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In Momoge Nature Reserve, three distinct water bodies were selected for the investigation of the composition, spectral characteristics, and sources of dissolved organic matter (DOM) utilizing three-dimensional excitation emission matrix spectroscopy in conjunction with parallel factor analysis (PARAFAC). Additionally, two-dimensional correlation spectroscopy combined with structural equation modeling was employed to analyze the variations of DOM components and their relationships with water quality parameters. The results indicated that the DOM in the water bodies originated from both endogenous and exogenous sources, which has obvious humification characteristics. Five components were identified as microbial metabolites (C1), fulvic acid-like (C2 and C4), humic acid-like (C3) and tryptophan-like (C5) through three-dimensional fluorescence coupled with PARAFAC. Of five components, C1content was the highest (41.37%). The changing sequence of DOM components along the direction of water flow was characterized by 2D-COS as follows: C4→C2→C3→C1→C5, with humic-like substances showing greater variation than tryptophan-like substances, and the content of tryptophan-like substances being relatively stable. The humification degree of DOM directly affected the water quality status with influence weight of 46.17%. The water quality was indirectly impacted by DOM components C2 and C3 with a 17.59% influence weight. Insight into the response mechanism of DOM properties to water quality in Momoge Nature Reserve could provide a theoretical basis for the ecological protection of nature reserves.

, correspAuthors=Feng QIAN, Yong-hui SONG, 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=Shan-shan ZHENG, Dong-ping LIU, Xiao-lin XIE, Feng QIAN, Hui-bin YU, Yong-hui SONG), CN=ArticleExt(id=1240689614286025410, articleId=1240689604525879458, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=莫莫格自然保护区水体DOM组成及其水质关联性, columnId=1234106388268503686, journalTitle=中国环境科学, columnName=环境生态, runingTitle=null, highlight=null, articleAbstract=

针对莫莫格自然保护区,选择3个水体,利用三维荧光光谱结合平行因子分析(PARAFAC)探究溶解性有机质(DOM)的组成、光谱特征和来源;采用二维相关光谱结合结构方程模型分析DOM组分变化及其与水质指标的响应关系.结果表明,水体DOM受内源和外源共同作用,腐殖化特征明显,蛋白质组分含量较低.PARAFAC共识别出微生物代谢产物(C1)、类富里酸(C2和C4)、类胡敏酸(C3)和类色氨酸(C5)等5种组分,其中C1组分含量最高(41.37%);DOM来源、组成、转化与保护区内水生动、植物生长环境下的微生物代谢过程紧密相关,采用2D-COS表征沿水流方向DOM组分的变化顺序为:C4→C2→C3→C1→C5,类富里酸(C2和C4)含量的变化幅度大于类色氨酸,类色氨酸的含量相对比较稳定.C1、C5组分与CODMn呈显著正相关,表明其具有同源性,主要来源于藻类生长死亡过程中产生的大量有机物.DOM来源和组成对水环境因子有直接或间接的影响,DOM主要通过腐殖化程度直接影响水质状态,影响权重为46.17%;DOM组分C2和C3间接影响水质状态,影响权重为17.59%.莫莫格自然保护区水体DOM组成与水环境因子响应机制的研究,可为自然保护区水生态保护提供理论依据.

, correspAuthors=钱锋, 宋永会, authorNote=null, correspAuthorsNote=
*责任作者,研究员,;
副研究员,
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郑珊珊(1999-),女,山东德州人,辽宁大学硕士研究生,主要研究方向为天然水体溶解性有机质光谱特征. .

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郑珊珊(1999-),女,山东德州人,辽宁大学硕士研究生,主要研究方向为天然水体溶解性有机质光谱特征. .

