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The effects of three different influent strategies on the protein content of extracellular polymeric substances(EPS)were investigated to assess their impact on sludge retention capacity of the CANON process. R1was operated under conventional influent strategy as the control group, while R2 and R3 were subjected to different variable influent strategies. After 90 days of operation, the SVI values in R1, R2, and R3 were 62.93, 53.10, and 57.59mL/g respectively indicating that the variable influent strategies could improve sludge settleability. The PN/PS ratios were significantly higher in R2(8.21)and R3(7.61)compared to R1(5.56). Three-dimensional fluorescence analysis revealed that the proportion of aromatic proteins in TB-EPS was highest in R2(32.47%), much higher than in R1(11.58%)and R3(10.5%). This indicated that the variable influent strategy promoted the formation of aromatic proteins in TB-EPS, enhancing the hydrophobicity of the sludge and improving settleability. The specific anaerobic ammonium oxidation activity(SAA)increased to 4.03, 4.68 and 4.36mg N/(g VSS· h)in R1, R2, and R3, respectively. Notably, the SAA in R2 and R3 exceeded that of the seed sludge, indicating the successful formation of mature CANON granular sludge. Although microbial activity in R2 and R3 was initially inhibited by loading fluctuations during early operation, the microbial communities gradually adapted to environmental fluctuations and regained stable metabolic activity, successfully operating the CANON process on day 54 and day 51, respectively. Total nitrogen removal efficiencies reached approximately 72.54%, 70.14%, and 73.75% in R1, R2 and R3 by day 90, demonstrating effective nitrogen removal performance.

, correspAuthors=Dong LI, 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=Dong LI, Yuan-xin WANG, Si-bo FU, Jie ZHANG), CN=ArticleExt(id=1241057219433787654, articleId=1241057215629554574, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=基于变量进水强化胞外聚合物蛋白质改善CANON污泥流失研究, columnId=1234106386565624579, journalTitle=中国环境科学, columnName=水污染与控制, runingTitle=null, highlight=null, articleAbstract=

对比研究了3种不同进水策略对CANON污泥EPS中蛋白质的影响,旨在探求变量进水策略对CANON污泥滞留能力的影响.R1采用常规进水策略作为对照组,而R2和R3采用不同的变量进水策略,分别启动CANON工艺.经过90d的运行后,R1,R2和R3反应器中SVI分别达到了62.93,53.10和57.59mL/g,这说明变量进水的策略可以改善污泥的沉降性能. R2和R3的PN/PS分别达到8.21和7.61,明显高于R1的5.56;三维荧光数据显示,R2的TB-EPS中芳香族蛋白占比达到32.47%,显著高于R1的11.58%和R3的10.5%;这表明变量进水策略会促进TB-EPS中芳香族蛋白的生成,进而提高污泥的疏水性,改善污泥沉降性能.比厌氧氨氧化活性(SAA)分别上升至4.03,4.68和4.36mg N/(g VSS· h),其中R2和R3污泥的SAA达到甚至超过了接种前厌氧氨氧化污泥的SAA,这说明反应器中已经形成了成熟的CANON颗粒污泥.虽然在反应初期R2和R3的微生物活性受到负荷波动的抑制,但随着时间的推移,微生物群体适应了环境变化,恢复了稳定的活性,分别在第54d和第51d实现了CANON工艺的启动.最终在第90d时,R1,R2和R3的总氮去除率分别达到了72.54%,70.14%和73.75%左右,实现了良好的脱氮性能.

, correspAuthors=李冬, authorNote=null, correspAuthorsNote=
* 责任作者,教授,
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李冬(1976-),女,辽宁丹东人,教授,博士,主要研究方向为水环境恢复理论及关键技术.发表论文200余篇..

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李冬(1976-),女,辽宁丹东人,教授,博士,主要研究方向为水环境恢复理论及关键技术.发表论文200余篇..

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李冬(1976-),女,辽宁丹东人,教授,博士,主要研究方向为水环境恢复理论及关键技术.发表论文200余篇..

