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Article(id=1241116652524335492, 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=1724774400000, receivedDateStr=2024-08-28, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773834868794, onlineDateStr=2026-03-18, pubDate=1742400000000, pubDateStr=2025-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773834868794, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773834868794, creator=13701087609, updateTime=1773834868794, 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=1546, endPage=1555, ext={EN=ArticleExt(id=1241116654017507749, articleId=1241116652524335492, tenantId=1146029695717560320, journalId=1234093305789726721, language=EN, title=Adsorption properties of extracellular organic matters from Microcystis aeruginosa by activated carbon, columnId=1234106388083954308, journalTitle=China Environmental Science, columnName=Environmental Ecology, runingTitle=null, highlight=null, articleAbstract=

This study investigates the adsorption and removal effects of powdered activated carbon on extracellular organic matters（EOM）from Microcystis aeruginosa（M. aeruginosa）at different growth phases and explores the removal efficiencies and adsorption mechanisms of characteristic organic components in EOM. The results indicated that the synergistic removal efficiency of organic components in M. aeruginosa EOM by powdered activated carbon was relatively low, ranging from 18.07%to 34.85%. Significant differences in adsorption efficiency were observed among different substance components, with the order of removal efficiency being microcystins>humic acids>proteins>polysaccharides. Each substance component exhibited varying proportions of easily adsorbable structures at different growth phases, leading to differences in adsorption capacity across phases. Easily adsorbable structures in polysaccharides were primarily released during the logarithmic phase, while those in proteins were predominantly secreted during the stable phase. Easily adsorbable structures in microcystins were predominantly secreted during the stable and decay phases, while the proportion of humic acid structure types showed no significant differences across phases. The adsorption process of activated carbon on M. aeruginosa EOM followed the principle of molecular-scale selective adsorption, primarily targeting low- and medium- molecular-weight substances, while exhibiting extremely poor adsorption performance for high- molecular-weight substances. This is a key factor contributing to the low removal efficiency of activated carbon for algal pollutants. This study provides significant scientific insights for the effective prevention and control of algal pollutants throughout the entire lifecycle of cyanobacterial blooms.

, correspAuthors=Feng SUN, 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=Feng SUN, Lei WU, Shuo YE, Xin DENG, Chao-yang ZHANG, Tong WANG, Hai-bing CONG), CN=ArticleExt(id=1241116656366318248, articleId=1241116652524335492, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=活性炭对铜绿微囊藻胞外有机物的吸附规律, columnId=1234106388268503686, journalTitle=中国环境科学, columnName=环境生态, runingTitle=null, highlight=null, articleAbstract=

重点考察了粉末活性炭对不同生长期铜绿微囊藻溶解性胞外有机物(EOM)的吸附去除效果，探究活性炭对不同时期铜绿微囊藻EOM特征性有机组分的去除率及吸附规律.结果发现，粉末活性炭对铜绿微囊藻EOM的有机组分协同去除率较低，仅为18.07%~34.85%，且对EOM中的不同物质组分呈现藻毒素>腐殖酸>蛋白质>多糖的明显吸附率差异.各物质组分在不同生长时期具有不同的易吸附型结构占比，因此导致不同时期吸附量也存在一定差异性.多糖中易吸附结构主要释放于对数期，蛋白质中易吸附结构多分泌于稳定期，藻毒素中多分泌于稳定期和衰亡期，而腐殖酸在各时期的结构类型占比差异并不显著.活性炭对铜绿微囊藻EOM的吸附过程遵循分子尺度选择吸附原则，以中低分子量物质为主，对高分子量物质吸附性极差，这也是导致活性炭对藻源污染物去除率低下的重要因素.本研究对于蓝藻爆发全周期藻源污染物的有效防控具有重要的科学意义.

, correspAuthors=孙凤, authorNote=null, correspAuthorsNote=
* 责任作者，副教授，
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孙凤(1986-)，女，山东烟台人，副教授，博士，主要从事水污染防治方面研究.发表论文30余篇..

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孙凤(1986-)，女，山东烟台人，副教授，博士，主要从事水污染防治方面研究.发表论文30余篇..

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孙凤(1986-)，女，山东烟台人，副教授，博士，主要从事水污染防治方面研究.发表论文30余篇..

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Advances in the study of microcystion toxin [J]. Acta Ecologica Sinica，2002，22(11):1968-1975., articleTitle=Advances in the study of microcystion toxin, refAbstract=null)], funds=[Fund(id=1241116665581203857, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, awardId=2022YFC3203602, language=CN, fundingSource=国家重点研发计划(2022YFC3203602), fundOrder=null, country=null), Fund(id=1241116665715421600, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, awardId=51708480, language=CN, fundingSource=国家自然科学基金资助项目(51708480), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241116656685085398, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, xref=null, ext=[AuthorCompanyExt(id=1241116656693474007, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, companyId=1241116656685085398, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=College of Environmental Science and Engineering, Yangzhou University, Yangzhou 225127, China), AuthorCompanyExt(id=1241116656706056920, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, companyId=1241116656685085398, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=扬州大学环境科学与工程学院，江苏 扬州 225127)])], figs=[ArticleFig(id=1241116663198838963, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=EN, label=Fig.1, caption=Differences in the content level（a）and release component（b）of M. aeruginosa at different cell growth phases, figureFileSmall=qD4jdfj8v8YkyatcKdiVmw==, figureFileBig=QZ6Xr+JgUl3YuXLokZYtXA==, tableContent=null), ArticleFig(id=1241116663328862401, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=CN, label=图1, caption=不同生长期铜绿微囊藻EOM的含量水平及释放组分差异

