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In this study, the components of dissolved organic matter (DOM) during the anaerobic-anoxic-aerobic (A2O) biological wastewater treatment process was analyzed by using fluorescence emission excitation matrix combined with parallel factor analysis(3D EEMs-PARAFAC), and the generation of nitrous oxide (N2O) in each unit was also quantified. Additionally, machine learning model was employed to further predict the response relationship between DOM components and N2O generation. Results showed that DOM in the influent of the wastewater treatment plants (WWTP) was primarily composed of four components, including tryptophan (C1), fulvic acid (C2), humic acid (C3), and tyrosine (C4), while C1 and C4 being the dominant components. The concentration of DOM decreased progressively throughout the treatment process, while the removal efficiency of readily biodegradable DOM (such as C1and C4) were significantly higher than that of C2 and C3. N2O emission was the major component of direct carbon emissions and showed significant spatial heterogeneity. The N2O emission amount of each unit ranked from high to low were observed in the following order: oxic tank, secondary sedimentation tank, anoxic tank, anaerobic tank, grille, and primary sedimentation tank. Shapley Additive exPlanation (SHAP) analysis revealed that C1 and C2 would significantly affect the N2O generation process, while the effects of C3 and C4 were negligible. Specifically, C1would enhance N2O generation, while C2 had an adverse effect. High-throughput sequencing results indicated that Methylotenera and Terrimonas, which could utilize readily biodegradable organic matter for denitrification, were the dominant bacterial genera in the sludge of WWTP. Overall, this study revealed disparate response between N2O generation and different DOM components during the A2O process, which would help to improve the current carbon emission accounting method of WWTPs and provide theoretical support for optimizing their low-carbon operation processes.

, correspAuthors=Zhen HU, 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=Hui-qi JIANG, Pei-han YU, Zhen HU, Yan-gang REN, Ze-yu HAO, Ke HAN, Chen-yang XUE, Jin-he WANG), CN=ArticleExt(id=1241408718865232138, articleId=1241408714519933112, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=A2O污水生物处理过程中DOM对N2O生成的影响, columnId=1234106386565624579, journalTitle=中国环境科学, columnName=水污染与控制, runingTitle=null, highlight=null, articleAbstract=

采用三维荧光-平行因子法(3D EEMs-PARAFAC)解析了厌氧-缺氧-好氧(A2O)污水生物处理过程中DOM特征,并对各工艺单元生成的N2O进行了定量分析,之后运用机器学习模型对二者的变化关系进行了响应预测.结果表明,污水处理厂进水中DOM主要包含类色氨酸C1,类富里酸C2,类腐殖酸C3和类酪氨酸C4四种组分,并以C1和C4为主,且各组分含量沿污水处理流程逐渐降低,易生物降解的C1和C4的去除速率明显高于C2和C3.N2O排放是直接碳排放的主要组成部分,其变化表现出明显的空间异质性,各处理单元N2O生成总量由高到低依次为好氧池、辐流沉淀池、缺氧池、厌氧池、细格栅、钟式沉砂池.Shapley Additive exPlanation(SHAP)分析表明,C1和C2对N2O生成影响较大,而C3和C4几乎没有影响,其中C1对N2O的生成表现出促进作用,C2则不利于N2O的生成.高通量测序结果表明,能够利用易生物降解有机物进行反硝化的MethyloteneraTerrimonas是污水处理厂内的优势菌属.本研究揭示了A2O污水生物处理过程中N2O生成对不同DOM组分的差异性响应,并为完善当前污水处理厂的碳排放核算方法并优化污水处理厂低碳运行工艺提供了理论支撑.

, correspAuthors=胡振, authorNote=null, correspAuthorsNote=
* 责任作者,教授,
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姜慧琪(2001-),女,河南周口人,山东大学硕士研究生,主要从事污水生物处理技术研究.发表论文8篇..

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姜慧琪(2001-),女,河南周口人,山东大学硕士研究生,主要从事污水生物处理技术研究.发表论文8篇..

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姜慧琪(2001-),女,河南周口人,山东大学硕士研究生,主要从事污水生物处理技术研究.发表论文8篇..

