派河水体中DOM的光谱分析及其来源解析
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摘要
派河是环巢湖流域重要入湖河流,为加强该流域环境综合治理,改善水环境质量,采集派河入河口水样,通过三维荧光光谱和紫外-可见吸收光谱,结合平行因子分析模型及相关性分析,进行DOM(dissolred organic matter,溶解性有机物)光谱学特性研究,分析派河水体DOM荧光组分来源及特征.结果表明:(1)水体中DOM含2类4种荧光组分,其中,类蛋白物质荧光组分(类色氨酸和类酪氨酸)占总组分荧光强度的68. 1%,类富里酸物质(紫外类富里酸和可见类富里酸)占总组分荧光强度的31. 9%;(2)采样点FI (荧光指数)大于1. 9,BIX (生物源指数)大于1. 0,派河上游HIX (腐殖化指数)小于1. 5,下游HIX范围为1. 5～3,表明派河DOM具有明显的生物源特征,水体腐殖化程度较低,上覆水体浮游动植物和生物细菌分布均匀且对水体环境有明显影响;(3)紫外-可见光吸收系数[a(280)和a(355)]可很好地表征派河水体中DOM相对含量,紫外-可见吸收光谱测定结果显示,水体中含大量性质相对稳定的有机物;(4)紫外类富里酸和类酪氨酸的荧光强度均与a(280)、a(355)呈显著正相关,表明水体DOM中紫外类富里酸和类酪氨酸组分的产生及来源具有一致性或相伴发生.研究显示,光谱分析法可有效表征派河水体中DOM兼具陆源和生物来源的双重特性.
In order to strengthen the environmental management and improve the quality of water environment in the Chaohu Lake,the parallel factor analysis model and correlation analysis, three-dimensional fluorescence excitation-emission matrix( 3 D-EEM) and ultraviolet-visible absorption spectrum( UV-Vis) were used to study the source and characteristics of DOM in water samples collected from the Pai River,one of the tributary rivers to the Chaohu Lake. The results showed that:( 1) There are four kinds of fluorescent components in the DOM,of which the protein-like substances( including tryptophan and tyrosine) and fulvic acid-like substances( including ultraviolet fulvic acid-like and visible fulvic acid-like) accounted for 68. 1% and 31. 9% of the total fluorescence intensity components,respectively.( 2) For the collected DOM,the fluorescence index( FI) was higher than 1. 9 and the biological index( BIX) was over 1. 0.The humification index( HIX) was less than 1. 5 in the upstream and varied from 1. 5 to 3 in the downstream. These indexes indicated that the DOM in the Pai River had obvious biological source characteristics,and the degree of water humification is relatively low. The zooplankton and biological bacteria in the overlying water body were uniform and their activities had obvious influence on the water environment.( 3) UV-Vis could be used to identify the relative size of the DOM and UV-Vis analysis revealed that the DOM contained a lot of relatively stable organic matter.( 4) The fluorescence intensity and ultraviolet-visible absorption coefficient[a( 280) and a( 355) ]of ultraviolet fulvic acid-like and tyrosine exhibited significant correlation,indicating that the sources and generation of component ultraviolet fulvic acid-like and tyrosine are consistent or concomitant. This study indicated that the spectral analysis can effectively track the land and biological source of DOM in Pai River.
In order to strengthen the environmental management and improve the quality of water environment in the Chaohu Lake,the parallel factor analysis model and correlation analysis, three-dimensional fluorescence excitation-emission matrix( 3 D-EEM) and ultraviolet-visible absorption spectrum( UV-Vis) were used to study the source and characteristics of DOM in water samples collected from the Pai River,one of the tributary rivers to the Chaohu Lake. The results showed that:( 1) There are four kinds of fluorescent components in the DOM,of which the protein-like substances( including tryptophan and tyrosine) and fulvic acid-like substances( including ultraviolet fulvic acid-like and visible fulvic acid-like) accounted for 68. 1% and 31. 9% of the total fluorescence intensity components,respectively.( 2) For the collected DOM,the fluorescence index( FI) was higher than 1. 9 and the biological index( BIX) was over 1. 0.The humification index( HIX) was less than 1. 5 in the upstream and varied from 1. 5 to 3 in the downstream. These indexes indicated that the DOM in the Pai River had obvious biological source characteristics,and the degree of water humification is relatively low. The zooplankton and biological bacteria in the overlying water body were uniform and their activities had obvious influence on the water environment.( 3) UV-Vis could be used to identify the relative size of the DOM and UV-Vis analysis revealed that the DOM contained a lot of relatively stable organic matter.( 4) The fluorescence intensity and ultraviolet-visible absorption coefficient[a( 280) and a( 355) ]of ultraviolet fulvic acid-like and tyrosine exhibited significant correlation,indicating that the sources and generation of component ultraviolet fulvic acid-like and tyrosine are consistent or concomitant. This study indicated that the spectral analysis can effectively track the land and biological source of DOM in Pai River.