ns表示无显著性差异P>0.05，**表示显著性差异P<0.01，***表示显著性差异P<0.001，下同

, figureFileSmall=qD4jdfj8v8YkyatcKdiVmw==, figureFileBig=QZ6Xr+JgUl3YuXLokZYtXA==, tableContent=null), ArticleFig(id=1241116663593103579, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=EN, label=Fig.2, caption=Overall organic content adsorption effects of activated carbon on M. aeruginosa EOM at different cell growth phases, figureFileSmall=TebwefTOa/WZNFay+JhHUA==, figureFileBig=l4I81dqbXKrK2D/Te5sSXw==, tableContent=null), ArticleFig(id=1241116663731515624, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=CN, label=图2, caption=活性炭对不同生长期铜绿微囊藻EOM总有机含量的吸附效果

吸附量及去除率组间差异标注于相应图例处：**表示显著性差异P<0.01，***表示显著性差异P<0.001

, figureFileSmall=TebwefTOa/WZNFay+JhHUA==, figureFileBig=l4I81dqbXKrK2D/Te5sSXw==, tableContent=null), ArticleFig(id=1241116663844761844, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=EN, label=Fig.3, caption=Adsorption effect of powdered activated carbon on polysaccharides in EOM of M. aeruginosa at different growth phases, figureFileSmall=zmt+aJQrMGWk+BPIdbqSrA==, figureFileBig=J74Ntpf+mUY+SnK+HGs7cg==, tableContent=null), ArticleFig(id=1241116664062865668, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=CN, label=图3, caption=粉末活性炭对不同生长期铜绿微囊藻EOM中多糖的吸附效果

吸附量及去除率组间差异标注于相应图例处：ns表示无显著性差异P>0.05，**表示显著性差异P<0.01

, figureFileSmall=zmt+aJQrMGWk+BPIdbqSrA==, figureFileBig=J74Ntpf+mUY+SnK+HGs7cg==, tableContent=null), ArticleFig(id=1241116664184500495, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=EN, label=Fig.4, caption=Adsorption effect of powdered activated carbon on proteins in EOM of M. aeruginosa at different growth phases, figureFileSmall=YsBjF6Ss6rcyCMsmxKd75Q==, figureFileBig=+xM8D3yBthF47KxzXlb29Q==, tableContent=null), ArticleFig(id=1241116664297746711, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=CN, label=图4, caption=粉末活性炭对不同生长期铜绿微囊藻EOM中蛋白质的吸附效果

吸附量及去除率组间差异标注于相应图例处：ns表示无显著性差异P>0.05，**表示显著性差异P<0.01，***表示显著性差异P<0.001，下同

, figureFileSmall=YsBjF6Ss6rcyCMsmxKd75Q==, figureFileBig=+xM8D3yBthF47KxzXlb29Q==, tableContent=null), ArticleFig(id=1241116664398410018, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=EN, label=Fig.5, caption=Adsorption effect of powdered activated carbon on humic acid in EOM of M. aeruginosa at different growth phases, figureFileSmall=S2251VAcFbrunXICCL4Spg==, figureFileBig=JIAqhyycNK57v0EeyrDbdg==, tableContent=null), ArticleFig(id=1241116664524239148, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=CN, label=图5, caption=粉末活性炭对不同生长期铜绿微囊藻EOM中腐殖酸的吸附效果, figureFileSmall=S2251VAcFbrunXICCL4Spg==, figureFileBig=JIAqhyycNK57v0EeyrDbdg==, tableContent=null), ArticleFig(id=1241116664679428406, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=EN, label=Fig.6, caption=Adsorption effect of powdered activated carbon on microcystins in EOM of M. aeruginosa at different growth phases, figureFileSmall=I82GWxRxhckBGFNoEIU9eA==, figureFileBig=cUlCFReCJ03CE5HglhB6sA==, tableContent=null), ArticleFig(id=1241116664838811971, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=CN, label=图6, caption=粉末活性炭对不同生长期铜绿微囊藻EOM中藻毒素的吸附效果, figureFileSmall=I82GWxRxhckBGFNoEIU9eA==, figureFileBig=cUlCFReCJ03CE5HglhB6sA==, tableContent=null), ArticleFig(id=1241116664935280978, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=EN, label=Fig.7, caption=Adsorption effect of powdered activated carbon on fluorescent organic matters in EOM of M. aeruginosa at different growth phases, figureFileSmall=Rdlbr0MiQKcc6OZ0PwvH5g==, figureFileBig=FiArULHxwPlAp0bt1yQTLw==, tableContent=null), ArticleFig(id=1241116665136607591, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=CN, label=图7, caption=粉末活性炭对不同生长期铜绿微囊藻EOM中荧光特征有机物的吸附效果, figureFileSmall=Rdlbr0MiQKcc6OZ0PwvH5g==, figureFileBig=FiArULHxwPlAp0bt1yQTLw==, tableContent=null), ArticleFig(id=1241116665266631026, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=EN, label=Table 1, caption=

Adsorption capacity of powdered activated carbon on overall organic content and each substance component of M. aeruginosa EOM at different growth phases

, figureFileSmall=null, figureFileBig=null, tableContent=
生长周期DOC(mg/g活性炭)多糖(mg/g活性炭)蛋白质(mg/g活性炭)腐殖酸(mg/g活性炭)藻毒素(µg/g活性炭)
对数期20.85±2.229.72±0.6640.75±2.723.27±0.1276.56±1.79
稳定期62.47±3.858.43±0.5695.92±4.804.21±0.0896.42±4.91
衰亡期81.98±4.008.67±0.6541.15±4.806.24±0.06217.24±1.20
), ArticleFig(id=1241116665430208896, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116652524335492, language=CN, label=表1, caption=