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运行参数数值
年处理水量(m3/a)7.3×107
进水COD(TN)平均浓度(mg/L)400(40)
出水COD(TN)平均浓度(mg/L)16(10)
碳源消耗量(t/10kt水)1
药剂消耗量(t/10kt水)0.50
耗电量(MW⋅h/a)34200
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进水COD(TN)平均浓度(mg/L)400(40)
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耗电量(MW⋅h/a)34200
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max depth6
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colsample bytree1.0
n estimators100
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A2O污水生物处理过程中DOM对N2O生成的影响
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姜慧琪 1 , 于沛涵 1 , 胡振 1, * , 任延刚 2, 3 , 郝泽育 1 , 韩珂 1 , 薛晨阳 3 , 王金鹤 4
中国环境科学 | 水污染与控制 2025,45(4): 1869-1877
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中国环境科学 | 水污染与控制 2025, 45(4): 1869-1877
A2O污水生物处理过程中DOM对N2O生成的影响
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姜慧琪1 , 于沛涵1, 胡振1, * , 任延刚2, 3, 郝泽育1, 韩珂1, 薛晨阳3, 王金鹤4
作者信息
  • 1.山东大学环境科学与工程学院,山东 青岛 266237
  • 2.中国科学院大学,北京 100049
  • 3.中国科学院生态环境科学研究中心,北京 100085
  • 4.山东建筑大学市政与环境工程学院,山东 济南 250101
  • 姜慧琪(2001-),女,河南周口人,山东大学硕士研究生,主要从事污水生物处理技术研究.发表论文8篇..

通讯作者:

* 责任作者,教授,
Effect of dissolved organic matter on N2O generation in A2O biological wastewater treatment process
Hui-qi JIANG1 , Pei-han YU1, Zhen HU1, * , Yan-gang REN2, 3, Ze-yu HAO1, Ke HAN1, Chen-yang XUE3, Jin-he WANG4
Affiliations
  • 1.School of Environmental Science and Engineering, Shandong University, Qingdao 266237, China
  • 2.University of Chinese Academy of Sciences, Beijing 100049, China
  • 3.Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
  • 4.School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan 250101, China
出版时间: 2025-04-20
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采用三维荧光-平行因子法(3D EEMs-PARAFAC)解析了厌氧-缺氧-好氧(A2O)污水生物处理过程中DOM特征,并对各工艺单元生成的N2O进行了定量分析,之后运用机器学习模型对二者的变化关系进行了响应预测.结果表明,污水处理厂进水中DOM主要包含类色氨酸C1,类富里酸C2,类腐殖酸C3和类酪氨酸C4四种组分,并以C1和C4为主,且各组分含量沿污水处理流程逐渐降低,易生物降解的C1和C4的去除速率明显高于C2和C3.N2O排放是直接碳排放的主要组成部分,其变化表现出明显的空间异质性,各处理单元N2O生成总量由高到低依次为好氧池、辐流沉淀池、缺氧池、厌氧池、细格栅、钟式沉砂池.Shapley Additive exPlanation(SHAP)分析表明,C1和C2对N2O生成影响较大,而C3和C4几乎没有影响,其中C1对N2O的生成表现出促进作用,C2则不利于N2O的生成.高通量测序结果表明,能够利用易生物降解有机物进行反硝化的MethyloteneraTerrimonas是污水处理厂内的优势菌属.本研究揭示了A2O污水生物处理过程中N2O生成对不同DOM组分的差异性响应,并为完善当前污水处理厂的碳排放核算方法并优化污水处理厂低碳运行工艺提供了理论支撑.

污水处理厂  /  氧化亚氮  /  溶解性有机物  /  厌氧-缺氧-好氧  /  碳排放

In this study, the components of dissolved organic matter (DOM) during the anaerobic-anoxic-aerobic (A2O) biological wastewater treatment process was analyzed by using fluorescence emission excitation matrix combined with parallel factor analysis(3D EEMs-PARAFAC), and the generation of nitrous oxide (N2O) in each unit was also quantified. Additionally, machine learning model was employed to further predict the response relationship between DOM components and N2O generation. Results showed that DOM in the influent of the wastewater treatment plants (WWTP) was primarily composed of four components, including tryptophan (C1), fulvic acid (C2), humic acid (C3), and tyrosine (C4), while C1 and C4 being the dominant components. The concentration of DOM decreased progressively throughout the treatment process, while the removal efficiency of readily biodegradable DOM (such as C1and C4) were significantly higher than that of C2 and C3. N2O emission was the major component of direct carbon emissions and showed significant spatial heterogeneity. The N2O emission amount of each unit ranked from high to low were observed in the following order: oxic tank, secondary sedimentation tank, anoxic tank, anaerobic tank, grille, and primary sedimentation tank. Shapley Additive exPlanation (SHAP) analysis revealed that C1 and C2 would significantly affect the N2O generation process, while the effects of C3 and C4 were negligible. Specifically, C1would enhance N2O generation, while C2 had an adverse effect. High-throughput sequencing results indicated that Methylotenera and Terrimonas, which could utilize readily biodegradable organic matter for denitrification, were the dominant bacterial genera in the sludge of WWTP. Overall, this study revealed disparate response between N2O generation and different DOM components during the A2O process, which would help to improve the current carbon emission accounting method of WWTPs and provide theoretical support for optimizing their low-carbon operation processes.