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figureFileSmall=MHNu/SKJ3TwTO6HWVEjfWQ==, figureFileBig=7urFSgHqLiW9BzsL0kl3EA==, tableContent=null), ArticleFig(id=1241057226589270916, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057215629554574, language=CN, label=图7, caption=微生物活性, figureFileSmall=MHNu/SKJ3TwTO6HWVEjfWQ==, figureFileBig=7urFSgHqLiW9BzsL0kl3EA==, tableContent=null), ArticleFig(id=1241057226689934223, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057215629554574, language=EN, label=Table 1, caption=

Operation conditions of reactors

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反应器进水Ⅰ(min)反应Ⅰ(min)进水Ⅱ(min)反应Ⅱ(min)沉淀(min)出水(min)
R1101203003010
R2512053003010
R3712033003010
), ArticleFig(id=1241057226811569056, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057215629554574, language=CN, label=表1, caption=

反应器运行工况

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反应器进水Ⅰ(min)反应Ⅰ(min)进水Ⅱ(min)反应Ⅱ(min)沉淀(min)出水(min)
R1101203003010
R2512053003010
R3712033003010
), ArticleFig(id=1241057226937398193, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057215629554574, language=EN, label=Table 2, caption=

Operation status of each stage

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阶段时间(d)曝/停时间(min)DO(mg O2/L)
1~715/450.20~0.30
8~4715/450.10~0.15
48~9030/300.10~0.15
), ArticleFig(id=1241057227235193803, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057215629554574, language=CN, label=表2, caption=

各阶段运行情况

, figureFileSmall=null, figureFileBig=null, tableContent=
阶段时间(d)曝/停时间(min)DO(mg O2/L)
1~715/450.20~0.30
8~4715/450.10~0.15
48~9030/300.10~0.15
), ArticleFig(id=1241057227386188762, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057215629554574, language=EN, label=Table 3, caption=

Average particle size and median particle size of the sludge in different conditions

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样品D[4,3](µm)Dx(50)(µm)
种泥133.6789.74
R1(30d)182.59129.72
R1(60d)210.70135.51
R1(90d)237.04155.71
R2(30d)197.84143.84
R2(60d)341.28195.55
R2(90d)441.49366.82
R3(30d)196.02120.42
R3(60d)303.17167.85
R3(90d)323.99199.13
), ArticleFig(id=1241057227491046375, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057215629554574, language=CN, label=表3, caption=

不同运行工况下污泥平均粒径及中值粒径

, figureFileSmall=null, figureFileBig=null, tableContent=
样品D[4,3](µm)Dx(50)(µm)
种泥133.6789.74
R1(30d)182.59129.72
R1(60d)210.70135.51
R1(90d)237.04155.71
R2(30d)197.84143.84
R2(60d)341.28195.55
R2(90d)441.49366.82
R3(30d)196.02120.42
R3(60d)303.17167.85
R3(90d)323.99199.13
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基于变量进水强化胞外聚合物蛋白质改善CANON污泥流失研究
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李冬 1, * , 王远欣 1 , 傅思博 1 , 张杰 1, 2
中国环境科学 | 水污染与控制 2025,45(5): 2481-2489
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中国环境科学 | 水污染与控制 2025, 45(5): 2481-2489
基于变量进水强化胞外聚合物蛋白质改善CANON污泥流失研究
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李冬1, * , 王远欣1, 傅思博1, 张杰1, 2
作者信息
  • 1.北京工业大学水质科学与水环境恢复工程北京市重点实验室,北京 100124
  • 2.哈尔滨工业大学城市水资源与水环境国家重点实验室,黑龙江 哈尔滨 150090
  • 李冬(1976-),女,辽宁丹东人,教授,博士,主要研究方向为水环境恢复理论及关键技术.发表论文200余篇..

通讯作者:

* 责任作者,教授,
Study on reducing CANON sludge loss by strengthening protein of EPS through variable influent strategies
Dong LI1, * , Yuan-xin WANG1, Si-bo FU1, Jie ZHANG1, 2
Affiliations
  • 1.Key Laboratory of Beijing Water Quality Science and Water Environment Recovery Engineering, Beijing University of Technology, Beijing 100124, China
  • 2.State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
出版时间: 2025-05-20
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对比研究了3种不同进水策略对CANON污泥EPS中蛋白质的影响,旨在探求变量进水策略对CANON污泥滞留能力的影响.R1采用常规进水策略作为对照组,而R2和R3采用不同的变量进水策略,分别启动CANON工艺.经过90d的运行后,R1,R2和R3反应器中SVI分别达到了62.93,53.10和57.59mL/g,这说明变量进水的策略可以改善污泥的沉降性能. R2和R3的PN/PS分别达到8.21和7.61,明显高于R1的5.56;三维荧光数据显示,R2的TB-EPS中芳香族蛋白占比达到32.47%,显著高于R1的11.58%和R3的10.5%;这表明变量进水策略会促进TB-EPS中芳香族蛋白的生成,进而提高污泥的疏水性,改善污泥沉降性能.比厌氧氨氧化活性(SAA)分别上升至4.03,4.68和4.36mg N/(g VSS· h),其中R2和R3污泥的SAA达到甚至超过了接种前厌氧氨氧化污泥的SAA,这说明反应器中已经形成了成熟的CANON颗粒污泥.虽然在反应初期R2和R3的微生物活性受到负荷波动的抑制,但随着时间的推移,微生物群体适应了环境变化,恢复了稳定的活性,分别在第54d和第51d实现了CANON工艺的启动.最终在第90d时,R1,R2和R3的总氮去除率分别达到了72.54%,70.14%和73.75%左右,实现了良好的脱氮性能.

CANON  /  变量进水  /  蛋白质组成  /  颗粒污泥  /  间歇曝气

The effects of three different influent strategies on the protein content of extracellular polymeric substances(EPS)were investigated to assess their impact on sludge retention capacity of the CANON process. R1was operated under conventional influent strategy as the control group, while R2 and R3 were subjected to different variable influent strategies. After 90 days of operation, the SVI values in R1, R2, and R3 were 62.93, 53.10, and 57.59mL/g respectively indicating that the variable influent strategies could improve sludge settleability. The PN/PS ratios were significantly higher in R2(8.21)and R3(7.61)compared to R1(5.56). Three-dimensional fluorescence analysis revealed that the proportion of aromatic proteins in TB-EPS was highest in R2(32.47%), much higher than in R1(11.58%)and R3(10.5%). This indicated that the variable influent strategy promoted the formation of aromatic proteins in TB-EPS, enhancing the hydrophobicity of the sludge and improving settleability. The specific anaerobic ammonium oxidation activity(SAA)increased to 4.03, 4.68 and 4.36mg N/(g VSS· h)in R1, R2, and R3, respectively. Notably, the SAA in R2 and R3 exceeded that of the seed sludge, indicating the successful formation of mature CANON granular sludge. Although microbial activity in R2 and R3 was initially inhibited by loading fluctuations during early operation, the microbial communities gradually adapted to environmental fluctuations and regained stable metabolic activity, successfully operating the CANON process on day 54 and day 51, respectively. Total nitrogen removal efficiencies reached approximately 72.54%, 70.14%, and 73.75% in R1, R2 and R3 by day 90, demonstrating effective nitrogen removal performance.