粉末活性炭对不同时期铜绿微囊藻EOM中总有机含量及各物质组分的吸附量

, figureFileSmall=null, figureFileBig=null, tableContent=
生长周期DOC(mg/g活性炭)多糖(mg/g活性炭)蛋白质(mg/g活性炭)腐殖酸(mg/g活性炭)藻毒素(µg/g活性炭)
对数期20.85±2.229.72±0.6640.75±2.723.27±0.1276.56±1.79
稳定期62.47±3.858.43±0.5695.92±4.804.21±0.0896.42±4.91
衰亡期81.98±4.008.67±0.6541.15±4.806.24±0.06217.24±1.20
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活性炭对铜绿微囊藻胞外有机物的吸附规律
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孙凤 * , 吴磊 , 叶硕 , 邓鑫 , 张朝阳 , 王彤 , 丛海兵
中国环境科学 | 环境生态 2025,45(3): 1546-1555
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中国环境科学 | 环境生态 2025, 45(3): 1546-1555
活性炭对铜绿微囊藻胞外有机物的吸附规律
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孙凤* , 吴磊, 叶硕, 邓鑫, 张朝阳, 王彤, 丛海兵
作者信息
  • 扬州大学环境科学与工程学院，江苏 扬州 225127

    • 孙凤(1986-)，女，山东烟台人，副教授，博士，主要从事水污染防治方面研究.发表论文30余篇..

通讯作者:

* 责任作者，副教授，
Adsorption properties of extracellular organic matters from Microcystis aeruginosa by activated carbon
Feng SUN* , Lei WU, Shuo YE, Xin DENG, Chao-yang ZHANG, Tong WANG, Hai-bing CONG
Affiliations
  • College of Environmental Science and Engineering, Yangzhou University, Yangzhou 225127, China
出版时间: 2025-03-20
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摘要
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重点考察了粉末活性炭对不同生长期铜绿微囊藻溶解性胞外有机物(EOM)的吸附去除效果，探究活性炭对不同时期铜绿微囊藻EOM特征性有机组分的去除率及吸附规律.结果发现，粉末活性炭对铜绿微囊藻EOM的有机组分协同去除率较低，仅为18.07%~34.85%，且对EOM中的不同物质组分呈现藻毒素>腐殖酸>蛋白质>多糖的明显吸附率差异.各物质组分在不同生长时期具有不同的易吸附型结构占比，因此导致不同时期吸附量也存在一定差异性.多糖中易吸附结构主要释放于对数期，蛋白质中易吸附结构多分泌于稳定期，藻毒素中多分泌于稳定期和衰亡期，而腐殖酸在各时期的结构类型占比差异并不显著.活性炭对铜绿微囊藻EOM的吸附过程遵循分子尺度选择吸附原则，以中低分子量物质为主，对高分子量物质吸附性极差，这也是导致活性炭对藻源污染物去除率低下的重要因素.本研究对于蓝藻爆发全周期藻源污染物的有效防控具有重要的科学意义.

铜绿微囊藻  /  胞外有机物  /  活性炭  /  吸附

This study investigates the adsorption and removal effects of powdered activated carbon on extracellular organic matters（EOM）from Microcystis aeruginosa（M. aeruginosa）at different growth phases and explores the removal efficiencies and adsorption mechanisms of characteristic organic components in EOM. The results indicated that the synergistic removal efficiency of organic components in M. aeruginosa EOM by powdered activated carbon was relatively low, ranging from 18.07%to 34.85%. Significant differences in adsorption efficiency were observed among different substance components, with the order of removal efficiency being microcystins>humic acids>proteins>polysaccharides. Each substance component exhibited varying proportions of easily adsorbable structures at different growth phases, leading to differences in adsorption capacity across phases. Easily adsorbable structures in polysaccharides were primarily released during the logarithmic phase, while those in proteins were predominantly secreted during the stable phase. Easily adsorbable structures in microcystins were predominantly secreted during the stable and decay phases, while the proportion of humic acid structure types showed no significant differences across phases. The adsorption process of activated carbon on M. aeruginosa EOM followed the principle of molecular-scale selective adsorption, primarily targeting low- and medium- molecular-weight substances, while exhibiting extremely poor adsorption performance for high- molecular-weight substances. This is a key factor contributing to the low removal efficiency of activated carbon for algal pollutants. This study provides significant scientific insights for the effective prevention and control of algal pollutants throughout the entire lifecycle of cyanobacterial blooms.