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ArticleFig(id=1240715197644592040, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689604525879458, language=EN, label=Table 1, caption=

Characteristics of five different components identified by the PARAFAC model

, figureFileSmall=null, figureFileBig=null, tableContent=
组分:Ex/EmEEM轮廓、光谱负载和EEM位置物质文献
C1:240(310)/420nm微生物代谢产物[41]
C2:265(365)/455nm类富里酸[42]
C3:290(390)/495nm类胡敏酸[43]
C4:260/445nm紫外光区类富里酸[44]
C5:225(280)/320nm类色氨酸[45]
), ArticleFig(id=1240715197724283818, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689604525879458, language=CN, label=表1, caption=

PARAFAC解析出的5个荧光组分特征

, figureFileSmall=null, figureFileBig=null, tableContent=
组分:Ex/EmEEM轮廓、光谱负载和EEM位置物质文献
C1:240(310)/420nm微生物代谢产物[41]
C2:265(365)/455nm类富里酸[42]
C3:290(390)/495nm类胡敏酸[43]
C4:260/445nm紫外光区类富里酸[44]
C5:225(280)/320nm类色氨酸[45]
), ArticleFig(id=1240715197820752812, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689604525879458, language=EN, label=Table 2, caption=

The weights of latent factors of water quality status

, figureFileSmall=null, figureFileBig=null, tableContent=
环境因子路径系数总权重(%)潜变量路径系数权重(%)观测变量路径系数因子权重(%)响应关系(%)
DOM来源1.08100DOM来源0.8982.41FI0.6243.9736.24
HIX0.7956.0346.17
DOM组成0.1917.59C20.9047.378.33
C31.0052.639.26
), ArticleFig(id=1240715197904638895, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689604525879458, language=CN, label=表2, caption=

水质状态影响因子权重赋值

, figureFileSmall=null, figureFileBig=null, tableContent=
环境因子路径系数总权重(%)潜变量路径系数权重(%)观测变量路径系数因子权重(%)响应关系(%)
DOM来源1.08100DOM来源0.8982.41FI0.6243.9736.24
HIX0.7956.0346.17
DOM组成0.1917.59C20.9047.378.33
C31.0052.639.26
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莫莫格自然保护区水体DOM组成及其水质关联性
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郑珊珊 1, 2 , 刘东萍 2 , 谢晓琳 2 , 钱锋 2, * , 于会彬 2 , 宋永会 2, **
中国环境科学 | 环境生态 2025,45(2): 1016-1026
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中国环境科学 | 环境生态 2025, 45(2): 1016-1026
莫莫格自然保护区水体DOM组成及其水质关联性
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郑珊珊1, 2 , 刘东萍2, 谢晓琳2, 钱锋2, * , 于会彬2, 宋永会2, **
作者信息
  • 1.辽宁大学环境学院,辽宁 沈阳 110036
  • 2.中国环境科学研究院,环境基准与风险评估国家重点实验室,北京 100012
  • 郑珊珊(1999-),女,山东德州人,辽宁大学硕士研究生,主要研究方向为天然水体溶解性有机质光谱特征. .

通讯作者:

*责任作者,研究员,;
副研究员,
The composition of DOM and its correlation with water quality in Momoge Nature Reserve
Shan-shan ZHENG1, 2 , Dong-ping LIU2, Xiao-lin XIE2, Feng QIAN2, * , Hui-bin YU2, Yong-hui SONG2, **
Affiliations
  • 1.College of Environment, Liaoning University, Shenyang 110036, China
  • 2.State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
出版时间: 2025-02-20
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针对莫莫格自然保护区,选择3个水体,利用三维荧光光谱结合平行因子分析(PARAFAC)探究溶解性有机质(DOM)的组成、光谱特征和来源;采用二维相关光谱结合结构方程模型分析DOM组分变化及其与水质指标的响应关系.结果表明,水体DOM受内源和外源共同作用,腐殖化特征明显,蛋白质组分含量较低.PARAFAC共识别出微生物代谢产物(C1)、类富里酸(C2和C4)、类胡敏酸(C3)和类色氨酸(C5)等5种组分,其中C1组分含量最高(41.37%);DOM来源、组成、转化与保护区内水生动、植物生长环境下的微生物代谢过程紧密相关,采用2D-COS表征沿水流方向DOM组分的变化顺序为:C4→C2→C3→C1→C5,类富里酸(C2和C4)含量的变化幅度大于类色氨酸,类色氨酸的含量相对比较稳定.C1、C5组分与CODMn呈显著正相关,表明其具有同源性,主要来源于藻类生长死亡过程中产生的大量有机物.DOM来源和组成对水环境因子有直接或间接的影响,DOM主要通过腐殖化程度直接影响水质状态,影响权重为46.17%;DOM组分C2和C3间接影响水质状态,影响权重为17.59%.莫莫格自然保护区水体DOM组成与水环境因子响应机制的研究,可为自然保护区水生态保护提供理论依据.