引文
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[12]姚昕,张运林,朱广伟,等.湖泊草、藻来源溶解性有机物及其微生物降解的差异[J].环境科学学报,2014,34(3):688-694.YAO Xin,ZHANG Yunlin,ZHU Guangwei,et al. Different degradation mechanism of dissolved organic matter derived from phytoplankton and macrophytes in Lake Taihu,China[J]. Acta Scientiae Circumstantiae,2014,34(3):688-694.
[13] YE Linlin,WU Xiaodong,LIU Bo,et al. Dynamics and sources of dissolved organic carbon during phytoplankton bloom in hypereutrophic Lake Taihu(China)[J]. Limnologica-Ecology and Management of Inland Waters,2015,54:5-13.
[14] BAI Ying,SU Rongguo,SHI Xiaoyong. Assessing the dynamics of chromophoric dissolved organic matter in the southern Yellow Sea by excitation:emission matrix fluorescence and parallel factor analysis(EEM-PARAFAC)[J]. Continental Shelf Research,2014,88:103-116.
[15]张广萍,周美正,张延,等.安徽派河流域水污染特征及原因分析[J].人民长江,2014(18):20-24.
[16] CORY R M,MCKNIGHT D M. Fluorescence spectroscopy reveals ubiquitous presence of oxidized and reduced quinones in dissolved organic matter[J]. Environmental Science&Technology,2005,39(21):8142-8149.
[17] MURPHY K R,BUTLER K D,SPENCER R G,et al.Measurement of dissolved organic matter fluorescence in aquatic environments:an interlaboratory comparison[J]. Environmental Science&Technology,2010,44(24):9405-9412.
[18] JAFFE R,BOTER J N,LU X,et al. Source characterization of dissolved organic matter in a subtropical mangrove-dominated estuary by fluorescence analysis[J].Marine Chemistry,2004,84(3/4):195-210.
[19] ZSOLNAY A,BAIGAR E,JIMENEZ M,et al. Differentiating with fluorescence spectroscopy the sources of dissolved organic matter in soils subjected to drying[J].Chemosphere,1999,38(1):45-50.
[20] ZHANG Yunlin,ZHANG Enlou,YIN Yan,et al.Characteristics and sources of chromophoric dissolved organic matter in lakes of the Yungui Plateau,China,differing in trophic state and altitude[J].Limnology and Oceanography,2010,55(6):2645-2659.
[21] ZHANG Yunlin,MARK-VAN D,LIU Mingliang,et al. The contribution of phytoplankton degradation to chromophoric dissolved organic matter(CDOM)in eutrophic shallow lakes:field and experimental evidence[J]. Water Research,2009,43(18):4685-4697.
[22] BATTIN T J.Dissolved organic matter and its optical properties in a blackwater tributary of the upper Orinoco River,Venezuela[J].Organic Geochemistry,1998,28(9/10):561-569.
[23] COBLE P G. Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy[J]. Marine Chemistry,1996,51(4):325-346.
[24] CHEN Jie,LEBOEUFE J,DAI Sheng,et al. Fluorescence spectroscopic studies of natural organic matter fractions[J].Chemosphere,2003,50(5):639-647.
[25] CHEN Wen,WESTERHOFF P,LEENHEER J A,et al.Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter[J]. Environmental Science&Technology,2003,37(24):5701-5710.
[26] NEBBIOSO A,PICCOLOA.Molecular characterization of dissolved organic matter(DOM):a critical review[J]. Analytical Bioanalytical Chemistry,2003,405(1):109-124.
