二龙湖表层水体有色溶解有机物的光学特性及来源

CDOM（colored dissolved organic material,有色溶解有机物）的光学特性可反映水体中内源物质与外源物质的比例,为了解二龙湖受到上游来水所含污染物的影响,利用荧光区域一体化技术和荧光指数分析水体中CDOM的荧光特性,进而判定水体污染状况,并结合CDOM荧光组分与水质参数之间的关系,探讨了不同季节二龙湖水体中CDOM光学特性在时空分布上的差异性以及CDOM的组成与来源.结果表明:①水相中CDOM表现出明显的季节性差异.其中,光谱斜率S_g（275~295 nm）和E_{250 nm:365 nm}〔a_CDOM（250）/a_CDOM（365）〕均表现为丰水期>平水期>枯水期,SUVA_{254 nm}表现为枯水期>平水期>丰水期.②水体中的荧光组分以外源组分R3（富里酸类物质）和R5（腐殖酸类物质）为主,在枯水期、丰水期和平水期分别占总荧光强度的70.0%、60.4%和51.3%.③在丰水期、枯水期、平水期,FI_{310 nm}平均值均大于0.8,FI_{370 nm}平均值均小于1.4,表明在3个水文期,微生物活动带来的内源CDOM在二龙湖南部较为明显.④ρ（DOC）（dissolved organic carbon,溶解性有机碳）与CDOM的荧光组分R2（色氨酸类组分）、R4（可溶性微生物副产物组分）和R5（腐殖酸类组分）均具有较好的相关性,相关系数（R）分别为0.71、0.80、0.73,表明DOC主要源于微生物代谢的可溶性副产物及浮游植物的降解.研究显示:水体中CDOM主要组成为内源的色氨酸与微生物蛋白质类副产物以及外源的富里酸类与腐殖酸类有机物;同时,由于冰冻、降水、生活污水排放、农业废水和水生植物等因素,导致湖泊中的CDOM的组分与来源十分复杂.      

有色可溶性有机物在线荧光技术在水质监测中的应用

FDOM（荧光有机物）在线荧光探头是采用激发波长370 nm和发射波长460 nm下荧光强度来计算水体CDOM（有色可溶性有机物）丰度的传感器,为探究该传感器在内陆水体水质监测中的应用和适用性,以水源供给水库千岛湖为案例,通过FDOM荧光探头监测该湖泊不同季节CDOM丰度,结合CDOM光谱吸收、ρ（DOC）（DOC表示溶解性有机碳）、ρ（TN）、ρ（TP）、ρ（COD_Mn）、ρ（DTN）（DTN表示溶解性总氮）、ρ（DTP）（DTP表示溶解性总磷）和ρ（Chla）等水质参数数据,揭示FDOM荧光强度与其他水质参数的耦合关系,检验FDOM荧光探头对有机物的监测能力.结果表明:①2014年5月千岛湖TLI平均值（38.4±4.4）显著高于2018年10月TLI平均值34.9±3.0（t-test,P < 0.001）,根据TLI及各水质参数平均值判定该湖处于中贫营养状态.②大部分水质参数呈现出由西北入湖河口向下游大坝出水口方向递减的趋势,表明上游新安江对该湖有机物具有较大的贡献.③FDOM荧光强度与CDOM吸收系数a（254）（R2=0.91,P < 0.01）、a（350）（R2=0.90,P < 0.01）均呈极显著正相关且具有较高的线性拟合优度,这意味着FDOM荧光强度可以很好地表征CDOM丰度.④FDOM荧光强度与ρ（DOC）（R2=0.49,P < 0.01）、ρ（TN）（R2=0.61,P < 0.01）、ρ（TP）（R2=0.75,P < 0.01）、ρ（COD_Mn）（R2=0.35,P < 0.01）、ρ（DTN）（R2=0.59,P < 0.01）、ρ（DTP）（R2=0.56,P < 0.01）、ρ（Chla）（R2=0.68,P < 0.01）均呈极显著正相关且与大多数水质参数具有相似的分布特征,并且能很好地识别潜在污染物高值区.研究显示,荧光探头在可见波长下所得陆源类腐殖酸FDOM荧光强度能很好地成为潜在污染物替代指标,并能有效呈现有机物分布特征,因而该技术在饮用水湖泊水质监测中具有潜在广阔的应用前景.      