自然保护区  /  溶解性有机质  /  三维荧光光谱  /  结构方程模型  /  响应机制

In Momoge Nature Reserve, three distinct water bodies were selected for the investigation of the composition, spectral characteristics, and sources of dissolved organic matter (DOM) utilizing three-dimensional excitation emission matrix spectroscopy in conjunction with parallel factor analysis (PARAFAC). Additionally, two-dimensional correlation spectroscopy combined with structural equation modeling was employed to analyze the variations of DOM components and their relationships with water quality parameters. The results indicated that the DOM in the water bodies originated from both endogenous and exogenous sources, which has obvious humification characteristics. Five components were identified as microbial metabolites (C1), fulvic acid-like (C2 and C4), humic acid-like (C3) and tryptophan-like (C5) through three-dimensional fluorescence coupled with PARAFAC. Of five components, C1content was the highest (41.37%). The changing sequence of DOM components along the direction of water flow was characterized by 2D-COS as follows: C4→C2→C3→C1→C5, with humic-like substances showing greater variation than tryptophan-like substances, and the content of tryptophan-like substances being relatively stable. The humification degree of DOM directly affected the water quality status with influence weight of 46.17%. The water quality was indirectly impacted by DOM components C2 and C3 with a 17.59% influence weight. Insight into the response mechanism of DOM properties to water quality in Momoge Nature Reserve could provide a theoretical basis for the ecological protection of nature reserves.