[27] BIRDWELL J E,ENGEL A S.Characterization of dissolved organic matter in cave and spring waters using UV-Vis absorbance and fluorescence spectroscopy[J].Organic Geochemistry,2010,41(3):270-280.
[28] HUGUET A,VACHER L,RELEXAN S S,et al. Properties of fluorescent dissolved organic matter in the Gironde Estuary[J].Organic Geochemistry,2009,40(6):706-719.
[29] WEISHAAR J L,AIKEN G R,BERGAMASCHI B A,et al.Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon[J].Environmental Science&Technology,2003,37(20):4702-4708.
[30] JAFFRAIN J,GERARD F,MEYERM,et al.Assessing the quality of dissolved organic matter in forest soils using ultraviolet absorption spectrophotometry[J]. Soil Science Society of America Journal,2007,71(6):1851-1858.
[31] STEDMON C A,MARKAGER S,KAAS H.Optical properties and signatures of chromophoric dissolved organic matter(CDOM)in danish coastal waters[J]. Estuarine Coastal and Shelf Science,2000,51(2):267-278.
[32] GUO Wendong,STEDMON C A,HAN Yuchao,et al. The conservative and non-conservative behavior of chromophoric dissolved organic matter in Chinese estuarine waters[J]. Marine Chemistry,2007,107(3):357-366.
[33]王福利,郭卫东.秋季南海珠江口和北部湾溶解有机物的光降解[J].环境科学学报,2010,30(3):606-613.WANG Fuli,GUO Weidong.Photodegradation of DOM in the Pearl River Estuary and the Beibu Gulf of the South China Sea in autumn[J].Acta Scientiae Circumstantiae,2010,30(3):606-613.
[34] ZHANG Yunlin,LIU Mingliang,QIN Baoqiang,et al.Photochemical degradation of chromophoric-dissolved organic matter exposed to simulated UV-B and natural solar radiation[J]. Hydrobiologia,2009,627(1):159-168.
[35]闫红丽.基于三维荧光光谱-平行因子分析技术的黄东海有色溶解有机物(CDOM)的分布特征研究[D].青岛:中国海洋大学,2012.
[36]江俊武,李帅东,沈胤胤,等.夏季太湖CDOM光学特性空间差异及其来源解析[J].环境科学研究,2017,30(7):1020-1030.JIANG Junwu,LI Shuaidong,SHEN Yinyin,et al. Spatial differences of optical properties of CDOM and their source apportionment in Taihu Lake in Summer[J]. Research of Environmental Sciences,2017,30(7):1020-1030.
[37]祝鹏,华祖林,张润宇,等.太湖溶解有机质光谱和氮磷污染的区域分布差异特征[J].环境科学研究,2010,23(2):129-136.ZHU Peng,HUA Zulin,ZHANG Runyu,et al. Characteristics of spatial distribution differences of spectrum of dissolved organic matter and nitrogen/phosphorus pollution in Taihu Lake[J].Research of Environmental Sciences,2010,23(2):129-136.
[38] CHEN Zhiqiang,LI Yan,PAN Jianming. Distributions of colored dissolved organic matter and dissolved organic carbon in the Pearl River Estuary,China[J]. Continental Shelf Research,2004,24(16):1845-1856.
[2] SULZBERGER B,DURISCH-KAISER E.Chemical characterization of dissolved organic matter(DOM):a prerequisite for understanding UV-induced changes of DOM absorption properties and bioavailability[J].Aquatic Sciences,2009,71(2):104-126.
[3] CHEN M,PRICE R M,YAMASHITA Y,et al.Comparative study of dissolved organic matter from groundwater and surface water in the florida coastal everglades using multi-dimensional spectrofluorometry combined with multivariate statistics[J].Applied Geochemistry,2010,25(6):872-880.
[4] KAMJUNKE N,TUMPLING W V,HERTKOMN,et al. A new approach for evaluating transformations of dissolved organic matter(DOM)via high-resolution mass spectrometry and relating it to bacterial activity[J].Water Research,2017,123:513-523.
[5] ZHENG Liuchun,SONG Zhaofeng,MENG Peipei,et al. Seasonal characterization and identification of dissolved organic matter(DOM)in the Pearl River,China[J]. Environmental Science Pollution Research International,2015,23(8):7462-7469.