环胶州湾河流入海口CDOM吸收光谱特征

为深入认识河流对胶州湾水体有机碳的贡献,于2016年4月-2017年2月对环胶州湾河流入海口进行双月采样,通过分析水体中DOC（溶解有机碳）和POC（颗粒有机碳）质量浓度及CDOM（有色溶解有机物）的吸收光谱特征,揭示环胶州湾入海口有机碳的分布特征,辨析CDOM的组成和来源,探讨其与主要环境因素的关系.结果表明:①环胶州湾河流入海口DOC和POC质量浓度范围分别为0.98~32.75和0.13~22.40 mg/L,其中李村河口最高,轮渡和大港相对较小.②a（355）（CDOM的吸收系数）变化范围为0.23~16.35 m-1,存在明显的季节性差异,与盐度成反比,其分布与DOC和POC基本一致.③研究区域水体中,表征CDOM分子组成、来源及芳香化程度的S_R[光谱斜率比,S_g（275~295 nm）/S_g（350~400 nm）]和A_{250 nm}/A_{365 nm}存在显著的时空差异.④夏季、秋季CDOM的整体分子量水平高于春季、冬季;轮渡、大港、板桥坊河和娄山河S_R相对较高,CDOM组成趋向于蛋白类或富里酸类物质.⑤轮渡、大港和镰湾河A_{250 nm}/A_{365 nm}相对较高,类腐殖质的芳香化程度较低,受海源控制;其他河口A_{250 nm}/A_{365 nm}相对较低,CDOM以陆源输入为主,其类腐殖质的芳香化程度较高,结构相对稳定而不易降解.⑥CCA（Canonical Correspond Analysis,典范对应分析）结果表明,DOC与CDOM吸收特性存在较好的相关性,河口CDOM主要来自地表径流,温度和DO是影响CDOM时空分布的主要因素.研究显示,CDOM的组成、降解的难易程度与来源密切相关,秋季生物量丰富,水体中腐殖酸所占比例增大,CDOM芳香度较高,不容易被降解.      

太湖典型草、藻型湖区有色可溶性有机物的吸收及荧光特性

2004年4月对太湖典型草、藻型湖区东太湖和梅梁湾有色可溶性有机物(CDOM)的吸收和荧光特性进行了研究.通过实验测定方法得到东太湖和梅梁湾CDOM的光谱吸收系数及其荧光值.结果表明,溶解性有机碳(DOC)的浓度在6.3～17.2 mg/L间变化,其均值为9.08±2.66 mg/L;CDOM在280 nm和355 nm的吸收系数分别为11.2～32.6 m^-1(平均值17.46m-1±5.75 m^-1)和2.4m～8.3 m^-1(平均值4.17 m^-1±1.47 m^-1);355 nm波长处CDOM的比吸收系数为0.31～0.64 L·(mg·m)^-1,平均值0.46L·(mg·m)^-1±0.08 L·(mg·m)^-1.355 nm的激发波长、450 nm的发射波长处的荧光值的变化范围0.50～3.91 nm^-1(平均值1.32nm-1±0.84 nm^-1).2类草、藻型湖区的DOC浓度、CDOM吸收系数、355 nm处荧光值均存在显著性差异,但CDOM比吸收系数和指数函数斜率则没有显著性差异,由此则反映了CDOM来源的一致性.CDOM的吸收系数与DOC浓度的相关性随波长的降低而增加,在短波部分存在明显的正相关.355 nm处的荧光值、DOC浓度与CDOM吸收系数存在如下显著性的正相关关系:F_n(355)=0.544(±0.035)a(355)-0.946(±0.152),DOC=1.537(±0.196)a(355)+2.683(±0.862).280～500 nm、280～360 nm、360～440 nm指数函数斜率分别为14.37μm^-1±0.73μm^-1、19.17μm-1±0.84μm^-1、13.38μm-1±0.82μm^-1.     