Microcystis aeruginosa  /  extracellular organic matters  /  activated carbon  /  adsorption
孙凤, 吴磊, 叶硕, 邓鑫, 张朝阳, 王彤, 丛海兵. 活性炭对铜绿微囊藻胞外有机物的吸附规律. 中国环境科学, 2025 , 45 (3) : 1546 -1555 .
Feng SUN, Lei WU, Shuo YE, Xin DENG, Chao-yang ZHANG, Tong WANG, Hai-bing CONG. Adsorption properties of extracellular organic matters from Microcystis aeruginosa by activated carbon[J]. China Environmental Science, 2025 , 45 (3) : 1546 -1555 .
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河流、湖泊、水库等水生生态系统极易发生水体富营养化，富营养化的加剧，导致水体缺氧、生态失衡，藻类大量繁殖，不仅严重破坏了水环境的生态平衡，还给饮用水的安全供给带来了巨大的挑战[1].研究表明，铜绿微囊藻在一系列物理、化学和生物等环境因素的共同作用下极易成为水华的优势种[2-4]，并在细胞生长代谢和衰亡裂解的生命周期中，不断地向水中释放大量的溶解性胞外有机物(EOM)[5].其EOM的成分极为繁杂，包含多糖、蛋白质、腐殖酸、脂肪酸、藻毒素及嗅味物质等，这些EOM物质的释放，会进一步加剧藻类水华的危害和水质的污染[6].研究发现，EOM易与水中微小无机物结合，形成扩大的有机胶体，不仅会增加水处理中混凝剂的用量，还会导致混凝絮体结构松散，从而降低混凝除藻效率，影响水处理运行效果[7-8].此外，传统水处理工艺在去除EOM中的大部分小分子和亲水性有机物时均存在效率瓶颈，难以实现有效去除[9].而大多强化处理工艺又可能在处理过程中改变藻细胞形态或EOM的组成，产生更多有害有机形式，例如，臭氧或高锰酸钾预氧化技术可能会触发铜绿微囊藻胞内有机物的释放，产生额外的其他有机结构，并在氯化消毒过程中促进新型消毒副产物，如卤代甲烷和三卤硝基甲烷等的形成[10].
相较之下，粉末活性炭因其高孔隙率和巨大的比表面积，能有效去除小分子量物质、疏水性和亲水性有机质以及可溶性微生物等，进而能够显著降低消毒副产物前体物的含量，从而改善水质[11-13].在我国，当净水厂面临铜绿微囊藻爆发引起的水体污染时，粉末活性炭通常会被迅速启用作为应急处理措施，以进行快速吸附，减轻水体中藻类及相关污染物的浓度[14].然而，EOM结构复杂、组分多样，活性炭对铜绿微囊藻产生的各类有机组分是否均具有显著的吸附去除效果；其在吸附过程中是可实现全部有机组分共同发生吸附反应的协同吸附，还是特定组分优先去除或不同程度去除的非同步吸附；活性炭对不同藻类爆发期产生的EOM是否具有一致的吸附规律；其能否在铜绿微囊藻爆发全周期作为去除藻源污染物的关键技术持续地确保供水安全；目前均尚未可知.研究指出，粉末活性炭对于高分子量有机物可能无法有效吸附[15-16].还有研究发现，粉末活性炭对亲水性有机物的吸附去除率也较低[17].因此，鉴于粉末活性炭对铜绿微囊藻EOM的针对性吸附效果及其吸附规律尚不明确，本研究针对不同时期铜绿微囊藻EOM的具体结构组分开展粉末活性炭吸附性能分析，旨在综合揭示铜绿微囊藻EOM的针对性吸附规律.
1　材料与方法
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1.1　铜绿微囊藻EOM的提取
实验采用的铜绿微囊藻(FACHB-912)购自中国科学院淡水藻种库，是蓝藻水华爆发时期常见的淡水优势藻种.在光照培养箱中用BG-11培养基进行培养，培养温度为25℃，光照条件为1000~2000lx，光暗周期为12h：12h，培养期间每天摇动锥形瓶2~3次，以维持藻液气体交换，避免缺氧[18]，并防止铜绿微囊藻细胞凝结成团.
从细胞培养初期开始，每2d取培养的铜绿微囊藻进行细胞密度测定，使用血球计数板(25×16型)在光学显微镜(Nikon E100，中国)下计数每单位体积的铜绿微囊藻细胞个数.每个时间测点的藻样计数3次，并以3次平均值绘制藻细胞生长曲线.细胞密度以cells/mL计.
铜绿微囊藻EOM提取过程如下：用超高速离心机(CR21GIII型，Beckman Coulter，美国)将不同生长阶段的铜绿微囊藻培养液在2500g离心15min.离心后的上清液用0.45µm的混合纤维滤膜进行抽滤，得到实验分析用铜绿微囊藻EOM.
1.2　吸附剂
本实验所用粉末活性炭购于国药集团化学试剂有限公司，性状为黑色粉末，pH值(50g/L，25℃)为5.0~7.0.
1.3　吸附实验方法
本实验先进行粉末活性炭剂量梯度实验，在确定最优剂量后进行吸附时间梯度实验，活性炭剂量梯度包括0，10，25，50，100，150，200，250，300mg/L；吸附时间梯度包括0，0.1，0.25，0.5，1，2，4，8h.其中，0mg/L作为粉末活性炭剂量梯度实验的对照组，0h(活性炭投加前)作为吸附时间梯度实验的对照组，每次实验设置3个平行.