CANON  /  variable influent  /  composition of protein  /  granular sludge  /  intermittent aeration
李冬, 王远欣, 傅思博, 张杰. 基于变量进水强化胞外聚合物蛋白质改善CANON污泥流失研究. 中国环境科学, 2025 , 45 (5) : 2481 -2489 .
Dong LI, Yuan-xin WANG, Si-bo FU, Jie ZHANG. Study on reducing CANON sludge loss by strengthening protein of EPS through variable influent strategies[J]. China Environmental Science, 2025 , 45 (5) : 2481 -2489 .
全程自养脱氮(CANON)工艺将短程硝化和厌氧氨氧化两个过程结合在一起,短程硝化过程为后续厌氧氨氧化提供必要的亚硝酸盐,厌氧氨氧化过程在厌氧条件下将氨氮转化为氮气[1].CANON工艺与传统废水脱氮工艺相比,能够有效降低废水处理过程中的曝气能耗且无需有机碳源,被认为是一种经济,高效的脱氮工艺[2-3].参与这些过程的功能菌包括氨氧化菌(AOB)和厌氧氨氧化菌(AnAOB),它们均为化能自养菌,生长速率缓慢,尤其是AnAOB世代周期长,极易流失,会影响系统的脱氮性能[4].因此生物质保留是CANON应用的关键,污泥应具有良好的滞留能力以保证系统内足够的生物量.
目前很多研究探讨了减少微生物流失的方法.生物膜法在全球范围内的污水厂被广泛采用,生物膜法是指微生物附着在某些固体载体上生长,继而形成生物膜的一种污水处理工艺.对于AnAOB这类自养微生物,生物膜系统可以形成生物膜进而减少微生物的流失.但是生物膜法需要向系统内投加大量的载体材料,增加运行成本.而在悬浮污泥体系中减少污泥流失的方法有调控水力剪切力[5-7],投加信号分子[8-9],添加金属离子[10-11]等.其中投加信号分子和金属离子的方法需要额外向体系中投加药剂,增添了运行成本;而采用调控水力剪切力的方式减少污泥的流失,本质上是促进微生物分泌胞外聚合物(EPS).EPS对污泥的性能非常重要,包括絮凝能力,沉降能力,通过紧密结合细胞加速微生物聚集体的形成,在促进微生物聚集,提升滞留能力方面有着重要作用[12-14].
有研究通过提高基质浓度的方式,提升了厌氧氨氧化反应器中的氮负荷,污泥的颜色随着AnAOB中细胞色素c的含量升高而愈加鲜红,同时伴随着AnAOB活性的升高,达到了110.42mg N/g VSS d[15];并且粒径逐渐增大,最终污泥的污泥平均粒径(D[4,3])达到410μm[16-17].在受到外界负荷波动的胁迫时,微生物会分泌EPS来应对恶劣环境,其中蛋白质具有较高的黏结强度和能力,其含量的增加有助于系统的稳定运行.此外发现EPS对于负荷的波动有较好的响应,负荷波动越大,EPS分泌的越多,有利于提高系统性能的稳定性[18-20].这意味着在CANON启动以及运行过程中,可以利用氮负荷波动刺激EPS的分泌,促成污泥的聚集,进而改善污泥的沉降性,从而有助于系统的长期稳定运行.
由于在实际的工程应用中,无法通过改变进水基质浓度的方式实现负荷的波动.基于此,本文提出一种新策略,即采用变量进水的方式,在反应器内营造氮负荷波动的环境,有助于污泥分泌EPS改善污泥的沉降性,进而实现功能微生物的有效保留,实现CANON工艺的稳定运行.实验采用序批式反应器(SBR)运行CANON工艺,旨在探究不同进水策略对污泥沉降性能,EPS中蛋白质组成和含量,污泥粒径,系统脱氮性能及相关功能菌活性等方面的影响.
反应器接种实验室中试A/O水箱中的硝化污泥以及厌氧氨氧化滤柱中反冲洗得到的少量厌氧氨氧化污泥;其中硝化污泥颜色发黑,呈絮状,沉降性较差.两种污泥以3:1的比例混合均匀,分别接种在反应器内.
实验用水采用人工配水模拟城市低氨氮废水,模拟废水的组成成分如下:(65±5)mg/L NH4+-N,1000mg/L NaHCO3,50mg/L MgSO4·7H2O,20mg/L KH2PO4,20mg/L CaCl2,微量元素浓缩液Ⅰ和Ⅱ浓度为1mL/L[21].
实验采用3个由有机玻璃制成的SBR反应器,有效容积为6L,分别命名为R1,R2和R3. 3个反应器采用间歇曝气的模式运行,每天运行3个周期,每个周期480min.本实验通过控制进水量实现对负荷的调控,具体运行情况如表1表2所示.
