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Article(id=1234106392148234982, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1234106384963400440, 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=1729180800000, receivedDateStr=2024-10-18, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772163492476, onlineDateStr=2026-02-27, pubDate=1750348800000, pubDateStr=2025-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772163492476, onlineIssueDateStr=2026-02-27, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772163492476, creator=13701087609, updateTime=1772163492476, updator=13701087609, issue=Issue{id=1234106384963400440, tenantId=1146029695717560320, journalId=1234093305789726721, year='2025', volume='45', issue='6', pageStart='2961', pageEnd='3552', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1772163490763, creator=13701087609, updateTime=1772163969484, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1234108392948682946, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1234106384963400440, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1234108392948682947, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1234106384963400440, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=3111, endPage=3117, ext={EN=ArticleExt(id=1234106395289768922, articleId=1234106392148234982, tenantId=1146029695717560320, journalId=1234093305789726721, language=EN, title=Removal of glyphosate via direct electron transfer based on PMS by adding NaOH and the corresponding mechanism, columnId=1234106386360103680, journalTitle=China Environmental Science, columnName=Water Pollution Control, runingTitle=null, highlight=null, articleAbstract=

The removal efficiency of glyphosate may be affected due to the quenching process of radicals by in-situ produced inorganic phosphorous. To address the problem, we have developed a novel approach to achieve the direct electron transfer between glyphosate and PMS by adding NaOH to adjust the pH values. The effectiveness and mechanisms of glyphosate degradation in various NaOH concentration were evaluated by several experiments: optimizing the concentrations of reactants, radical trapping tests, and electron paramagnetic resonance (EPR) characterization. Varying pH could change the morphologies of glyphosate and PMS, as a result, accompanied the various glyphosate removal rate. Under alkaline condition, the mechanisms of glyphosate degradation depended on the direct electron transfer process, and insignificant contribution of hydroxyl and sulfate radicals. Thus, it effectively prevented the negative effects on radical oxidation by produced inorganic phosphorous during glyphosate removal processes. As a result, glyphosate (10mg/L) was completely decomposed after five minutes with the addition of 5mmol/L PMS and 6mmol/L NaOH.

, correspAuthors=Ya-song CHEN, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Ying WANG, Chi ZHANG, Jia-qi WANG, Ya-song CHEN, Xiao-qiang AN, Hua-chun LAN), CN=ArticleExt(id=1234106398385164443, articleId=1234106392148234982, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=碱调控过硫酸盐直接电荷转移氧化草甘膦及其机制, columnId=1234106386565624579, journalTitle=中国环境科学, columnName=水污染与控制, runingTitle=null, highlight=null, articleAbstract=

针对高级氧化降解草甘膦过程中原位产生无机磷淬灭自由基而影响去除效率问题，开发出投加NaOH调节pH值实现过硫酸盐直接电荷转移氧化草甘膦的新策略.通过反应物浓度调控、自由基捕获及电子顺磁共振表征等手段，深入考查了NaOH投加量对草甘膦去除的重要贡献及其作用机制.研究结果表明，反应溶液pH值影响草甘膦和PMS的存在形态，进而导致草甘膦的去除率有所差异.碱性条件下，草甘膦的降解遵循直接电荷转移机制，而自由基对草甘膦分解的贡献较小，因此可以有效避免反应过程中原位生成的无机磷对自由基氧化过程的不利影响.在PMS和NaOH浓度分别为5mmo/L和6mmol/L的条件下，反应5min即可实现10mg/L草甘膦的完全分解.

, correspAuthors=陈亚松, authorNote=null, correspAuthorsNote=
* 责任作者，正高级工程师，
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王颖(1989-)，女，吉林长春人，助理研究员，博士，主要从事高级氧化水处理技术研究.发表论文10余篇..

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王颖(1989-)，女，吉林长春人，助理研究员，博士，主要从事高级氧化水处理技术研究.发表论文10余篇..

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王颖(1989-)，女，吉林长春人，助理研究员，博士，主要从事高级氧化水处理技术研究.发表论文10余篇..