nature reserve  /  dissolved organic matter  /  three-dimensional excitation emission matrix spectroscopy  /  structural equation modeling  /  response mechanism
郑珊珊, 刘东萍, 谢晓琳, 钱锋, 于会彬, 宋永会. 莫莫格自然保护区水体DOM组成及其水质关联性. 中国环境科学, 2025 , 45 (2) : 1016 -1026 .
Shan-shan ZHENG, Dong-ping LIU, Xiao-lin XIE, Feng QIAN, Hui-bin YU, Yong-hui SONG. The composition of DOM and its correlation with water quality in Momoge Nature Reserve[J]. China Environmental Science, 2025 , 45 (2) : 1016 -1026 .
溶解性有机质(DOM)通常是指能通过0.45µm滤膜的有机物,其结构中含有羟基、羧基、氨基等多种官能团[1],主要来源于土壤、动植物残体、活藻排泄物以及生活污水、农业径流和工业废水等人为负荷[2].DOM是水生态系统中有机碳的主要形式,在全球碳循环中起着至关重要的作用[3].DOM的含量及组成结构在时空分布上存在较大差异,对水体生态环境状况具有很好的指示作用[4-5].此外,DOM中的高化学活性组分,可通过络合与吸附作用影响重金属、氮、磷的形态和含量;可与污染物形成水溶性聚合物影响水生系统中化合物的生物利用度;还能够与水消毒剂反应产生致癌消毒副产物(DBP),潜在影响人体健康[6-7].
目前DOM表征方法主要有荧光光谱、色谱、紫外可见吸收光谱和核磁共振谱等技术.其中三维荧光光谱(3D-EEMs)作为一种简单、快速、高灵敏度和低成本的方法,已被广泛用于定量表征水生DOM及其在诸如河流、河口、湖泊、海水以及地下水等不同水环境中的动态变化.早期主要通过识别特定峰:A峰和C峰(代表腐殖质物质,包括腐殖酸和黄腐酸)、T峰和B峰(类似于色氨酸、苯丙氨酸和酪氨酸的蛋白质物质)、以及M峰(类似于微生物腐殖酸)等[8-9],定量表征DOM组分特征.
近年来,3D-EEMs与平行因子分析(PARAFAC)、区域积分和自组织图谱相结合来揭示DOM的结构组成和来源[10].二维相关光谱(2D-COS)是追踪复杂混合物(如DOM)在金属添加、pH值、时间和温度等外部扰动下细微响应的另一种有效技术[11-13].传统的2D-COS通常基于PARAFAC方法得出的最大荧光强度(Fmax)进行分析,无法识别不同组分之间的微小变化,而以水流方向为扰动因素,基于PARAFAC得出的激发载荷,能够区分不同组分之间的变化顺序[14].
松嫩平原在候鸟迁徙中扮演着重要的停歇地角色,大量学者对松嫩平原白鹤迁徙模式、土壤微生物组成、土壤剖面腐殖质分布特征及地下水氟和砷的动态变化等方面进行了研究[15-18],但尚缺乏对松嫩平原为代表的候鸟迁徙地水体DOM组成、来源等特征的了解.基于此,笔者以莫莫格自然保护区3个水体为研究对象,分析该区域水环境质量,利用3DEEMs-PARAFAC和2D-COS分析方法研究该保护区水体DOM的光谱特性,揭示DOM的分布、来源和组成;采用冗余分析(RDA)和结构方程模型(SEM)阐释水质和荧光组分的响应关系,旨在为莫莫格自然保护区水体水生态保护及水环境管理提供理论依据.
莫莫格自然保护区(45°42′25″~46°18′0″N,123°27′0″~124°4′34″E)位于吉林省白城市镇赉县东部,总面积1440km2.保护区内水系丰富、湖泊泡沼分布广泛,东部紧邻嫩江,南部为洮儿河,二龙涛河自西北流向东南,分别注入洮儿河和嫩江.该区域水源主要来自于区外地势较高地方的地下水、二龙涛河的地下潜流和大气降水,形成了泡沼相连的明水面.保护区位于欧亚大草原与东亚阔叶林的过渡地带,动植物资源丰富,主要植被类型为人工林、芦苇-碱蓬和农田植被,同时拥有丰富的野生动物资源,其中鸟类有17目55科298种,莫莫格自然保护区还是白鹤、东方白鹳等珍稀禽类与其他濒危物种的重要迁徙停歇地[19].