NH4+-N采用纳氏试剂光度法测定;NO2--N采用N-(1-萘基)-乙二胺光度法测定;NO3--N采用紫外分光光度法;水温,DO和pH值采用WTW Oxi296在线测定仪实时监测;混合液悬浮固体含量(MLSS)和挥发性悬浮固体含量(MLVSS)采用标准重量法测定;污泥形态采用OLYMPUS DP27型显微镜观测;颗粒粒径分布采用Mastersizer 2000激光粒度仪测定;EPS采用热消解法进行提取[22],其中蛋白质(PN)采用改良lowery法测定,多糖(PS)采用蒽酮硫酸法测定[23].
AOB,NOB和AnAOB的活性分别采用比氨氧化速率(SAOR),比亚硝酸盐氧化速率(SNOR)和比厌氧氨氧化速率(SAA)来表征.在每个反应器中各取两组100mL泥水混合物置于烧杯中,用去离子水冲洗3次,分别向其中添加微量元素和氮源.氮源为50mg/L的NH4+-N和50mg/L的NO2--N.其中测量SAOR和SNOR的烧杯通过空气泵曝气保证好氧环境并搅拌,DO保持在(4±0.5)mg O2/L;测量SAA的烧杯不进行曝气,只进行搅拌.温度维持在25℃,每30min取一次水样,持续120min.根据氮浓度的变化曲线得到相应功能菌的活性.
式中:SAOR为比氨氧化速率,mg N/(g VSS·h);SNOR为比亚硝酸盐氧化速率,mg N/(g VSS·h);SAA为比厌氧氨氧化速率,mg N/(g VSS·h);(NH4+-N)0为0时刻的氨氮浓度,mg/L;(NH4+-N)tt时刻的氨氮浓度,mg/L;(NO2--N)0为0时刻的亚硝酸盐氮浓度,mg/L;(NO2--N)tt时刻的亚硝酸盐氮浓度,mg/L;(NO3--N)0为0时刻的硝酸盐氮浓度,mg/L;(NO3--N)tt时刻的硝酸盐氮浓度,mg/L;t为反应时间,h;MLVSS为挥发性悬浮固体含量,mg/L.
使用热消解法提取出来EPS作为待测样品,采用上海棱光F97Pro荧光分光光度计,选择扫描参数为:激发波长范围为200~400nm,发射波长范围为250~550nm,激发波长间隔5nm,发射波长间隔1nm,激发/发射带宽为5nm;扫描速度30000nm/min,增益电压(PMT)为500V.得到扫描数据之后,采用MATLAB toolbox DOM Fluor工具包对得到的结果进行平行因子分析(PARAFAC),用于解构荧光物质组分,以区分和定量不同的荧光组分.
3组反应器的生物量以及污泥沉淀性能的变化情况如图1所示.接种时混合污泥的MLSS和MLVSS分别为2265和1252mg/L,污泥容积指数(SVI)为105.80mL/g.接种初期污泥的沉降性较差,在运行初期被大量淘洗出反应器,导致第14d各个反应器内MLSS都呈现下降的趋势. R1对照组的生物量在第42d开始缓慢上升,随后逐渐稳定至2085mg/L,相较初期下降了180mg/L.而R2和R3的生物量第28d便开始回升,最终分别达到2585和2369mg/L,相较刚接种时分别上升了320和104mg/L.表明变量进水的策略有效减少了CANON污泥的流失.
从污泥沉降性角度来看,不同的进水策略对污泥颗粒化进程产生了不同程度的影响.总体来看,3个反应器中污泥的沉降性能随着反应的进行都在逐渐改善,经过84d的运行,R1,R2和R3污泥的SVI分别下降到62.93,53.10和57.59mL/g.这说明,变量进水的策略可以改善污泥的沉降性能从而减少微生物的流失.
值得注意的是,R1在运行到第56d之后,尽管污泥的SVI仍然在下降但是污泥的f值却降低了.有研究表明,Ca2+,Mg2+等金属离子会提高污泥中无机质的含量,使得污泥表现出较好的沉降性能[24].推测是因为长期处于低基质且无负荷波动的环境下,导致污泥无机质的占比升高,从而展现出较好的沉降性能.采用变量进水策略的R2和R3,两者污泥的沉降性能得到了显著提升并且污泥中有机质的含量也在不断升高,f值与SVI基本呈现负相关.这说明R2和R3污泥沉降性能的改善与污泥中有机质占比提升有关.相比于R3,R2的SVI值在56d之后便降低到60mL/g以下,沉降性能的改善优于R3.这解释了R2的生物量高于R3的生物量.
3组反应器中污泥的粒径变化如表3所示.接种的污泥是来自A/O水箱中的硝化污泥和少量滤柱中厌氧氨氧化污泥混合而成的污泥,初始D[4,3]为133.67μm.之后从反应器中间位置取样采集均质的泥水混合物进行粒径分析检测.