wastewater treatment plant (WWTP)  /  nitrous oxide (N2O)  /  dissolved organic matter (DOM)  /  anaerobic-anoxic-aerobic(A2O)  /  carbon emission
姜慧琪, 于沛涵, 胡振, 任延刚, 郝泽育, 韩珂, 薛晨阳, 王金鹤. A2O污水生物处理过程中DOM对N2O生成的影响. 中国环境科学, 2025 , 45 (4) : 1869 -1877 .
Hui-qi JIANG, Pei-han YU, Zhen HU, Yan-gang REN, Ze-yu HAO, Ke HAN, Chen-yang XUE, Jin-he WANG. Effect of dissolved organic matter on N2O generation in A2O biological wastewater treatment process[J]. China Environmental Science, 2025 , 45 (4) : 1869 -1877 .
研究表明,我国污水处理厂产生的二氧化碳(CO2)当量约18.7t/a,占全社会碳排放总量的1%~2%,污水处理厂已成为重要碳排放源[1].生物处理是当前我国普遍采用的污水处理方法,其中超过30%的污水处理厂采用厌氧-缺氧-好氧(A2O)工艺[2].A2O工艺过程中产生的碳排放可分为间接碳排放和直接碳排放,前者为污水处理厂运行期间的各种能耗和药耗,后者主要是来自生物反应过程中的温室气体如甲烷(CH4),氧化亚氮(N2O)的逸散.一般认为,间接碳排放是污水处理厂碳排放的主要贡献因子[3].然而,研究表明[4],全球范围内污水处理厂产生的直接碳排放量每年高达650Gg CO2-eq,与其能耗产生的间接碳排放量相当.因此,深入研究污水处理厂直接碳排放的产生机制并探索有效控制措施,对于全面实现污水处理厂的低碳运行至关重要.
作为生物脱氮过程中的副产物以及中间产物,N2O的全球变暖潜能在百年时间尺度是CO2的273倍,其对污水处理过程所造成温室效应贡献可达80%以上[5].因此,探索污水生物处理过程中N2O产生机制及其影响因素对降低污水处理厂直接碳排放具有重要意义.一般认为,污水生物处理过程中生成的N2O主要来源于生物脱氮时发生的各类反硝化过程[6].除某些特定细菌因缺失氧化亚氮还原酶(Nos),导致其反硝化作用的最终产物是N2O而非N2外,我国污水处理厂普遍存在进水碳氮比(C/N)偏低的问题,碳源不足往往导致Nos受抑制,使得中间产物N2O不能进一步被还原为氮气(N2),是反硝化作用中N2O大量积累的主要原因[7].因此,碳源作为微生物的能量来源以及反硝化过程的电子供体,能够直接影响N2O的生成.
在生物降解过程中,各种有机碳必须首先解聚并溶解在水中形成溶解性有机碳(DOC),才能被微生物分解利用[8].污水处理厂中化学需氧量(COD)的78.1%~86.5%由溶解性有机物(DOM)构成,它们作为微生物的电子供体和营养源与微生物的生长和代谢过程有着密切联系[9].在水体流动过程中DOM会不断发生光化学降解和微生物降解,改变水体溶解氧水平和氧化还原电位,影响N2O的生成[10].自然生态系统中,DOM与N2O生成存在显著关联.通过应用机器学习构建预测模型,有研究证明了河流生态系统中DOM浓度与N2O排放通量间存在正相关性[11].同时,溶解态N2O浓度还与水体中DOM的组成密切相关,河流水体中易降解的蛋白质类DOM能够促进N2O的产生释放[12],稻田中腐殖质类难降解的DOM组分与N2O的排放呈负相关关系[13].类似的,污水生物处理工艺内部存在不同的微环境和多样的微生物代谢机制,常伴随DOM组分含量以及N2O生成量的变化.然而,目前有关污水生物处理过程中DOM与N2O的沿程变化特征以及两者间的响应关系尚缺乏深入解析.