综合考虑研究区面积及湖盆形状、水动力条件、补排水条件等因素,采用网格式布设的方法,于2022年9月在莫莫格泡布设了19个地表水监测点位(图1),其中珠山泡设置了6个采样点(1#、2#、3#、4#、5#、14#),元宝吐泡设置了6个采样点位(6#、7#、8#、9#、12#、13#),局址岛设置了7个采样点(10#、11#、15#、16#、17#、18#、19#).用采样器采集0.5m深度的水样,装于1L无菌聚乙烯瓶中,并在10h内运输至实验室,于-20℃条件下保存.
采用便携式水质监测仪(YSI 600)现场测定pH值.采集的原水样于实验室测定化学需氧量(CODCr)、高锰酸盐指数(CODMn)、氨氮(NH3-N)、总氮(TN)、总磷(TP)、溶解性总固体(TDS)、五日生化需氧量(BOD5)和叶绿素a(Chl a),其中CODCr采用重铬酸钾法(GB 828—2017)测定;CODMn采用滴定法(GB 11892—89)测定;NH3-N采用纳氏试剂分光光度法(HJ 535—2009)测定;TN采用碱性过硫酸钾消解紫外分光光度法(HJ 636—2012)测定;TP采用钼酸铵分光光度法(GB 11893—89)测定;TDS采用重量法测定[20];BOD5采用稀释与接种法(HJ 505—2009)测定;Chl a采用分光光度法(HJ 897—2017)测定.
原水样经0.45 µm滤膜过滤后,使用F-7000型荧光分光光度计对DOM样品进行荧光测量.该仪器使用150W氙弧灯作为激发光源,PMT电压设定为700V.激发波长(Ex)范围为200~450nm,发射波长(Em)范围为260~550nm.扫描速度为2400nm/min,激发和发射带通宽度均为5nm,响应时间为0.5s.为了校正内滤效应,将Milli-Q超纯水作为空白对照样品,将其从所有样品的EEM中减去.按照先前研究方法[21],进行了一阶和二阶瑞利散射和拉曼散射的去除.使用Ex为350nm、Em为371 ~ 428nm的拉曼散射峰下的面积将荧光发射矩阵(EEM)转换为拉曼单位(R.U.).
使用MATLAB R2021b中的drEEM工具箱(版本0.6.3),基于保护区采集的样本3D-EEMs进行PARAFAC建模[22].使用非负性约束的2~7组分模型计算PARAFAC,然后使用核心一致性检验、残差分析和拆半分析确定荧光组分的数量,通过输出的Fmax估算每个PARAFAC组分的丰度百分比[23].通过日本关西大学开发的“2D Shige”软件,利用各组分的激发波长绘制同步异谱图和异步异谱图,获得DOM各组分的变化顺序[24-25].基于OpenFluor数据库对DOM组分进行筛分对比,采用Canoco 5.0软件进行RDA分析,利用AMOS 27软件构建结构方程模型,利用Origin 2023进行其他图形的绘制.
本研究以pH值、TDS、CODCr、CODMn、TN、NH3-N、TP、Chl a和BOD5等9项指标的浓度指示莫莫格自然保护区水体的水环境质量(图2),可以看出,保护区水体整体的pH值介于7.69~8.92,均值8.31,呈现弱碱性,与该区域水化学类型密切相关[26];CODCr和CODMn的平均浓度分别为42和11.68mg/L,高于《地表水环境质量标准》(GB 3838—2002)Ⅴ类标准.而TP、TN和NH3-N的平均浓度分别为0.07,0.82和0.47mg/L,达到《地表水环境质量标准》(GB 3838—2002)Ⅲ类标准.3个水体中的CODCr、CODMn、TDS和TN浓度均呈现出局址岛>元宝吐泡>珠山泡的规律;而TP、Chl a与BOD5浓度在空间上变化趋势与之相反.
利用3D-EEMs来识别DOM荧光峰的特征,具有直观且省时的优点[27].3个水体中典型的三维荧光光谱如图3所示,尽管强度存在差异,但类腐殖质样区域(Ex:300~400nm,Em:400~500nm)和类色氨酸区域(Ex:225~237/270~280nm,Em:330~370nm)存在7个明显的荧光峰[28-30].值得注意的是,具有难降解特征的类胡敏酸荧光峰(峰H和F)在水生和陆地环境中被广泛发现,该组分具有高分子量的疏水结构[31],并被证明可以保护蛋白质物质免受生物降解[32].各采样点的光谱轮廓非常相似,类腐殖质区域荧光强度最强,表明类腐殖质组分在各采样点中均占主导地位,且比其他有机成分更难降解.类腐殖质峰一般表征陆源性有机物质,多数来源于植物残留物的降解产物.