3个反应器在运行初期粒径都有小幅度升高,结合同时期各个反应器内MLSS的下降趋势,推测可能是由于流失了大量絮状污泥,而沉降性能好的污泥一般粒径较大,导致反应器中粒径大的污泥占比提升,进而观察到了粒径的升高.
随着反应的进行,3个反应器的粒径总体呈现显著上升的趋势. Vlaeminck等[25]研究指出,在微生物生长过程中,小颗粒污泥在EPS的作用下逐渐聚集成大颗粒.其中R2呈现出最快的颗粒化速度,在第90d时D[4,3]达到了441.49μm,其次是R3,D[4,3]达到了323.99μm,R1的D[4,3]为237.04μm.与R1相比,R2和R3的D[4,3]都有显著增加.其中R2污泥的粒径增长速率最快,推测可能是R2反应器内负荷波动更大,促使微生物发生自聚集.另外,结合前文的分析,R2和R3污泥的SVI分别下降到53.10和57.59mL/g,表明系统内污泥的沉降性能得到改善,这也印证了污泥粒径增大,颗粒污泥增多.值得注意的是,R3反应器中污泥的中值粒径(Dx(50))和D[4,3]相差较大.这一结果在图2中也有所反映,R3的粒径分布图呈现出多峰的特征.这可能是由于R3中本身中等大小的颗粒分泌更多的EPS,粒径发生了显著变化,造成颗粒分布的不均匀[26].
运行期间污泥的形态及颜色变化如图3所示.如图3(a)所示,接种污泥由大量呈现暗黄色的絮状污泥以及少量浅红色的颗粒污泥组成.图3(b),(c)和(d)分别是第90d时R1,R2和R3反应器中的污泥.观察图3(c)和(d)中间位置的大颗粒,是由多个小颗粒聚集而成,推测是因为R2和R3大量分泌EPS,将小颗粒紧密黏附在一起,进而形成了大颗粒.相较于R1,R2和R3污泥的结构更密实且光滑.可以发现颗粒核心位置颜色偏红,到了边界区域颜色逐渐变淡,呈现出淡黄色,颗粒核心区域红色的加深表明AnAOB活性增强[15,27].这意味着R2和R3中已出现成熟的CANON污泥,好氧的AOB位于外层而厌氧的AnAOB位于颗粒的内层核心,这与前人研究中的结果一致[28-30].这表明变量进水的策略可以促进污泥的颗粒化.而相较于R3,R2污泥显得更加致密和光滑,这说明R2的进水策略更有利于污泥絮体黏附聚集成颗粒.
EPS是微生物分泌于细胞外的大分子聚合物,能够促进细胞的聚集,其在促进污泥颗粒化以及维持结构稳定性方面起到重要的作用[13].因此进一步探讨不同进水策略对EPS组成的影响. EPS中的主要成分是PN和PS,本节以PN和PS的总和代表EPS.
实验过程中R1,R2和R3污泥的EPS含量变化如图4所示.在实验启动初期,3个反应器中污泥的PN和PS都处于较低的水平,分别为22.31和3.75mg/g VSS.有研究指出,EPS对于CANON颗粒污泥的结构强度具有重要作用[25]. R1反应器作为对照组,采用常规进水的方式,在运行56d后污泥的EPS含量逐渐稳定在68.22mg/g VSS,增长速度较为缓慢.而R2,R3采用了变量进水的方式,营造了负荷波动的环境,促进污泥中EPS的分泌以应对环境的变化,使得R2和R3的EPS含量相较于R1有明显的提升[16,20].值得注意的是,第84d时R2中的EPS含量为96.84mg/g VSS,高于同时间R3的85.12mg/g VSS,这说明更大的负荷波动,更利于EPS的分泌.EPS含量与微生物的生长期密切相关;在对数生长期时,EPS随着培养时间的增加而增加[31].
PN中含有大量结构松散的疏水性氨基酸,由于氨基的水解而携带正电荷,PS由于羟基的水解携带负电荷,更高的PN/PS意味着更高的正电荷,可以中和EPS的负电荷,进而减弱污泥之间的静电斥力,增强污泥絮体的黏附性,从而加速污泥的颗粒化[32].R1反应器中的PN含量增长趋势与EPS总量一致,PN/PS基本稳定在5.44左右.而R2和R3反应器经历了氮负荷的波动,两者的PN含量分别上升到86.33和75.88mg/g VSS,PN/PS分别上升到8.21和7.61.这表明,变量进水策略会通过改变EPS中PN和PS的占比提升污泥的疏水性,进而影响污泥的聚集性能.相较于R1和R3,R2污泥具有更高的PN/PS,表明R2污泥具有更高的疏水性,从而污泥具有更强的稳定性和沉降性能,该结果与R2的SVI和D[4,3]等结果一致.
为了进一步验证负荷波动对EPS组成的影响,分别对种泥以及第84d时的R1,R2和R3污泥的EPS上清液进行三维荧光分析,如图5所示.采用平行因子分析法,解构荧光物质组分[33].其中占比最多的成分峰A,出现在Ex/Em=275~285/330~352nm,为色氨酸蛋白类物质;其次为峰B,出现在Ex/Em=275/310~322nm,为酪氨酸与类蛋白物质;峰C位于Ex/Em=215~225/354~368nm,为芳香族蛋白;占比最少的成分为峰D,出现在Ex/Em=250~285/438~452nm,被认为腐殖酸类物质.