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figureFileBig=kUJ6iWJQklJirlIEmNCCVw==, tableContent=null), ArticleFig(id=1234106407868486512, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106392148234982, language=EN, label=Table 1, caption=

The pH values in various NaOH concentration adding

, figureFileSmall=null, figureFileBig=null, tableContent=
NaOH添加量(mmol/L)草甘膦初始pH值(10mg/L)加入NaOH(6mmol/L)后溶液pH值加入NaOH和PMS(5mmol/L)后溶液pH值
04.29--
44.2911.809.29
64.2912.0210.04
104.2912.1411.48
204.2912.3812.18
504.2912.7312.70
), ArticleFig(id=1234106408015287159, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106392148234982, language=CN, label=表1, caption=

NaOH浓度对反应溶液pH值的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
NaOH添加量(mmol/L)草甘膦初始pH值(10mg/L)加入NaOH(6mmol/L)后溶液pH值加入NaOH和PMS(5mmol/L)后溶液pH值
04.29--
44.2911.809.29
64.2912.0210.04
104.2912.1411.48
204.2912.3812.18
504.2912.7312.70
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碱调控过硫酸盐直接电荷转移氧化草甘膦及其机制
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王颖 1 , 张驰 2, 3 , 王佳琪 2, 3 , 陈亚松 2, 3, * , 安晓强 1 , 兰华春 1
中国环境科学 | 水污染与控制 2025,45(6): 3111-3117
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中国环境科学 | 水污染与控制 2025, 45(6): 3111-3117
碱调控过硫酸盐直接电荷转移氧化草甘膦及其机制
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王颖1 , 张驰2, 3, 王佳琪2, 3, 陈亚松2, 3, * , 安晓强1, 兰华春1
作者信息
  • 1.清华大学，水质与水生态研究中心，北京 100084
  • 2.中国长江三峡集团有限公司，长江生态环境工程研究中心，湖北 武汉 430010
  • 3.长江经济带生态环境国家工程研究中心，湖北 武汉 430010

    • 王颖(1989-)，女，吉林长春人，助理研究员，博士，主要从事高级氧化水处理技术研究.发表论文10余篇..

通讯作者:

* 责任作者，正高级工程师，
Removal of glyphosate via direct electron transfer based on PMS by adding NaOH and the corresponding mechanism
Ying WANG1 , Chi ZHANG2, 3, Jia-qi WANG2, 3, Ya-song CHEN2, 3, * , Xiao-qiang AN1, Hua-chun LAN1
Affiliations
  • 1.State Key Joint Laboratory of Environment Simulation and Pollution Control, Tsinghua University, Beijing 100084, China
  • 2.Yangtze River Eco-Environmental Engineering Research Center, China Three Gorges Corporation, Wuhan 430010, China
  • 3.National Engineering Research Center for Eco-environment Protection of Yangtze River Economic Belt, Wuhan 430010, China
出版时间: 2025-06-20
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针对高级氧化降解草甘膦过程中原位产生无机磷淬灭自由基而影响去除效率问题，开发出投加NaOH调节pH值实现过硫酸盐直接电荷转移氧化草甘膦的新策略.通过反应物浓度调控、自由基捕获及电子顺磁共振表征等手段，深入考查了NaOH投加量对草甘膦去除的重要贡献及其作用机制.研究结果表明，反应溶液pH值影响草甘膦和PMS的存在形态，进而导致草甘膦的去除率有所差异.碱性条件下，草甘膦的降解遵循直接电荷转移机制，而自由基对草甘膦分解的贡献较小，因此可以有效避免反应过程中原位生成的无机磷对自由基氧化过程的不利影响.在PMS和NaOH浓度分别为5mmo/L和6mmol/L的条件下，反应5min即可实现10mg/L草甘膦的完全分解.

pH值  /  过一硫酸盐(PMS)  /  草甘膦  /  无机磷  /  电子转移过程

The removal efficiency of glyphosate may be affected due to the quenching process of radicals by in-situ produced inorganic phosphorous. To address the problem, we have developed a novel approach to achieve the direct electron transfer between glyphosate and PMS by adding NaOH to adjust the pH values. The effectiveness and mechanisms of glyphosate degradation in various NaOH concentration were evaluated by several experiments: optimizing the concentrations of reactants, radical trapping tests, and electron paramagnetic resonance (EPR) characterization. Varying pH could change the morphologies of glyphosate and PMS, as a result, accompanied the various glyphosate removal rate. Under alkaline condition, the mechanisms of glyphosate degradation depended on the direct electron transfer process, and insignificant contribution of hydroxyl and sulfate radicals. Thus, it effectively prevented the negative effects on radical oxidation by produced inorganic phosphorous during glyphosate removal processes. As a result, glyphosate (10mg/L) was completely decomposed after five minutes with the addition of 5mmol/L PMS and 6mmol/L NaOH.