整体而言,珠山泡采样点中的色氨酸样和腐殖质样物质的含量明显较低,荧光强度低于其他采样点.采样点13#位于研究区北侧点位,峰A荧光强度最高,表明研究区域北侧水体有机物以降解产物类富里酸物质为主;由于采样点13#对采样点9#处水体的补给作用,使得采样点9#附近水质变差.采样点15#的A峰和C峰的荧光强度最大,说明该采样点主要以藻类及浮游植物代谢、腐解产生的内源污染为主;而采样点16#的水质有所提升,与该点位所在区域的水生植被相对较少有关.
根据3D-EEMs计算了荧光指数(FI)、腐殖化指数(HIX)和自生源指数(BIX),这3个指数经常用于分析和揭示DOM的来源和组成.FI能较好地反映芳香性和非芳香性氨基酸对于DOM荧光强度的相对贡献,被认为是DOM来源和降解程度的指示因子[33].从图4(a)看出,各采样点FI值介于1.53~1.60,差异不大,说明研究区域地表水体受到内源与外源的双重影响.HIX是衡量DOM腐殖化程度的常用指标,数值越高表明其腐殖化水平越高,芳香性越强[34].由图4(b)可知,HIX值均大于0.8,介于0.87~0.91之间,HIX值呈现出珠山泡>元宝吐泡>局址岛的规律,其中珠山泡的HIX值最高,说明研究区域北部地区地表水腐殖化程度普遍较强,可能是由于该地区木质素含量高的水生植物密度较大,土壤有机质较高,进入水体的腐殖酸类DOM含量较多.BIX用于表征DOM中内源性物质的比例,该研究区域呈现出珠山泡>元宝吐泡>局址岛的变化趋势,各采样点BIX值均小于0.8,表明该区域水体整体上自生源贡献较少,即类蛋白组分占比较少,生物可利用性低,可能是由于9月份浮游植物和藻类生长旺盛产生较多的有机质,水体中的自生源有机质在微生物作用下发生降解,逐步转化为腐殖质.该研究区域所在保护区与辽河保护区和太白山保护区水体类似,DOM受外源与内源共同影响,蛋白质组分含量较低,呈现出腐殖化较高的特点,人类活动对DOM的影响不大[35-36].
基于对3D-EEMs数据的PARAFAC建模,从莫莫格自然保护区水体中识别出5个DOM组件,其EEM轮廓、位置和Ex/Em负载如表1所示.组分1(C1)被认为是微生物代谢产物,对应传统峰中的M峰,可能来源于微生物及水中藻类降解产生的芳香族高分子物质,为新产生且相对不稳定的DOM组分,与生物活动相关,在湿地和农业等环境中较为常见[37].组分2(C2)由两个峰组成,该组分光谱特征类似于陆源类腐殖质中的类富里酸A和C,主要源于有机物的光降解产物及微生物氧化产物;组分3(C3)具有H和F荧光峰的特征,指示类胡敏酸物质,主要源于木质素等物质的降解,表征DOM的腐殖化程度,为相对较稳定的组分;组分4(C4)属于紫外光区类富里酸,与传统A峰相比有一定的红移,可能反映了更多的太阳辐射对该研究区域水体的影响,据报道该组分是光产物和/或光难降解成分[38];组分5(C5)对应于类色氨酸物质,与藻类、浮游植物释放物质等内源污染有关.
莫莫格自然保护区19个采样点的DOM荧光组分的荧光强度和相对比例分布情况如图5所示.可以看出,C1和C2的荧光强度在各个采样点中均最高,说明该研究区域以类富里酸和微生物代谢产物为主,与寻峰法溯源结果特征一致(图3).C3和C5的荧光强度呈现出平行的数值,这意味着类胡敏酸和酪氨酸样组分的相对含量非常相似,相同的变化模式表明,DOM的不同化学构成导致其在稳定性和生物降解能力上存在差异[39].除采样点12#外,元宝吐泡其他采样点的荧光强度普遍高于珠山泡和局址岛的荧光强度,主要体现在微生物代谢产物和类腐殖质组分,表明元宝吐泡附近水体有机物的光降解与微生物降解过程较为活跃,与该区域水生植物及浮游生物的丰富度较大有关.采样点12#附近水体各组分荧光强度均最低,其布设在三分干渠上,表明附近水体对莫莫格泡的补给作用,使得泡内水质有所提升.局址岛各采样点水体DOM组分的荧光强度波动较大,说明汇水区的分布可能由于水流流向的不同而影响DOM组分的含量.区域DOM组分的相对分布在空间上几乎没有差异,其中代表自生源类腐殖质组分C1占主导地位,为41.37%,说明9月份莫莫格泡水体的微生物活性较高;其次是C2和C4,占34.73%,与陆地输入有关;蛋白类物质C5占比较低(12.61%),说明人为因素对水体中的有机质影响较小,污染物主要与鸟类鱼类等动物的排泄物、底泥内源释放以及水生植物有关.综上,研究区域水体主要以类腐殖质(C1、C2和C4)为主,类腐殖质多为分子量和芳香性较高的有机物质,主要受水生植物、藻类或底泥的影响,这与夏季潮河流域的特征类似,马卓妮等[40]在潮河流域水体中提取出4种荧光组分,其中类腐殖质物质占比最高(83%±11%),其来源主要是河流底泥或水生植物根际有机质的溶出.