有研究指出腐殖酸类物质对于颗粒污泥的聚集是不利的[34].可以注意到,所有污泥样品的LB-EPS中的组分以及构成比例都大致相似,只存在峰A和峰D,且峰A占比远大于峰D.其中R2和R3的TB-EPS中腐殖酸类物质的占比极低,仅有1.3%和2.35%.前文的分析指出,R2和R3反应器中污泥的粒径相较于R1有显著的增长,由此可以推测变量进水的策略可以促进污泥分泌EPS,同时对EPS的结构组成有很大的影响,变量进水的策略显著提高了污泥EPS中蛋白质的占比,有利于污泥的聚集.有研究指出芳香族蛋白等蛋白类物质在维持颗粒污泥的稳定结构过程中起着重要的作用[35-37]. 3个反应器在运行84d之后的TB-EPS中均出现了峰C,R2的芳香族蛋白占比达到32.47%,显著高于R1的11.58%和R3的10.5%.这不仅说明变量进水策略可以刺激污泥分泌更多的芳香族蛋白,也意味着R2的变量进水策略优于R3的变量进水策略.
反应器运行全程时CANON系统的氮浓度变化如图6所示.硝化污泥的活性恢复较好,氨氮去除率可以达到48.8%.但是3组反应器出水的硝酸盐氮浓度过高,分别达到了26.17,16.72和14.04mg/L,导致系统的总氮去除率极低,仅有10.97%,9.00%和13.67%;ΔNO3--N/ΔNH4+-N分别达到了0.786,0.718和0.631,而CANON系统的ΔNO3--N/ΔNH4+-N理论值为0.11[38].显然,这是由于亚硝酸盐氧化所致,可能是因为当前系统的DO有利于NOB的生长,这对于CANON工艺的长期运行造成了很大的困难.
许多研究表明,AOB和NOB对氧气的亲和力不同,在低DO情况下,NOB活性将会受到抑制而AOB受到影响较小[39-40].此前有研究在主流条件下运行CANON系统,采用低DO(0.06~0.17mg O2/L),在HRT为2~6h的条件下,实现了对NOB活性的有效抑制并最终实现CANON系统的稳定运行[30,41].因而选择降低DO,对NOB进行选择性抑制同时保证AnAOB的活性.在第8d更改曝气策略,降低曝气强度,将好氧阶段的DO维持在0.1~0.15mg O2/L,进入阶段Ⅱ,据报道此DO设置有利于CANON的运行[1].可以看到,在第8d之后,3组反应器的出水氨氮浓度迅速升高;尽管由于曝气强度的减少造成了氨氮转化量的降低,但是出水硝酸盐氮浓度大幅度下降,ΔNO3--N/ΔNH4+-N逐渐降至0.289,0.301和0.337,这意味着3组反应器内的NOB活性得到了一定的抑制.随着反应的进行,3组反应器的总氮去除率逐渐升高.
到达第47d后,R1实现了CANON的启动.由于AnAOB对于DO较为敏感,通常在CANON系统中设置较低的DO浓度[42].因此,为了提升总体的氮去除效果,在第47d时调整曝气策略,维持曝气强度不变,延长曝气时间,将曝停比改为1:1,即曝气30min停曝30min,进入阶段Ⅲ.在更改了曝气策略之后,R2和R3分别在第54和51d实现CANON的启动.
采用低DO间歇曝气的策略既保证了AOB的活性,减少对AnAOB活性的抑制;另一方面抑制了NOB的活性,保证厌氧氨氧化过程亚硝酸盐的供应[26]. R2和R3采用变量进水策略,初期氮去除率整体低于R1,启动时间较长,这说明微生物在面对负荷波动的不利环境后活性减弱,需要一定时间来适应这种波动的环境,因此脱氮性能的提升相对缓慢.最终在经过90d的运行,3个反应器的总氮去除率分别达到了72.54%,70.14%和73.75%,均实现了良好的脱氮性能.这表明尽管采用变量进水的策略会在反应初期会削弱系统脱氮性能,但是历时90d仍可以实现稳定运行,实现良好的脱氮性能.