[6]何伟,白泽琳,李一龙,等.溶解性有机物特性分析与来源解析的研究进展[J].环境科学学报,2016,36(2):359-372.HE Wei,BAI Zelin,LI Yilong,et al.Advances in the characteristics analysis and source identification of the dissolved organic matter[J].Acta Scientiae Circumstantiae,2016,36(2):359-372.
[7]卢松,江韬,张进忠,等.两个水库型湖泊中溶解性有机物三维荧光特征差异[J].中国环境科学,2015,35(2):516-523.LU Song,JIANG Tao,ZHANG Jinzhong,et al. Three-dimensional fluorescence characteristic differences of dissolved organic matter(DOM)from two typical reservoirs[J]. China Environmental Science,2015,35(2):516-523.
[8] ROCHELLE-NEWALL E J,FISHER T R.Chromophoric dissolved organic matter and dissolved organic carbon in Chesapeake Bay[J].Marine Chemistry,2002,77(1):23-41.
[9] ZIEGELGRUBER K L,ZENG Teng,ARNOLD W A,et al.Sources and composition of sediment pore-water dissolved organic matter in prairie pothole lakes[J].Sciences of Limnology and Oceanography,2013,58(3):1136-1146.
[10] GUO Xujing,YUAN Donghai,LI Qiang,et al. Spectroscopic techniques for quantitative characterization of Cu(Ⅱ)and Hg(Ⅱ)complexation by dissolved organic matter from lake sediment in arid and semi-arid region[J]. Ecotoxicology and Environmental Safety,2012,85(3):144-150.
[11]蔡文良,许晓毅,杜娴,等.嘉陵江重庆段DOM三维荧光光谱的平行因子分析[J].环境科学研究,2012,25(3):276-281.CAI Wenliang,XU Xiaoyi,DU Xian,et al.Factor analysis with EEM on dissolved organic matter in Chongqing section of Jialing River[J].Research of Environmental Sciences,2012,25(3):276-281.
[12]姚昕,张运林,朱广伟,等.湖泊草、藻来源溶解性有机物及其微生物降解的差异[J].环境科学学报,2014,34(3):688-694.YAO Xin,ZHANG Yunlin,ZHU Guangwei,et al. Different degradation mechanism of dissolved organic matter derived from phytoplankton and macrophytes in Lake Taihu,China[J]. Acta Scientiae Circumstantiae,2014,34(3):688-694.
[13] YE Linlin,WU Xiaodong,LIU Bo,et al. Dynamics and sources of dissolved organic carbon during phytoplankton bloom in hypereutrophic Lake Taihu(China)[J]. Limnologica-Ecology and Management of Inland Waters,2015,54:5-13.
[14] BAI Ying,SU Rongguo,SHI Xiaoyong. Assessing the dynamics of chromophoric dissolved organic matter in the southern Yellow Sea by excitation:emission matrix fluorescence and parallel factor analysis(EEM-PARAFAC)[J]. Continental Shelf Research,2014,88:103-116.
[15]张广萍,周美正,张延,等.安徽派河流域水污染特征及原因分析[J].人民长江,2014(18):20-24.
[16] CORY R M,MCKNIGHT D M. Fluorescence spectroscopy reveals ubiquitous presence of oxidized and reduced quinones in dissolved organic matter[J]. Environmental Science&Technology,2005,39(21):8142-8149.
[17] MURPHY K R,BUTLER K D,SPENCER R G,et al.Measurement of dissolved organic matter fluorescence in aquatic environments:an interlaboratory comparison[J]. Environmental Science&Technology,2010,44(24):9405-9412.
[18] JAFFE R,BOTER J N,LU X,et al. Source characterization of dissolved organic matter in a subtropical mangrove-dominated estuary by fluorescence analysis[J].Marine Chemistry,2004,84(3/4):195-210.
[19] ZSOLNAY A,BAIGAR E,JIMENEZ M,et al. Differentiating with fluorescence spectroscopy the sources of dissolved organic matter in soils subjected to drying[J].Chemosphere,1999,38(1):45-50.
[20] ZHANG Yunlin,ZHANG Enlou,YIN Yan,et al.Characteristics and sources of chromophoric dissolved organic matter in lakes of the Yungui Plateau,China,differing in trophic state and altitude[J].Limnology and Oceanography,2010,55(6):2645-2659.