采用2D-COS表征沿水流方向DOM组分的变化顺序(图6).在同步光谱图中(图6(a)),C2与C4呈正相关关系,在异步光谱图中(图6(b)),C2与C4呈负相关关系,根据Noda规则,荧光组分的变动顺序为C4→C2.在同步光谱图(图6(c))和异步光谱图(图6(d))中,C2与C3均呈正相关关系,表明荧光组分的变化顺序为C2→C3.C1与C3的荧光峰在同步图谱上呈正相关(图6(e)),而在异步图谱上呈负相关(图6(f)),因此,C1和C3的变动顺序为C3→C1.在C1与C5的同步和异步图谱上(图6(g)和(h)),两者的荧光峰都呈现正相关,即C1→C5.综上分析,DOM组分的变化顺序为:C4→C2→C3→C1→C5,这表明类腐殖质含量的变化幅度大于蛋白类物质,类色氨酸的含量相对比较稳定,间接证明了该研究区域生活污水排放较少,受人类活动的影响较少.
基于荧光组分、荧光指数和环境因子对研究区域进行相关性分析(图7),结果表明,C2和C3具有显著相关性(P<0.01),表明C2和C3具有同源性,均来源于陆源类腐殖质.C5与C1、C4之间也呈现显著相关性,朱爱菊等[46]对亚热带入海河流处养虾塘水体的研究也显示类腐殖质与类蛋白质之间有较强的相关性;此外有研究表明陆源类腐殖质与海洋源类腐殖质也可由相同荧光团产生[47].水体中的Chl a可在一定程度上揭示内源有机质生产潜力,该研究区域内Chl a与C4和C5组分呈显著相关性,表明水体DOM降解转化过程中生物作用显著[48].C1、C5组分与CODMn存在显著正相关(P<0.01),可能是由于藻类在生长和死亡过程中产生大量有机物,这些有机物在降解过程中会进一步导致水体中的CODMn浓度升高.C4与TP、TN呈显著相关(P<0.01),C1与TN呈显著相关性(P<0.05).C5和TP之间存在着显著的负相关关系(P<0.01),说明色氨酸浓度的增加会导致P营养盐含量下降,这可能与P营养元素是蛋白质类有机质中的重要组成成分有关.孟永霞等[49]研究表明,匹里青河中DOM荧光组分与TN、TP等相关性较好.冯可心等[50]在对丹江口水库的研究中发现,TP和TN等营养盐与DOM组分存在显著相关性.由此可见,水体中的DOM荧光组分及特征与N、P等元素的迁移转化密切相关.HIX与C3、C4存在显著正相关(P<0.05),与C5呈显著负相关(P<0.01),FI与C4组分存在显著相关性(P<0.01),这反映了该研究区域水体中DOM组分及其来源之间具有一致性的变化规律[48].陶勇等[51]在对临江河的研究中也发现,HIX与类腐殖质组分存在显著的正相关关系(P<0.01),与类蛋白质组分存在显著的负相关关系(P<0.01).总体来看,DOM组分对研究区域水体水质指标具有一定的环境指示意义.
采用Canoco 5.0软件对地表水体样本的水环境因子与DOM荧光组分进行RDA分析(图8),以识别影响该地区DOM分布的主控因子,同时也为构建SEM模型做基础数据准备.可以看出,RDA1和RDA2共同解释了总体变化的90.26%,其中CODMn、TN和CODCr是影响各采样点水体DOM分布的主要环境因子.水体DOM荧光组分特征受多种环境因子共同影响,其中DOM组分与TN、CODMn、CODCr、TDS和NH3-N存在显著正相关,与TP和BOD5呈显著负相关.各采样点主要分布在两个排序轴相交处,反映了研究区域水质状况较为统一,空间差异并不明显.综上,CODMn、TN和CODCr是影响研究区域水体中DOM分布的主要环境因子.
DOM来源和组成对水质参数有一定影响[52].为进一步探究DOM与水环境因子的关联性,根据RDA分析结果,设置DOM来源、DOM组成和水质指标作为潜变量,以各潜变量对应的荧光指数、DOM荧光组分和水体理化指标作为观测变量,建立了以水质指标为模型出口的DOM荧光组分与主要环境因子的响应关系概念模型.