pH  /  PMS  /  glyphosate  /  inorganic phosphorous  /  electron transfer process
王颖, 张驰, 王佳琪, 陈亚松, 安晓强, 兰华春. 碱调控过硫酸盐直接电荷转移氧化草甘膦及其机制. 中国环境科学, 2025 , 45 (6) : 3111 -3117 .
Ying WANG, Chi ZHANG, Jia-qi WANG, Ya-song CHEN, Xiao-qiang AN, Hua-chun LAN. Removal of glyphosate via direct electron transfer based on PMS by adding NaOH and the corresponding mechanism[J]. China Environmental Science, 2025 , 45 (6) : 3111 -3117 .
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草甘膦作为除草剂被广泛应用于预防病原体感染和提高作物产量过程中[1]，这使其成为水和土壤中普遍存在的一类污染物.环境中存在的草甘膦对植物、动物和人类具有潜在危害，被国际癌症研究机构归类为可能致癌物[2].工业中生产1t草甘膦农药约产生5~6t母液，母液中含有1%草甘膦、1%~ 4%甲醛、甲醇、氯甲烷、甲缩醛等物质，而经纳滤处理后的母液废水中仍残留高达200~3000mg/L的草甘膦[3].粘土、生物炭、活性炭等吸附剂常用于去除水中的草甘膦，然而溶液中共存有机物对吸附位点的竞争影响了草甘膦的去除率，同时存在吸附饱和再生液二次污染的风险[4].采用生物滤池和活性污泥法处理此类废水时，草甘膦结构中C-N键易被草甘膦氧化还原酶破坏生成毒性更强且难以矿化的氨甲基膦酸，增加了生态环境风险[5].而高级氧化技术因具备反应速度快、处理效率高、矿化性能好等特点在工业废水处理中极具应用前景[6]，但是，基于自由基活性物种的高级氧化技术处理含磷有机废水时，溶液中共存的无机阴离子，如磷酸根、碳酸根、氯等离子可能发生自由基淬灭副反应，导致活性物种减少而降低污染物去除效率[7].
基于过硫酸盐的非自由基氧化过程因其受溶液中共存离子干扰小和高反应选择性的特点，近年来在水处理中备受关注.一般情况下，采用催化剂活化过硫酸盐产生单线态氧或高价金属等活性物质的方式实现目标污染物的间接氧化去除.近来研究发现，在不添加催化剂条件下苯酚、胺、硫醇等富含电子基团的有机污染物与PMS间可发生直接氧化作用，实现从污染物到氧化剂的直接电子转移.需要指出的是，草甘膦排放废水中难处理的甲醇回收液和氯甲烷碱洗废液均呈碱性，该碱性条件下具有活化过硫酸盐产生自由基降解污染物的作用，然而如何调控废水pH值实现非自由基路径下草甘膦的降解，仍是有待探索的科学领域.
本文即模拟草甘膦排放废水的碱性特征，通过添加氢氧化钠调节溶液pH值，构建基于过硫酸盐的非自由基路径降解草甘膦.区别于传统碱作用下过硫酸盐的自由基氧化机制，草甘膦结构中的氨基、羧基和膦酰活性基团有助于草甘膦和PMS间发生直接电子转移，从而避免原位生成无机磷对自由基氧化效率的影响.研究考查了反应条件对草甘膦去除效率的影响，并解析了污染物降解机制，以期为有机磷废水的高效处理提供有效策略.
1　材料与方法
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1.1　材料
草甘膦(GYP，上海麦克林生化科技有限公司);过一硫酸盐(PMS，分子量：307，北京伊诺凯科技有限公司);氢氧化钠(NaOH)、氢氧化钾(KOH)、氢氧化钙(Ca(OH)2)、硫代硫酸钠(Na2S2O3)、乙酸钠、2,2'-联氮-双-3-乙基苯并噻唑啉-6-磺酸(ABTS)、碘化钾(KI)均购置于国药试剂有限公司;甲醇(MeOH)、叔丁醇(TBA)、糠醇(FFA)、乙酸均购置于北京汇海科仪科技有限公司;2,2,6,6-四甲基哌啶氧化物(TEMP)、5,5-二甲基-1-吡咯啉-N-氧化物(DMPO)均购置于北京同仁试剂公司.上述试剂均为分析纯，高纯氩气(Ar2)为普莱克斯公司提供.
1.2　实验过程