因此,本研究选取了以A2O为主体工艺的实际城市污水处理厂为研究对象,分析了工艺沿程DOM的迁移转化规律以及N2O生成特征,并结合机器学习模型量化了DOM各组分对N2O生成的影响;同时结合微生物群落结构特征分析,初步探讨了DOM影响N2O生成的微生物作用机制,为今后污水处理厂低碳运行相关工艺的优化提供了理论基础.
本研究所选污水处理厂位于山东省济南市,采用A2O工艺,处理能力为200000m3/d.进水组成主要是城市生活污水和小部分工业废水,进水中COD,BOD5,TN分别为400,150,40mg/L.设计出水水质达《城镇污水处理厂污染物排放标准》(GB18918-2002)一级A标准.
为研究污水处理过程中DOM转化及N2O生成规律,根据处理工艺功能区的划分,通过在系统沿程布点,于细格栅、钟式沉砂池、A2O生物反应池、辐流沉淀池各单元反应区分别布设采样点.具体工艺流程及采样点布设位置见图1.
于各采样点用氟化聚乙烯采样桶盛装采集污水水样并取3份平行样品,采集后的样品经过0.45µm醋酸纤维滤膜过滤,于48h内使用国家标准方法[14]对样品中的氨氮(NH4+-N),硝态氮(NO3--N),亚硝态氮(NO2--N),总氮(TN)和混合液挥发性悬浮固体浓度(MLVSS)进行测定.使用总有机碳分析仪(TOC-L,Shimadzu,Japan)测定水体溶解性有机碳(DOC)浓度,使用荧光分光光度计(F-4700,Hitachi,Japan)测定DOM的荧光激发发射矩阵(EEM).
于每日8:00,12:00,15:00,18:00在采样单元使用漂浮型气体通量箱进行气样采集(每2min采集一次,共采集3次),零气流量为15L/min,覆水面积为0.08m2,通过取样口用气体采样袋收集.气体中的N2O(CH4)浓度通过气相色谱仪(7890B,Agilent,USA)测定.N2O(CH4)的释放通量计算公式如下:
式中:F为N2O(CH4)释放通量,μg/(m2·min);C为N2O(CH4)浓度,10-6Fflush为载气流速,L/min;M为N2O(CH4)的摩尔质量,g/mol;P为采样时的大气压,kPa;T0为标准热力学温度,273K;22.4为气体标况摩尔体积常数,L/mol;S为通量箱覆水面积,m2p0为标准大气压,101kPa;T为采样时的环境温度,K.
在采集气体通量样品的同时,利用上部空间法对污水中的溶解态N2O进行采集测定[15].结合各单元尺寸参数,将单元内N2O释放量(mg)与N2O溶解量(mg)求和得到该单元N2O生成总量(mg).
从好氧池末端采集泥水混合样,使用冷冻离心机(5430R,Eppendorf,Germany)在转速为5000r/min,温度为4℃的条件下进行泥水分离获得底泥样品,将样本送往北京诺禾致源科技股份有限公司对微生物V3-V4区域的16S rRNA基因进行扩增和分析,并基于Illumina NovaSeq PE250平台进行高通量测序.微生物16S rRNA基因序列已提交至NCBI数据库中,登录号为PRJNA1194736.
本研究基于排放因子法,参照《IPCC国家温室气体清单指南》和《城镇污水处理厂污染物去除协同控制温室气体核算技术指南(试行)》提供的参数数据及核算方法,开展厂内碳排放核算.核算边界为厂内各污水处理单元,核算的碳排放类型有直接碳排放和间接碳排放,前者包括去除COD产生的碳排放,去除TN产生的碳排放以及外加碳源氧化产生的碳排放,后者包括电力消耗产生的碳排放和药剂消耗产生的碳排放.
CH4和N2O排放因子均通过实测数据计算所得;电力排放因子数据来源于生态环境部环境规划院发布的《中国区域电网二氧化碳排放因子研究(2023)》;其余污水厂的实际运行基础数据见表1.