每次实验前用0.20mol/L的KH2PO4和0.20mol/L的Na2HPO4储备液调节铜绿微囊藻EOM溶液的初始pH值为7.0.将相应剂量的粉末活性炭与铜绿微囊藻EOM置于300mL的锥形瓶中进行吸附实验.吸附过程维持于恒温振荡培养箱中，温度为30℃，振荡速度为200r/min，粉末活性炭剂量梯度的吸附实验于吸附2h后取样，吸附时间梯度实验于不同吸附时间点取样.所取水样用0.45µm的混合纤维滤膜过滤，滤液用于后续吸附效能指标测定分析.通过单因素方差分析对比不同时期铜绿微囊藻EOM的活性炭吸附量及去除率，并通过Tukey检验确定其组间差异的显著性.
1.4　铜绿微囊藻EOM吸附效能表征
1.4.1　DOC测定
采用DOC评估铜绿微囊藻EOM的总有机含量变化，并计算粉末活性炭吸附去除率.DOC通过总有机碳分析仪(型号TOC4200，日本岛津)测定.
1.4.2　多糖测定
采用苯酚-硫酸法测定样品中多糖含量.分别取2mL不同浓度梯度葡萄糖标准溶液与待测样品于不同试管中，分别加入6%苯酚溶液1mL和浓硫酸5mL，充分振荡，水浴加热15min，取出在室温冷却25min后，用UV759S型紫外-可见分光光度计于490nm波长测吸光度.以多糖浓度为横坐标、吸光度为纵坐标绘制标准曲线并通过标准曲线回归方程计算样品多糖含量.
1.4.3　蛋白质测定
采用考马斯亮蓝法来测定样品中的蛋白质含量.分别取1mL不同浓度梯度牛血清蛋白(BSA)标准溶液与待测样品于不同试管中，再加入4mL考马斯亮蓝G-250染料试剂，充分振荡2~5min，用UV759S型紫外-可见分光光度计于595nm波长测定吸光度.以蛋白质溶液浓度为横坐标、吸光度为纵坐标绘制标准曲线并通过标准曲线回归方程计算样品蛋白质浓度.
1.4.4　腐殖酸测定
采用紫外分光光度法测定样品中腐殖酸含量.将5mL不同浓度梯度腐殖酸标准溶液与待测样品充分振荡后用UV759S型紫外-可见分光光度计于265nm波长测定其吸光度.以腐殖酸浓度为横坐标、吸光度为纵坐标绘制标准曲线并通过标准曲线回归方程计算样品中腐殖酸含量.
1.4.5　藻毒素测定
采用酶联免疫试剂盒(Beacon，美国)，使用酶标仪(Multiskan FC型，赛默飞世尔，中国)测定样品中藻毒素含量.实验中藻毒素含量以多种藻毒素的共同测定值显示，以总MCs(µg/L)含量计.
1.4.6　铜绿微囊藻EOM吸附前后荧光特征有机物光谱学测定
使用三维荧光光谱法分析铜绿微囊藻EOM吸附前后的组分结构变化.采用荧光分光光度计(型号F-7000，日本Hitachi)进行测定，使用1cm荧光比色皿.设置仪器参数为：激发波长220~ 400nm，发射波长250~550nm，激发狭缝5nm，发射狭缝1nm，光电倍增管电压725V，扫描速度12000nm/ min.测定前以超纯水为空白对照，数据导出后使用origin软件绘制等高线图.
2　结果与讨论
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2.1　不同生长周期铜绿微囊藻EOM的释放
铜绿微囊藻生长曲线如图1(a)所示，可将铜绿微囊藻细胞的生长划分为4个时期，即适应期(0~6d)、对数期(7~40d)、稳定期(41~70d)和衰亡期(>70d).选取第20，50，80d分别作为对数期、稳定期和衰亡期铜绿微囊藻EOM的代表试验点.铜绿微囊藻在对数期(20d)的EOM中DOC含量最低，仅为34.61mg/L，稳定期(50d)的EOM中DOC含量升至64.24mg/L，而衰亡期(80d)的EOM中的DOC含量最高，达到了70.57mg/L.这一现象说明：从对数期到稳定期，由于藻细胞大量生长繁殖，代谢产物不断分泌释放到细胞外，溶解于水体中，导致水中DOC含量显著上升；而稳定期到衰亡期，随着藻细胞的不断死亡裂解，细胞内有机物不断释放渗出，使得铜绿微囊藻细胞的代谢及胞外释放量远远大于其细胞内源代谢量，从而导致DOC浓度进一步增加.这一发现与已有研究结果一致[19-20].
此外，由图1(b)可见，在铜绿微囊藻生长的对数期、稳定期、衰亡期，其EOM中多糖、蛋白质、腐殖酸及藻毒素含量也各有不同，四种组分均呈现依生长期含量增多的趋势.这说明，铜绿微囊藻的多糖、蛋白质、腐殖酸和藻毒素均在细胞生长繁殖过程中同时产生胞内包裹和胞外自然分泌代谢，胞内物质会在细胞衰亡时随细胞裂解而产生部分释放，导致其衰亡期相应物质含量仍持续增高.其中，藻毒素在对数期和稳定期含量较低，且变化不大(组间差异P>0.05)，而在衰亡期含量出现急剧升高(与其他两时期组间差异P<0.001)，说明藻毒素主要合成且包裹于细胞内部，在细胞破损裂解时才会产生大量释放.
2.2　粉末活性炭对铜绿微囊藻EOM总有机含量的吸附去除效果