通过烧杯实验评价碱性条件下过硫酸盐降解草甘膦性能.首先，取50mL新配制一定浓度的草甘膦溶液于烧杯中，通过添加NaOH进一步调节溶液pH值，加入PMS氧化剂后即开始氧化反应.反应一定时间后，取一定体积反应液混合于等体积硫代硫酸钠溶液中淬灭氧化性物质并结束反应，混合液经0.22µm水系滤膜处理后采用离子色谱测定水中草甘膦和无机磷浓度，并检测碱与过硫酸盐氧化剂加入后草甘膦溶液的pH值，分析其对降解效率的影响.进行自由基捕获实验时，在上述过程基础上向草甘膦溶液中添加一定量MeOH、TBA或FFA，分别作为羟基和硫酸根自由基及单线态氧淬灭剂.通过惰性氩气除氧判断超氧自由基的作用，进而确定草甘膦降解过程中的活性物种类型.
1.3　分析方法
1.3.1　草甘膦和无机磷浓度测定
使用离子色谱仪检测水中草甘膦和无机磷浓度(Dionex Integrion HPIC 5000，赛默飞世尔科技公司).采用AS19和AG19型号色谱柱，35mmol/L的KOH为淋洗液，以流速1mL/min等度洗脱，通过比较草甘膦剩余含量与初始含量推算其去除率.
1.3.2　PMS浓度测定
采用ABTS显色法测定PMS浓度.ABTS显色剂配制如下：取10g乙酸钠溶于23mL的乙酸溶液中，保持乙酸缓冲溶液的pH值在4附近，称取0.274g ABTS溶解到缓冲溶液中，并添加一定量的KI溶液混合搅拌至溶液呈透明，用去离子水定容为250mL后存于4℃冰箱备用.
测定PMS浓度时，取50µL样品置于ABTS(2mL)和去离子水(0.5mL)的混合液中，摇匀后暗处静止放置30min，采用分光光度计测量λ = 425nm处的吸光度.当PMS浓度高于4mmol/L时，对样品稀释进行浓度检测.
1.3.3　电子顺磁共振测试
采用电子顺磁共振波谱仪(EPR，JES-FA 200，日本电子)对碱/PMS体系中的活性物种进行检测，以DMPO和TEMP为自旋捕获剂判断羟基和硫酸根自由基及单线态氧的作用.仪器参数设置如下：频率为8960.521MHz，功率为2mW，扫描时间为1min，中心位置319.221mT，扫描宽度±7.5mT.
1.3.4　电化学测试
通过开路电压实验验证草甘膦和过硫酸盐之间的电子转移过程.实验采用三电极体系，阳极为圆形玻碳电极，阴极为铂片，参比电极为AgCl/Ag电极，电解液为50mmol/L硫酸钠.
2　结果与讨论
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2.1　碱调控过硫酸盐降解草甘膦性能
由于10mg/L的草甘膦溶液pH值仅为4.29左右，通过投加NaOH方式研究了不同pH值下5mmol/L过硫酸盐降解草甘膦的性能.如图1所示，保持草甘膦和PMS浓度不变，NaOH投加量从0mmol/L增加到6mmol/L时，草甘膦的去除率逐渐升高，继续增加NaOH添加量则导致草甘膦去除率的逐渐下降，最优条件下反应5min即可实现草甘膦完全分解.这表明碱可以有效调控过硫酸盐降解草甘膦，草甘膦去除率随NaOH浓度升高呈现先增加后减小的原因可能如下：一是产生的反应性物质参与了竞争导致的[8]，二是受不同pH值下污染物和氧化剂存在形态性质的影响[9].
2.2　草甘膦降解机制
2.2.1　原位生成无机磷对降解效率的影响
为了揭示PMS氧化草甘膦过程中原位生成无机磷的作用，以氢氧化钙(等浓度氢氧根)替换氢氧化钠加入到草甘膦溶液中，使钙离子与草甘膦分解产生的无机磷原位形成微溶于水的磷酸钙沉淀.由图2可以看到，钙离子的加入未影响草甘膦的去除效率，表明草甘膦的分解不受无机磷生成的影响，活性自由基在本反应体系中可能未发挥主导作用.考虑到在草甘膦初始浓度为10mg/L，反应100min后无机磷的生成量相对较小(图2(b)，约为0.65mg/L)，进一步提升草甘膦的初始浓度到50, 100和200mg/L开展草甘膦氧化降解实验.如图3所示，随着草甘膦初始浓度提升到200mg/L，反应30min后其去除率从100%降低到72%左右.钙离子的加入仍未对草甘膦的分解过程造成显著影响，而此时体系中产生的无机磷含量已达22.4mg/L，说明反应生成无机磷对草甘膦/NaOH/PMS体系未产生抑制作用，而草甘膦的分解可能基于非自由基的氧化机制.
2.2.2　反应活性物质的鉴定