为进一步量化DOM各组分对N2O生成的贡献,本文采用极限梯度提升(XGBoost)模型和Shapley Additive exPlanation (SHAP)算法对所采集的数据进行预测分析.XGBoost是一种基于梯度提升决策的改进算法,它可以高效地构建提升树,并解决分类和回归问题[16].图2为XGBoost的算法流程示意图,所输入的数据集为DOM组分相对比例及单位生物N2O生成量,其中分为80%测试集20%训练集.在模型评估阶段,选择均方根误差RMSE和R2分数作为模型预测效果的评估指标[17].表2展示了本研究中相关的XGBoost参数.SHAP用于解释模型的输出,使用博弈论中的Shapley值来解释模型的每个预测,同时提供了一种方法来理解模型的每个特征对个别预测结果的贡献大小[16].在本研究中,通过Summary Plot概要图表征各特征值的高低情况以及每个特征的正负贡献情况.
使用微软Office Excel 2021对原始数据进行处理,机器学习模型由Python完成,利用Matlab R2023b对EEM数据进行平行因子分析,其余绘图均由Origin 2024完成.
采用PARAFAC模型方法对EEM样本数据进行分析,共解析出了4种荧光组分.其中组分C1(Ex/Em=276/335nm和Ex/Em=230/335)以及组分C4(Ex/Em=220/332nm)为类色氨酸和类酪氨酸,属于蛋白质类荧光组分,具有较好的可生物降解性[18].组分C2(Ex/Em=317/387nm和Ex/Em=237/387nm)和C3(Ex/Em=256/446nm和Ex/Em=363/446nm)为类富里酸和类腐殖酸,属于腐殖质类荧光组分,生物可利用性较差[18].图3展示了污水处理厂沿程DOC浓度及DOM组分含量的变化情况.进入生化段后,DOC浓度呈现整体降低的趋势,表明生化段对DOM的削减起着关键作用.进水中的DOM组分主要为C1和C4,两者占比之和为80.9%.处理过程中,C1和C4的去除率分别为81.9%和100%,而C2和C3的去除率仅为20.4%和49.8%.Yu等[19]在对A2O污水处理厂中DOM进行表征的过程中同样发现,生物处理过程对色氨酸和酪氨酸表现出了较高去除率(58.78%~98.31%),而对腐殖质类物质的去除率仅在10%以下.这主要是因为低分子量DOM组分很容易被微生物同化,而腐殖质类物质则更顽固[20].
污水经过细格栅和钟式沉砂池后,DOM各组分含量并未发生明显变化,说明物化处理单元对水中有机物的去除贡献较低.当污水进入厌氧池后,DOM开始被活性污泥大量吸附降解,Tang等[21]在对A2O沿程DOM的变化研究中证实了厌氧处理环节在去除DOM过程中发挥着关键作用.易生物降解的C1和C4组分在厌氧池处荧光强度分别降低了68.9%和61.4%,说明微生物更倾向于首先利用其中易分解的不稳定物质[22].由于DOM在厌氧阶段已被大量吸附降解,因此缺氧池处DOM各组分含量的下降相较变缓,荧光强度下降值均在40%以下.好氧池和辐流沉淀池处C4组分含量有所下降,可能是相关反硝化菌消耗C4作为电子供体进行了反硝化过程.
污水处理厂碳排放核算结果显示,间接碳排放占污水厂总碳排放量的66.44%,处于Xi等[23]统计研究的数值范围内,其中电耗以及药耗产生的间接碳排放分别在总碳排放中占比53.95%和12.49%.直接碳排放在总碳排放中占比33.56%,N2O是直接碳排放的主要组成部分,其在总碳排放中占比11.44%,对总碳排放的贡献仅次于药耗.