不同生长期(对数期、稳定期、衰亡期)铜绿微囊藻EOM的粉末活性炭吸附效果如图2及表1所示.整体来看，粉末活性炭对铜绿微囊藻EOM的DOC去除效果并不佳，去除率甚至低于40%，这说明粉末活性炭对铜绿微囊藻EOM并不具备显著的有机组分协同吸附效果.随着粉末活性炭投加量的增加，不同时期铜绿微囊藻EOM的DOC去除率也相应增大.当粉末活性炭投加量达到300mg/L，对数生长期铜绿微囊藻EOM的DOC吸附量最少，为20.85mg/g活性炭，去除率仅为18.07%；稳定生长期铜绿微囊藻EOM的DOC吸附量为62.47mg/g活性炭，去除率为29.17%；衰亡期铜绿微囊藻EOM的DOC吸附量最多，为81.98mg/g活性炭，去除率为34.85%.这说明粉末活性炭对不同时期铜绿微囊藻产生的EOM吸附量和去除率均具有显著性差异，稳定期与衰亡期组间差异P<0.01，对数期与其他两时期组间差异P<0.001.当然这可能有两种原因：其一，不同时期铜绿微囊藻产生的EOM总量不同，越高的EOM初始含量水平越利于推动粉末活性炭吸附反应正向进行；其二，不同时期铜绿微囊藻产生的EOM物质组分结构或组分含量占比不同，更易于被粉末活性炭吸附去除的物质组分在衰亡期铜绿微囊藻EOM中最多，稳定期铜绿微囊藻EOM中次之，对数生长期铜绿微囊藻EOM中较少.这也说明粉末活性炭对铜绿微囊藻EOM中各有机组分的共同吸附去除能力有限，仅可实现部分有机物质结构的吸附截留.
2.3　粉末活性炭对铜绿微囊藻EOM中不同物质组分的吸附效果
不同生长期铜绿微囊藻EOM的物质组分与其特性差异极有可能是制约粉末活性炭吸附效果的关键，为了进一步研究粉末活性炭对铜绿微囊藻EOM的针对性吸附规律，本研究考察了粉末活性炭对铜绿微囊藻EOM中多糖、蛋白质、腐殖酸和藻毒素4种典型有机物的吸附规律.
2.3.1　粉末活性炭对铜绿微囊藻EOM中多糖的吸附效果
不同生长期铜绿微囊藻EOM中多糖在粉末活性炭吸附作用下的去除效果如图3所示，吸附量列于表1.通过图3(a)发现，对数期、稳定期、衰亡期的多糖浓度随粉末活性炭投加量增大而呈略微递减的趋势.当粉末活性炭投加量达到300mg/L时，对数期多糖吸附量为9.72mg/g活性炭，稳定期多糖吸附量为8.43mg/g活性炭，衰亡期多糖吸附量为8.67mg/g活性炭，活性炭对各时期多糖的吸附量基本一致，并无显著差异(P>0.05).这说明铜绿微囊藻于不同生长周期释放的多糖含量虽有不同，但其易于活性炭吸附的组分结构可能并无差异且含量甚微，极有可能在铜绿微囊藻对数生长期已完成易吸附多糖结构的完全释放，而在稳定期和衰亡期以分泌不易吸附结合型多糖为主.对于所研究的活性炭投加量来说，对数期的低含量多糖已使活性炭达到该组分结构的吸附饱和态.吸附去除率数据显示，各时期铜绿微囊藻EOM中多糖的去除率仅有6.50%~8.83%，这说明粉末活性炭对铜绿微囊藻EOM中的多糖表现出较差的吸附效果.可能是多糖具有一定的黏性[21]，易堵塞活性炭吸附孔隙，降低其吸附率所致；也可能是多糖中大多物质分子量超出活性炭吸附尺度范围所致[22-23].此外，本文也进一步考察了粉末活性炭投加量为200mg/L时，吸附时间对铜绿微囊藻EOM中多糖去除效果的影响，如图3(b)所示.可看出粉末活性炭对不同时期铜绿微囊藻EOM中多糖的吸附均呈现为0~1h的快速吸附和1~8h的慢速吸附两阶段吸附反应，且在一阶段快速吸附后即近乎达到吸附平衡.这说明多糖中少部分可吸附型分子结构在0~1h即可被活性炭快速吸附，而多糖中大部分不易吸附型分子结构在吸附时间持续延长下仍不可被活性炭吸附结合.这也进一步说明，多糖的吸附量少、去除率低，并不是由其吸附速率导致的，而是由其物质结构超出吸附尺度范围所致.
2.3.2　粉末活性炭对铜绿微囊藻EOM中蛋白质的吸附效果
不同生长期铜绿微囊藻EOM中蛋白质在粉末活性炭吸附作用下的去除效果如图4所示，吸附量列于表1.通过图4(a)发现，稳定期铜绿微囊藻EOM中的蛋白质随粉末活性炭投加量增大而呈现的吸附去除趋势更明显，在300mg/L活性炭投加量时蛋白质吸附量为95.92mg/g活性炭，去除率相对更高，可达到18.85%.而对数期蛋白质在初始含量较低(126.49mg/L)的条件下吸附量仅40.75mg/g活性炭，仅可实现9.67%的去除率.这说明铜绿微囊藻对数期和稳定期所释放的蛋白质结构可能并不相同，稳定期所分泌的蛋白质从结构类型或分子尺度上更易与活性炭发生吸附结合.衰亡期蛋白质初始含量较高(195.22mg/L)，仍呈现出41.15mg/g活性炭的低吸附量和6.32%的更低去除率.可能原因有二：其一，衰亡期铜绿微囊藻所分泌的胞外蛋白质结构类型或分子尺度以不易与活性炭吸附结合型为主；其二，衰亡期由于铜绿微囊藻细胞破损而释放出的胞内蛋白质也超出了活性炭的吸附尺度，相应降低了活性炭对总蛋白质的吸附率.本文也进一步考察了粉末活性炭投加量为200mg/L时，吸附时间对铜绿微囊藻EOM中蛋白质去除率的影响，如图4(b)所示.粉末活性炭对对数期和衰亡期的铜绿微囊藻EOM中蛋白质仍在0~1h即可达到吸附平衡，而对稳定期铜绿微囊藻EOM中蛋白质的吸附过程延长至2h到达平衡，这说明虽然稳定期铜绿微囊藻所分泌的可吸附型蛋白质结构含量有所增多，但其与活性炭并不能实现完全的迅速结合，需要延长吸附时间以加大吸附量.这也进一步说明活性炭对蛋白质类物质组分并不具有吸附优势.
2.3.3　粉末活性炭对铜绿微囊藻EOM中腐殖酸的吸附效果
不同生长期铜绿微囊藻EOM中腐殖酸在粉末活性炭吸附作用下的去除效果如图5所示，吸附量列于表1.图5(a)中，对数期、稳定期、衰亡期腐殖酸的吸附量差异显著(P<0.001)，分别为3.27，4.21，6.24mg/g活性炭，该递增趋势与腐殖酸在三时期的初始含量规律基本一致，这说明腐殖酸吸附量的显著性差异极有可能是由其初始含量的明显不同所导致的.