分别以甲醇、叔丁醇和糠醇作为羟基自由基、硫酸根自由基及单线态氧淬灭剂，解析草甘膦/NaOH/PMS体系中存在的活性物种.如图4(a)所示，当NaOH和PMS浓度分别为6,5mmol/L时，甲醇和叔丁醇的添加未对草甘膦的去除过程产生影响，表明自由基不是PMS氧化草甘膦的主要因素.体系中通入氮气排除溶解氧的情况下，草甘膦去除过程仍未发生明显变化，表明超氧自由基也不是导致草甘膦降解的主要活性物种.关于碱活化过硫酸盐的报道中，以过一硫酸盐或过二硫酸盐为氧化剂降解有机物过程中，超氧自由基发挥不可或缺的作用[10-11].而本研究中未检测到常见活性自由基，表明草甘膦/NaOH/PMS体系不是传统的自由基氧化机制，这可能与草甘膦结构有关.FFA的添加使草甘膦去除率下降到30%以下，说明可能存在单线态氧的非自由基氧化机制.值得注意的是，草甘膦去除率降低也可能是FFA消耗PMS氧化剂导致的[12]，因此，增加FFA添加量到氧化剂的100倍，其完全抑制了草甘膦的分解，说明FFA作为捕获剂验证单线态氧的方法有待研究.通过EPR对反应体系中的活性物种类型加以进一步鉴定，如图4(b)所示，DMPO捕获剂添加时未检出羟基自由基和硫酸根自由基信号峰，证实了非自由基反应路径.而检测到的TEMPO信号峰归属于1O2加成产物，也可能是PMS自分解或直接氧化TEMP导致的(图4(b)插图)[13].因此，草甘膦的分解归因于PMS的非自由基主导的高级氧化过程.
2.2.3　PMS与草甘膦间电子转移过程
自由基捕获实验和EPR实验结果表明草甘膦/PMS体系中没有常见的自由基，猜测草甘膦和PMS之间发生了直接的电子转移，进一步通过开路电压实验进行验证，结果如图5(a)所示.首先，在电解质溶液中加入PMS溶液，电压稳定后加入草甘膦.从图5(a)可以看到，草甘膦加入后电压减小，说明PMS和草甘膦之间发生了电子转移[14].表1展示了向10mg/L草甘膦溶液中加入碱和氧化剂后溶液pH值的变化.草甘膦因其结构中含有膦酰基、羧基和氨基基团使其初始pH值为4.29，添加NaOH后草甘膦溶液的pH值在11~13范围内，加入5mmol/L的PMS氧化剂后溶液的pH值降低，其数值影响草甘膦与PMS在溶液中的存在形态.
根据pKa值(2.2，5.6和10.2)[15]绘制出草甘膦在pH值为0~14范围内的存在形态分布，如图5(b)所示，草甘膦结构中-NH-在酸性条件下发生质子化，以COOH-CH2-NH2+-CH2-PO(OH)2(α1)的形态存在.10mg/L草甘膦溶液中加入5mmol/L酸性PMS后溶液的pH值小于4.29，此时草甘膦和PMS主要以COOH-CH2-NH2+-CH2-PO(OH)O-(α2，>70%)和HSO5-形式存在，草甘膦的浓度几乎不发生变化，说明两者之间不发生反应.随着溶液pH值的增加，羧基、膦酰基和氨基逐步发生去质子化作用[16]，NaOH添加量为6mmol/L时，加入PMS后溶液pH值为10.04，此时草甘膦和PMS分别以COO--CH2-NH2+-CH2-PO(O-)2(α3，>50%)、COO--CH2-NH-CH2-PO(O-)2(α4，<50%)和HSO5-(β1，<50%)及SO52-(β2，>50%)形式存在，两者之间相互作用导致草甘膦反应5min后得以完全去除.根据草甘膦各形态组分占比，绘制了草甘膦和PMS之间物种-物种随pH值变化曲线(图5(c)).当pH值为10.04时，草甘膦和PMS主要发生k1α3β1、k2α3β2、k3α4β1和k4α4β2 4个反应过程，其贡献与系数k有关.NaOH添加量在0~50mmol/L范围内变化时，反应溶液的pH值逐渐升高，草甘膦去除率呈现先升高后降低的趋势，说明k大小顺序可能为(k2、k3)>k1>k4.总的来说，草甘膦分解过程中反应溶液的pH值决定污染物和氧化剂的存在形态，进而影响草甘膦的去除效率.因此，相对于单线态氧的作用，草甘膦和PMS之间发生电子转移更好的诠释了NaOH添加量对草甘膦去除效率的影响.
需要指出的是，图3中向200mg/L草甘膦溶液加入6mmol/L NaOH和5mmol/L PMS后，溶液的pH值逐渐降低到4，小于50和100mg/L草甘膦初始浓度下溶液pH值的变化.根据草甘膦去除率和反应溶液pH值的关系，推断草甘膦浓度升高其去除率降低的原因是由pH减小所导致，而不是氧化剂浓度变化的原因(200mg/L草甘膦在反应30min后PMS有剩余).
2.3　PMS浓度对降解效率的影响