[21] ZHANG Yunlin,MARK-VAN D,LIU Mingliang,et al. The contribution of phytoplankton degradation to chromophoric dissolved organic matter(CDOM)in eutrophic shallow lakes:field and experimental evidence[J]. Water Research,2009,43(18):4685-4697.
[22] BATTIN T J.Dissolved organic matter and its optical properties in a blackwater tributary of the upper Orinoco River,Venezuela[J].Organic Geochemistry,1998,28(9/10):561-569.
[23] COBLE P G. Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy[J]. Marine Chemistry,1996,51(4):325-346.
[24] CHEN Jie,LEBOEUFE J,DAI Sheng,et al. Fluorescence spectroscopic studies of natural organic matter fractions[J].Chemosphere,2003,50(5):639-647.
[25] CHEN Wen,WESTERHOFF P,LEENHEER J A,et al.Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter[J]. Environmental Science&Technology,2003,37(24):5701-5710.
[26] NEBBIOSO A,PICCOLOA.Molecular characterization of dissolved organic matter(DOM):a critical review[J]. Analytical Bioanalytical Chemistry,2003,405(1):109-124.
[27] BIRDWELL J E,ENGEL A S.Characterization of dissolved organic matter in cave and spring waters using UV-Vis absorbance and fluorescence spectroscopy[J].Organic Geochemistry,2010,41(3):270-280.
[28] HUGUET A,VACHER L,RELEXAN S S,et al. Properties of fluorescent dissolved organic matter in the Gironde Estuary[J].Organic Geochemistry,2009,40(6):706-719.
[29] WEISHAAR J L,AIKEN G R,BERGAMASCHI B A,et al.Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon[J].Environmental Science&Technology,2003,37(20):4702-4708.
[30] JAFFRAIN J,GERARD F,MEYERM,et al.Assessing the quality of dissolved organic matter in forest soils using ultraviolet absorption spectrophotometry[J]. Soil Science Society of America Journal,2007,71(6):1851-1858.
[31] STEDMON C A,MARKAGER S,KAAS H.Optical properties and signatures of chromophoric dissolved organic matter(CDOM)in danish coastal waters[J]. Estuarine Coastal and Shelf Science,2000,51(2):267-278.
[32] GUO Wendong,STEDMON C A,HAN Yuchao,et al. The conservative and non-conservative behavior of chromophoric dissolved organic matter in Chinese estuarine waters[J]. Marine Chemistry,2007,107(3):357-366.
[33]王福利,郭卫东.秋季南海珠江口和北部湾溶解有机物的光降解[J].环境科学学报,2010,30(3):606-613.WANG Fuli,GUO Weidong.Photodegradation of DOM in the Pearl River Estuary and the Beibu Gulf of the South China Sea in autumn[J].Acta Scientiae Circumstantiae,2010,30(3):606-613.
[34] ZHANG Yunlin,LIU Mingliang,QIN Baoqiang,et al.Photochemical degradation of chromophoric-dissolved organic matter exposed to simulated UV-B and natural solar radiation[J]. Hydrobiologia,2009,627(1):159-168.
[35]闫红丽.基于三维荧光光谱-平行因子分析技术的黄东海有色溶解有机物(CDOM)的分布特征研究[D].青岛:中国海洋大学,2012.
[36]江俊武,李帅东,沈胤胤,等.夏季太湖CDOM光学特性空间差异及其来源解析[J].环境科学研究,2017,30(7):1020-1030.JIANG Junwu,LI Shuaidong,SHEN Yinyin,et al. Spatial differences of optical properties of CDOM and their source apportionment in Taihu Lake in Summer[J]. Research of Environmental Sciences,2017,30(7):1020-1030.
[37]祝鹏,华祖林,张润宇,等.太湖溶解有机质光谱和氮磷污染的区域分布差异特征[J].环境科学研究,2010,23(2):129-136.ZHU Peng,HUA Zulin,ZHANG Runyu,et al. Characteristics of spatial distribution differences of spectrum of dissolved organic matter and nitrogen/phosphorus pollution in Taihu Lake[J].Research of Environmental Sciences,2010,23(2):129-136.
[38] CHEN Zhiqiang,LI Yan,PAN Jianming. Distributions of colored dissolved organic matter and dissolved organic carbon in the Pearl River Estuary,China[J]. Continental Shelf Research,2004,24(16):1845-1856.
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