然而，不同时期铜绿微囊藻EOM中腐殖酸的去除率均接近50%，即活性炭不论在初始腐殖酸含量低的对数期还是初始腐殖酸含量高的衰亡期均可实现基本固定占比的腐殖酸吸附.这说明粉末活性炭对不同时期铜绿微囊藻EOM中的腐殖酸去除率受其中易吸附型腐殖酸结构的含量占比所限，由于铜绿微囊藻产生的腐殖酸中仍有一半含量的物质结构不易与粉末活性炭发生吸附结合，因而在各时期均产生约50%的吸附去除率，且无显著差异(P>0.05).当然，不同的铜绿微囊藻生长周期中腐殖酸结构类型占比并不完全一致，对数期腐殖酸产量低，衰亡期腐殖酸产量高，其不易被粉末活性炭吸附结合的腐殖酸含量也由少增多，这也是导致粉末活性炭对对数期、稳定期、衰亡期的腐殖酸去除率呈略微递减趋势的原因.此外，粉末活性炭对铜绿微囊藻EOM中腐殖酸的吸附去除速率如图5(b)所示.当粉末活性炭投加量为200mg/L时，其吸附表现为0~0.5h的快速吸附和0.5~8h的慢速吸附，这也进一步证实了，粉末活性炭对于铜绿微囊藻EOM中易发生吸附结合的腐殖酸结构类型均具有极高和极快的吸附能力.
2.3.4　粉末活性炭对铜绿微囊藻EOM中藻毒素的吸附效果
不同生长期铜绿微囊藻EOM中藻毒素在粉末活性炭吸附作用下的去除效果如图6所示，吸附量列于表1.
如图6(a)显示，粉末活性炭对藻毒素具有显著的吸附去除效果，当粉末活性炭投加量达到300mg/L时，藻毒素去除率可达到53.39%~64.63%，甚至高于粉末活性炭对腐殖酸的去除率.这说明藻毒素的分子结构或分子尺度更易于通过活性炭的微孔表面吸附结合.铜绿微囊藻衰亡期藻毒素大量释放时，粉末活性炭呈现的吸附效果最佳，可实现藻毒素64.63%的高效去除，吸附量达到217.24µg/g活性炭.而在稳定期，虽然粉末活性炭对藻毒素的吸附去除率计算值仍较高，与衰亡期基本一致，但由于藻毒素初始含量较低，其吸附量相对较低，为96.42µg/g活性炭.这说明稳定期与衰亡期中易吸附型藻毒素的占比基本一致，粉末活性炭对于其中高占比的易吸附型藻毒素具有很好的吸附去除效果.对数期藻毒素初始含量与稳定期差异不大(P>0.05，图1(b))，而吸附量(76.56µg/g活性炭)和去除率(53.39%)却显著低于稳定期和衰亡期(P<0.01)，这说明对数期易吸附型藻毒素占比与稳定期和衰亡期具有一定差异性，易吸附型藻毒素在对数期产生相对较少(但仍高于其他物质组分的易吸附型结构占比)，多形成并分泌于稳定期和衰亡期，尤其在细胞破损裂解的衰亡期随初始释放量的增大而产生更大吸附量，表现出相较于其他两时期更显著的吸附量差异(P<0.001).此外，粉末活性炭对铜绿微囊藻EOM中藻毒素的吸附去除速率如图6(b)所示.在投加200mg/L的粉末活性炭时，其对藻毒素的吸附仍表现为0~1h的快速吸附即达到吸附平衡.
2.4　粉末活性炭对铜绿微囊藻EOM中特征有机组分的吸附差异分析
图3~图6可发现，粉末活性炭对铜绿微囊藻EOM中不同类型物质组分具有不同的吸附去除率，以藻毒素的去除率最高，腐殖酸次之，蛋白质和多糖依次更低.这种物质组分间的吸附差异性极有可能是导致图2中活性炭对EOM整体有机含量的协同吸附效果较差的主要原因.另外，活性炭对铜绿微囊藻不同生长周期产生的EOM的吸附差异也主要由各时期释放的物质组分结构不同所致.总体来看，多糖中易于活性炭吸附的分子结构比例较低，且主要分布于对数期的释放过程；蛋白质中易于活性炭吸附的分子结构比例仍较低，但该部分结构多于稳定期分泌；腐殖酸在各时期的结构类型含量比差异并不显著，基本可实现相应易吸附结构的高效去除；藻毒素中易于活性炭吸附的分子结构比例最高，且稳定期和衰亡期的该结构占比相对对数期更高.然而活性炭对EOM中不同类型物质组分具有不同吸附去除率的原因何在？其吸附差异究竟在于活性炭对不同物质结构具有优先和滞后的吸附次序？还是活性炭不选择物质结构，选择同时吸附各物质组分中适合自己的分子尺度，因适合吸附尺度的组分含量不同而出现差异？
为了探究这一机制，本研究采用三维荧光光谱对活性炭吸附铜绿微囊藻EOM的过程进行追踪分析.铜绿微囊藻EOM中包含五类具有荧光特征强度的有机物质：A、B区的类酪氨酸和芳香族蛋白物质、C区的类富里酸物质、D区的类色氨酸蛋白质和溶解性微生物代谢产物、以及E区的类腐殖酸物质.图7展示了粉末活性炭对不同生长期铜绿微囊藻EOM中五类荧光特征有机物的去除效果.从图7(a)、(b)、(c)对比的吸附过程来看，图7(b)系列均相对于图7(a)表现出明显的荧光峰削减趋势，图7(c)系列相对于图7(b)的削减则不如前者，这与图3~6中有机组分的吸附速率结果一致.此外，在图7(a)、(b)、(c)中荧光峰的削减过程中，A、B、C、D、E区的荧光特征有机物均呈现相同由快到慢的削减，这说明粉末活性炭在其吸附过程中没有出现相同时间下只吸附某种物质而延迟吸附其他物质的现象，其对各区的荧光特征有机物吸附不分先后.当然由于各类有机物的吸附去除率不同，因此其实现的是同时不同程度的吸附去除.从图7(A)、(B)、(C)对比的铜绿微囊藻生长期来看，粉末活性炭对不同时期铜绿微囊藻EOM中荧光特征有机物的吸附规律基本一致，各时期均表现为五区荧光物质同时吸附，C区、E区的类富里酸、类腐殖酸物质吸附比例更大，但并未随不同时期EOM中物质含量的多少或结构类型的差异而出现优先或滞后吸附.