由于溶液pH值对草甘膦降解过程极其重要，考查了酸性PMS的添加对溶液pH值和草甘膦降解效率的影响，图6表示草甘膦和NaOH浓度分别为10mg/L和6mmol/L时，添加2~15mmol/L的PMS对草甘膦去除效率的影响.结果表明，草甘膦的去除率随PMS浓度增加呈现先增加后减少的趋势，与NaOH浓度对草甘膦去除的影响趋势一致.根据表1,10mg/L草甘膦加入6mmol/L NaOH后溶液的pH值从4.29升高到12.02，加入5mmol/L酸性PMS后pH值降低到10.04.由此可知，加入PMS浓度越小反应溶液的pH值越高，加入PMS浓度小于5mmol/L时反应溶液的pH值均高于10.02，但PMS浓度过小或pH值过高均不利于草甘膦的分解.当PMS添加量高于5mmol/L时，反应溶液的pH值小于10.02，接近于低浓度NaOH的影响.当反应溶液pH值在7.00~10.02的范围时，k2α3β2和k3α4β1的作用高于k1α3β1，而加入15mmol/L的PMS后溶液的pH值呈酸性，草甘膦的去除率相对较低.因此，碱调控PMS氧化草甘膦过程中，草甘膦、NaOH和PMS的浓度均会决定溶液的pH值最终影响污染物降解效率.当PMS添加量为5-8mmol/L时，草甘膦的去除效率最佳，但考虑到氧化剂成本，选择5mmol/L PMS为最优浓度.综合以上分析，草甘膦和PMS间的电子转移依赖于反应溶液的pH值，由于初始草甘膦pH值呈现酸性，需利用碱性溶液调控反应的pH值.
本文基于草甘膦结构中磷酸基团、氨基和羧基3个可能存在的活性位点，构建了PMS氧化的非自由基电荷转移过程.与自由基氧化路径相比，电荷转移直接发生在草甘膦和PMS氧化剂之间，此过程完全利用了PMS的氧化能力，因此处理效率高.非自由基反应过程对有机物具有特殊的高反应活性，几乎不受共存离子和水基质中天然有机物的影响.PMS诱导的草甘膦降解过程无需外加能源或催化剂，并巧妙利用草甘膦废水排放车间中甲醇回收液和氯甲烷碱洗水洗废液的碱性特征，降低了草甘膦处理成本，为实现以污治污高效低耗的废水处理过程提供新思路[17].
3　结论
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3.1　草甘膦和PMS间通过直接电子转移实现有机膦的高效分解，该非自由基路径避免了原位生成无机磷对自由基的淬灭作用.
3.2　草甘膦、NaOH和PMS的浓度是决定溶液pH值的关键因素.
3.3　反应溶液的pH值影响草甘膦和PMS的存在形态，各形态的氧化还原性质决定了草甘膦的去除率.
基金
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  • 国家自然科学基金青年基金项目(52100096)
  • 中国三峡集团项目(202203015)
文献
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2025年第45卷第6期
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  • 接收时间：2024-10-18
  • 首发时间：2026-02-27
  • 出版时间：2025-06-20
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  • 收稿日期：2024-10-18
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国家自然科学基金青年基金项目(52100096)
中国三峡集团项目(202203015)
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    1.清华大学，水质与水生态研究中心，北京 100084
    2.中国长江三峡集团有限公司，长江生态环境工程研究中心，湖北 武汉 430010
    3.长江经济带生态环境国家工程研究中心，湖北 武汉 430010

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2种不同金属材料的力学参数
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Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
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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