为了验证系统运行过程中相关功能菌的活性,测定了各反应器不同时期污泥的SAOR,SNOR和SAA,如图7所示.对刚接种的污泥测定菌群活性,此时混合污泥的SAOR,SNOR和SAA分别为8.86,12.06和4.64mg N/(g VSS·h).结果表明,接种污泥中NOB活性较高,导致了短程硝化过程的恶化.与系统在阶段Ⅰ整体脱氮性能较差相对应,随后进入阶段Ⅱ.在第28d测得3个反应器的SNOR均大幅度下降,与此同时SAOR也有小幅度下降,可见控制DO的策略在有效抑制NOB活性的同时,也对AOB造成了不利影响.值得注意的是,3个反应器中的SAA也大幅下降,推测是因为微生物进入反应器后尚未形成颗粒,AnAOB直接暴露于曝气的环境之中,导致其活性被抑制. R2反应器SAOR和SAA在3个反应器中下降幅度最大,推测是由于微生物尚未适应负荷波动的环境,活性减弱.和阶段Ⅰ相比,阶段Ⅱ中SNOR尽管已经得到大幅度的降低,分别达到了4.87,4.65和5.08mg N/(g VSS·h);但是SAOR仍然较低,只有6.09,5.71和5.87mg N/(g VSS·h),此时氨氧化不完全成为了系统脱氮性能差的主要原因[43].
因此第47d调整曝气策略,进入阶段Ⅲ.在第56d时3组反应器的SAOR分别为7.92,7.79和8.07mg N/(g VSS· h),相较阶段Ⅱ有一定升高.此时3组反应器的SNOR仍在下降.有研究表明,形成成熟的CANON颗粒污泥是保证CANON系统中功能菌活性的前提[44].反应进行到84d,R1,R2和R3反应器的SNOR分别降低到2.76,2.68和2.54mg N/(g VSS·h),SAOR分别上升到9.56,9.78和9.65mg N/(g VSS·h),SAA上升到4.03,4.68和4.36mg N/(g VSS·h),3组反应器均成功实现了对NOB活性的选择性抑制.有研究发现,在低DO间歇曝气后,NOB活性被抑制同时相对丰度有一定下降,而在大颗粒中AnAOB的丰度显著上升[26].此阶段R2和R3的SAA的上升幅度相较于R1实现了较大的提升,与前人研究中anammox颗粒污泥的0.2~1.1g N/(g VSS· d)处于同一数量级[45].这说明微生物面对负荷的波动,将污泥絮体黏附起来[46],形成了分明的分层结构,外层的AOB大量消耗氧气,使得内部的AnAOB处于缺氧状态,使得R2和R3的SAA高于R1.
3.1 采用变量进水策略的实验组R2和R3经过90d的运行SVI最终分别稳定在53.10和57.59mL/g,且两者的f值基本呈现上升的趋势,维持在0.62左右,具有良好的沉降性能和生物活性.变量进水策略可以提高CANON系统污泥的沉降性能.
3.2 R2的TB-EPS中芳香族蛋白占比达到32.47%,显著高于R1的11.58%和R3的10.5%.结果显示变量进水的策略可以促进TB-EPS中芳香族蛋白的生成,进而提高污泥的疏水性,有利于污泥聚集.
3.3 R1,R2和R3的平均粒径分别达到了237.04,441.49和323.99μm.采用变量进水的策略易于形成AOB在外层,AnAOB位于内部的颗粒污泥结构,有利于保证功能菌的活性.
3.4 R2和R3在反应初期受到负荷波动的影响,微生物活性受到抑制,但很快得到适应,分别在54d和第51d实现了CANON工艺的启动.在第90d时,R1,R2和R3的总氮去除率分别达到了72.54%,70.14%和73.75%左右.
  • 北京高校卓越青年科学家计划项目(BJJWZYJH01201910005019)
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2025年第45卷第5期
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  • 接收时间:2024-10-12
  • 首发时间:2026-03-18
  • 出版时间:2025-05-20
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  • 收稿日期:2024-10-12
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北京高校卓越青年科学家计划项目(BJJWZYJH01201910005019)
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    1.北京工业大学水质科学与水环境恢复工程北京市重点实验室,北京 100124
    2.哈尔滨工业大学城市水资源与水环境国家重点实验室,黑龙江 哈尔滨 150090

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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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