这说明，活性炭对铜绿微囊藻EOM的吸附过程不分吸附次序，极有可能遵循的是分子尺度原则.活性炭只选择吸附适宜自身吸附孔隙的物质分子予以去除，多糖和蛋白中适合吸附的分子尺度比例低，而腐殖酸和藻毒素中适合吸附的分子尺度比例高.研究证实，多糖类物质基本由高分子化合物组成，分子量高达几万到几千万Da[23]，而芳香族蛋白质、溶解性微生物代谢产物也主要由大于50000Da的高分子量化合物组成，500~5000Da的低中分子量物质较少，相比之下，类腐殖酸物质多由500~5000Da的低中分子量物质组成[24]，藻毒素分子尺度更是主要呈现于800~1100Da之间的低分子量区间[25].因此，活性炭对铜绿微囊藻EOM中有机物的选择性吸附以中低分子量尺度为主，对5000Da以上的大分子物质吸附效果甚微.综合以上分析，粉末活性炭在铜绿微囊藻爆发的整个生命周期仍可作为去除藻源污染物的应急措施，但其处理效率较低，只能去除部分中低分子量有机物，需结合其他能够去除大分子有机物的有效技术联合运行；或在氧化降解大分子有机物的前提下增设活性炭深度处理，去除残留小分子有机物，以持续保障供水水质.
3　结论
收起
3.1　铜绿微囊藻EOM的有机含量随生长周期的推移而不断增加，其多糖、蛋白质、腐殖酸和藻毒素均在细胞生长繁殖过程中同时产生胞内包裹和胞外自然分泌代谢，部分胞内物质还会在细胞衰亡时随细胞裂解而产生相应释放.
3.2　粉末活性炭对铜绿微囊藻EOM的有机物协同去除率整体较低，对数期、稳定期、衰亡期铜绿微囊藻EOM的DOC去除率仅为18.07%、29.17%和34.85%.
3.3　粉末活性炭对铜绿微囊藻EOM中各有机组分的吸附去除率随活性炭投加量的增加而升高，在200~300mg/L活性炭投加量时可达到所有组分的最高吸附去除率，且各组分基本可在0~1h的快速吸附阶段迅速达到吸附平衡.
3.4　粉末活性炭对铜绿微囊藻不同生长时期产生的EOM中各物质组分具有一定的吸附差异规律.多糖中易于活性炭吸附的分子结构比例较低，且主要释放于对数期，导致各时期多糖在初始含量不同条件下吸附去除率差异较大，但吸附总量基本一致；蛋白质中易于活性炭吸附的分子结构比例仍较低，但该部分结构多于稳定期分泌，稳定期蛋白质吸附量和吸附去除率均高于其他两时期；腐殖酸在各时期的结构类型含量比差异并不显著，基本可实现相应易吸附结构的高效去除，各时期吸附去除率差异不大，而因初始含量不同产生显著吸附量差异；藻毒素分子结构更易于通过活性炭的表面吸附结合，且易吸附型藻毒素多分泌于稳定期和衰亡期，尤其在大量释放的衰亡期产生更显著的吸附量差异.
3.5　粉末活性炭对各生长时期铜绿微囊藻EOM中的不同物质组分呈现明显的吸附差异规律，吸附去除率：藻毒素>腐殖酸>蛋白质>多糖.这主要是由于活性炭对铜绿微囊藻EOM的吸附过程遵循分子尺度选择吸附原则，选择性吸附中低分子量为主的物质组分，这也是导致铜绿微囊藻生长周期中活性炭对藻源污染物去除率低下的重要因素.
基金
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  • 国家重点研发计划(2022YFC3203602)
  • 国家自然科学基金资助项目(51708480)
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2025年第45卷第3期
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  • 接收时间：2024-08-28
  • 首发时间：2026-03-18
  • 出版时间：2025-03-20
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国家重点研发计划(2022YFC3203602)
国家自然科学基金资助项目(51708480)
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    扬州大学环境科学与工程学院，江苏 扬州 225127

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genus		 种数
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species		 占总种数比例
Percentage of
total species (%)		 属
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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
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红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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