基于上述概念模型,利用AMOS 27软件对模型参数进行估计,选取最大似然法进行参数估计,得到模型评价指标和路径系数(图9).DOM来源、组成与水质的响应关系模型评价指标主要表现为:卡方值=18.541,P=0.356>0.05,说明样本数据协方差矩阵与隐含协方差矩阵不存在显著的差异,样本数据能够较好拟合模型;卡方自由度比为1.091,介于1~3之间.GFI为0.827,CFI为0.989,TLI为0.981,IFI为0.989,NFI为0.886,RFI为0.812,这几个指标均符合0.8或0.9的评判标准;RMSEA值为0.071,符合0.08的评判标准.PCFI为0.600、PNFI为0.538,符合0.5的评判标准.上述拟合度指标均符合一般的判断标准,表明模型拟合度良好,可以基于模型路径系数进一步分析变量间的相关性,解析DOM来源、组成与水质的响应关系.
根据构建的模型中各变量之间的路径系数(图9),可以进一步计算得出DOM来源、组成对水质状态的影响权重(表2).在SEM中,将各因子的路径系数与总路径系数的比值作为该因子的权重.SEM分析表明,DOM的来源及组成结构对水质状态存在直接或间接的影响,基于表中各指标的权重赋值,通过权重加权叠加方法,获得DOM来源及组分对水质状态影响的综合评价结果.DOM来源主要有两条路径影响水质状态,一条直接路径以及一条间接路径.直接路径对水质因子的影响权重为82.41%,远大于间接路径对水质因子的影响权重(17.59%),直接影响权重主要通过FI(36.24%)和HIX(46.17%)影响水质状态.其通过DOM组成间接对水质状态的影响权重为17.59%,包括类富里酸(C2)和类胡敏素(C3),影响权重分别为8.33%和9.26%.综上,DOM来源和组成可以直接或间接影响水质状态,其主要通过腐殖化程度(HIX)直接影响水质状态,通过DOM组分(C2和C3)间接影响水质状态.
3.1 自然保护区水体DOM具有外源与内源双重特性,自生源贡献较弱,腐殖化程度较强,与该区域水生植物及浮游生物的丰富度较大有关.
3.2 自然保护区水体DOM包括微生物代谢产物(C1)、类富里酸(C2和C4)、类胡敏酸(C3)和类色氨酸(C5)等5种组分,其中C1组分含量最高(41.37%);DOM组分的变化顺序为:C4→C2→C3→C1→C5,类腐殖质含量的变化幅度大于类色氨酸,类色氨酸的含量相对比较稳定.
3.3 相关性分析和冗余分析发现,C1、C5组分与CODMn呈显著正相关,CODMn、TN和CODCr是影响研究区域水体中DOM分布的主要环境因子.
3.4 DOM来源和组成可直接或间接影响水质状态,DOM主要通过腐殖化程度直接影响自然保护区水质状态,影响权重为46.17%;DOM组分C2和C3间接影响自然保护区水质状态,影响权重分别为8.33%和9.26%.
  • 长江生态环境保护修复联合研究项目(第二期)(2022-LHYJ-02-0304)
  • 国家重点研发计划项目(2021YFC3201500)
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2025年第45卷第2期
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  • 接收时间:2024-08-01
  • 首发时间:2026-03-17
  • 出版时间:2025-02-20
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  • 收稿日期:2024-08-01
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长江生态环境保护修复联合研究项目(第二期)(2022-LHYJ-02-0304)
国家重点研发计划项目(2021YFC3201500)
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    1.辽宁大学环境学院,辽宁 沈阳 110036
    2.中国环境科学研究院,环境基准与风险评估国家重点实验室,北京 100012

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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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