图4(a)图4(b)分别展示了污水处理厂沿程N2O生成特征和水质中不同形态无机氮含量的变化.N2O的生成表现出较大的空间异质性,各处理单元N2O生成总量由高到低依次为好氧池(78198.15mg)、辐流沉淀池(39827.59mg)、缺氧池(21302.34mg)、厌氧池(15495.58mg)、细格栅(31.79mg)、钟式沉砂池(8.13mg).细格栅和钟式沉砂池水体中的DOM和NH4+-N几乎没有变化,表明在物化处理阶段中未进行明显的生物脱氮过程,但观测到较高溶解态N2O浓度和N2O释放通量.排水管道中形成的特定微生物群落在降解有机物的过程中,会产生大量温室气体,进而对下游污水厂的碳排放产生重要影响[24].因此污水管道中的微生物在进入污水处理厂之前可能进行了自然代谢活动,产生了一定量的N2O并溶解在水中,进入污水处理厂后,污水中溶解的部分N2O由于水面迅速变宽阔以及水流扰动而释放出来[25].厌氧池处由于污泥外回流的稀释作用,污泥吸附作用和微生物的降解,NH4+-N浓度,C1和C4组分均大量削减,并在该阶段观察到N2O总量明显的增长趋势,可能来源于反硝化过程N2O的产生和积累[26].A2O污水处理工艺中内回流携带的较多NO3--N在进入缺氧池后被反硝化菌迅速还原进行反硝化作用,因此在缺氧池处观察到较低NO3--N浓度(1.03mg/L)以及C1和C4组分含量的下降.由于污水流动过程中溶解态N2O的积累以及缺氧池反硝化过程生成N2O,导致了缺氧池处N2O总量高于厌氧池.好氧单元C4组分含量的下降可能是源于好氧反硝化菌的消耗,同时由于溶解态N2O的沿程积累效应,导致该单元溶解态N2O浓度高于厌氧池和缺氧池,在剧烈的曝气作用下,溶解的N2O从液面被吹脱至大气中,因此在该单元监测到了较高N2O释放通量(731.16mg/(m2·d)).Sun等人[27]在对全尺寸A2O污水处理工艺沿程N2O生成特征的研究中同样发现,在调研的所有污水处理单元中,好氧池处N2O释放通量最高.DOM和无机氮含量的变化表明辐流沉淀池有着良好的缺氧反硝化环境,由于该单元污泥停留时间较长,系统内仍有大量的微生物消耗C4进行反硝化作用产生N2O[26],导致该单元出现一定浓度的溶解态N2O (4.34μg/L),但由于水流相对平缓,并未观察到较多N2O的释放.
由上述分析可知,DOM降解与N2O生成的核心单元均位于生化处理阶段,微生物在其中发挥着核心作用.为了消除各工艺单元由于运行条件不同造成的数据差异,明确单位污水中微生物利用DOM不同组分对N2O生成的影响,基于训练好的XGBoost模型和SHAP算法,计算得到DOM各组分相对比例对单位生物N2O生成量(mg N2O/mg VSS)的SHAP绝对平均值,如图5(a)所示.DOM组分对N2O生成的影响程度各异,其中C2对N2O的生成影响程度最大,可以认为是主要的预测因子,C1影响程度次之,C3和C4对N2O的产生影响较小.图5(b)SHAP特征摘要图表明,随着C1相对比例的增大,其对N2O生成的促进作用更为明显.C2则表现出与C1相反的影响趋势,C2的相对比例越高,越不利于N2O的生成.C3和C4对N2O生成的影响较弱,不是预测N2O生成的关键特征.该结果与先前的研究结果一致.Amaral等[28]在探讨河口排放的温室气体与DOM组成间关系的过程中发现,N2O的产生与DOM中蛋白类物质密切相关,色氨酸组分会促进N2O的生成.Barnes等[29]发现蛋白质类荧光团与反硝化速率呈正相关关系,进而影响了反硝化过程中N2O的生成.与蛋白类组分相比,腐殖质类组分属于稳定的难降解有机物,不容易被细菌群落作为碳源利用.有研究表明,N2O的累积排放量与DOM的可利用性呈显著正相关关系,且易降解的类色氨酸等物质会在微生物的作用下逐渐转化为难降解的类腐殖质组分[30-31].因此,当水体DOM富含较多C1时,微生物代谢活动旺盛,更有利于反硝化作用的进行并产生N2O.然而,随着C1的不断消耗,C2的相对比例上升,此时由于缺乏易利用碳源,微生物的反硝化过程受到限制,N2O的生成随之减少.
