II),生成的Fe(II)活化PAA产生RO、HO和Fe(Ⅳ)等活性物种,进而导致OTC氧化分解.
3.2 酸性条件下,Fe(Ⅲ)/PAA体系降解OTC效率更高,其主要通过活性物种氧化降解;而中性和碱性条件下,OTC主要依靠PAA的氧化分解.
3.3 在Fe(Ⅲ)/PAA体系中,PAA和Fe(Ⅲ)浓度增大能够提高OTC的降解率,但其过量反而会导致抑制作用;SO42-、NO3-和HCO3-对OTC去除几乎无影响,但Cl-和HA均会抑制OTC的降解.
3.4 Fe(Ⅲ)/PAA体系能够有效降解TC(84.6%)和CTC(57.9%)等其它四环素类抗生素,说明该体系具有一定的应用性和推广性.
  • 国家重点研发计划(2023YFB2390100)
  • 西南交通大学新型交叉学科培育基金项目(2682024QZ007)
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2025年第45卷第3期
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  • 接收时间:2024-08-26
  • 首发时间:2026-03-18
  • 出版时间:2025-03-20
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  • 收稿日期:2024-08-26
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国家重点研发计划(2023YFB2390100)
西南交通大学新型交叉学科培育基金项目(2682024QZ007)
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    西南交通大学环境科学与工程学院,四川 成都 611756

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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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