对污水处理厂活性污泥的微生物群落特征进分析发现(图6),门水平上,污水处理厂中优势菌门包括变形菌门(Proteobacteria),拟杆菌门(Bacteroidota)和放线菌门(Actinobacteriota),其中变形菌门和拟杆菌门是反硝化的代表菌门.属水平上,主要优势菌属包括甲基营养型反硝化菌属(Methylotenera),硝化螺菌属(Nitrospira)和Terrimonas.Methylotenera中的某些特定菌种已被证明具有反硝化能力[32].Nitrospira是亚硝酸盐氧化的主要细菌,广泛存在于与氮循环相关的自然和工程生态系统中[33].Terrimonas是典型的好氧异养反硝化菌[34].从微生物群落的构成来看,与氮代谢相关的功能性菌群在污水处理厂中处于优势地位,表明该厂活性污泥具备良好的硝化和反硝化能力.
DOM组成特征以及微生物群落结构共同对N2O的生成起着重要调控作用.在本研究中,检测到的优势菌属大多具有反硝化能力,且对环境中碳底物非常敏感[32],当有较多易降解碳源C1时,微生物代谢过程活跃,反硝化过程增强并生成更多N2O[35].而随着C1不断被利用转化,难降解组分C2占比不断升高,无法为反硝化细菌提供充足的电子供体,导致反硝化菌群之间的竞争加剧,进而限制了微生物反硝化过程的进行并导致N2O的大量生成.Ding等[13]的研究支持了上述观点,DOM组成特性可能通过影响微生物群落功能调节N2O生成,其中色氨酸类物质和富里酸类物质与N2O排放量分别呈正相关和负相关关系.
因此,本研究建议污水处理厂在选择外加碳源时,除考虑去除效率和运行成本外,应尽量降低易生物降解物质组分的相对比例,以减少直接碳排放.此外,目前在对污水处理厂进行碳排放核算的过程中,温室气体排放因子一般都是直接选取IPCC提供的建议值,该值的确定只是源于N2O排放对氮输入响应的简单线性假设[36],忽略了对碳输入特别是碳源组分的响应.由于上述分析结果表明污水生物处理过程中DOM特征同样影响N2O的生成,因此建议把DOM组成特征值一并纳入对温室气体排放因子的计算中,并基于反应动力学机制构建N2O排放与DOM的时空动态关系模型,进而修正IPCC对N2O排放因子的建议值,从而提升碳排放核算结果的准确性.
3.1 采用3D EEMs-PARAFAC方法解析了污水生物处理工艺沿程DOM变化特征,发现物化处理阶段对DOM几乎没有影响,DOM各组分含量在进入生化段后逐渐降低;类色氨酸C1和类酪氨酸C4是水体DOM的主要组成,A2O污水处理工艺对两者的去除程度远大于类富里酸C2和类腐殖酸C3.
3.2 碳排放核算结果表明,N2O在直接碳排放中占比11.44%,其对总碳排放的贡献仅次于药耗.污水处理厂内N2O的生成表现出较大的空间异质性,各处理单元N2O生成总量由高到低依次为好氧池、辐流沉淀池、缺氧池、厌氧池、细格栅、钟式沉砂池.
3.3 通过SHAP模型算法解析并量化了DOM各组分对N2O生成的影响贡献,发现C2对N2O生成的影响程度最大,可以作为N2O生成的主要影响预测因子,C1次之,C3和C4则对N2O的生成几乎没有影响;其中C1对N2O的生成具有促进作用,C2则不利于N2O的生成.高通量测序的结果表明,该污水处理厂内的优势菌属为MethyloteneraNitrospiraTerrimonas,其中MethyloteneraTerrimonas有利用易生物降解有机物进行反硝化的能力.
3.4 本研究揭示了A2O污水处理工艺中N2O生成对不同DOM组分的差异性响应.为减少直接碳排放,建议污水处理厂选择外加碳源时,在保障处理效率与经济成本的同时,应尽量降低易生物降解物质组分的相对比例.此外,建议将DOM纳入N2O排放因子的计算中,以进一步提升碳排放核算结果准确性.
  • 国家自然科学基金资助项目(52170043)
  • 国家重点研发计划课题(2021YFC3200602)
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  • 收稿日期:2024-10-23
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国家自然科学基金资助项目(52170043)
国家重点研发计划课题(2021YFC3200602)
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    1.山东大学环境科学与工程学院,山东 青岛 266237
    2.中国科学院大学,北京 100049
    3.中国科学院生态环境科学研究中心,北京 100085
    4.山东建筑大学市政与环境工程学院,山东 济南 250101

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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
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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