城市不同类型水体有色可溶性有机物来源组成特征

过去几十年里,我国飞速的工业活动和城市化进程对城市地表水体生态系统产生巨大影响,地表水体水质变化直接影响城市居民用水安全、城市景观维护及城市热点区域碳循环过程.通过2020年6月采集长春市各类水体（城市河流、公园湖泊及水库）共50个样品,结合光谱吸收及三维荧光光谱-平行因子分析法（EEMs-PARAFAC）分析了各类水体的有色可溶性有机物（CDOM）光学特性、组成特征及潜在来源.结果表明,长春市城市河流DOC浓度显著高于水库水体（t-test,P<0.05）.城市河流水体的CDOM吸收系数a₂₅₄均值显著大于公园湖泊和水库（t-test,P<0.05）,表明城市河流水体中CDOM浓度最高.CDOM光谱吸收斜率S_275-295与光谱吸收斜率比S_R均值均表现为公园湖泊>水库>城市河流（t-test,P<0.001）.平行因子分析法解析三维荧光光谱得到3个荧光组分,陆源类腐殖酸C1（E_x=260 nm,E_m=452 nm）、微生物作用类腐殖酸C2（E_x=245/290 nm,E_m=388 nm）和类色氨酸C3（E_x=275 nm,E_m=340 nm）.城市河流水体各组分荧光强度均值均显著高于公园湖泊与水库（t-test,P<0.005）,水库水体陆源类腐殖酸C1荧光强度均值显著高于微生物作用类腐殖酸C2和类色氨酸C3（t-test,P<0.005）,城市居民生活污水排放对长春市城市水体,尤其是城市河道中有机碳贡献较大,且该部分有机质中微生物降解潜力强的类蛋白组分贡献率高.因此,应加强城市污水排放管控以有效保障长春市城市水体经济、环境与生态功能的发挥.     

长江中下游浅水湖泊紫外辐射的衰减

基于对长江中下游22个浅水湖泊有色可溶性有机物吸收的测量,运用经验模式估算了紫外辐射(UV-B、UV-A)在长江中下游湖泊的衰减及对应的穿透深度,并利用在武汉东湖实测的紫外辐射衰减进行了检验.结果表明,UV-B波段的320nm和UV-A波段的380nm衰减系数变化范围分别为2.05～21.00m^-1,1.07～12.85m^-1,对应的1%穿透深度分别为0.22～2.25m,0.36～4.29m.估算得到的紫外辐射衰减系数与DOC浓度均存在显著性正相关,但UV-B波段要高于UV-A波段.武汉东湖实测的紫外辐射衰减检验发现,基于CDOM吸收系数估算UV-B辐射衰减较为精确,而由于浮游植物吸收和悬浮物散射等影响对UV-A波段估算精度则明显下降.     

Removal of chromophoric dissolved organic matter under combined photochemical and microbial degradation as a response to different irradiation intensities

Throughout the freshwater continuum, Dissolved Organic Carbon (DOC) and the colored fraction, Chromophoric Dissolved Organic Material (CDOM), are continuously being added, removed, and transformed, resulting in changes in the chromophoricity and lability of organic matter over time. We examined, experimentally, the effect of increasing irradiation-intensities on the combined photochemical and microbial degradation of CDOM and DOC. This was done by using a simulated mixed water column: aged water from a humic lake was exposed to four irradiation-intensities – representing winter, early and late spring, and summer conditions (0.10, 0.16, 0.36, and 0.58 W/m²) – and compared with dark controls over 37 days. We found a linear relationship between CDOM degradation and irradiation-intensities up to 0.36 W/m²; the degradation rate saturated at higher intensities, both at specific wavelengths and for broader intervals. After 37 days at high irradiation-intensity, CDOM absorption of irradiation at 340 nm had been reduced by 41%; 48% of DOC had been removed and DOC degradation continued to increase. Aromaticity (SUVA₂₅₄) declined significantly over 37 days at the two lowest but not at the two highest UV- intensities; levels in unexposed control water remained constant. Direct observations of the humic lake showed that CDOM absorption of irradiation (340 nm) declined by 27% from winter to summer. A model based on hydrological CDOM input and CDOM degradation calculated from field measurements of UV-radiation and experimental CDOM degradation with UV-exposure from sunlight accurately predicted the annual course as observed in the lake. With no external CDOM input, 92% of the CDOM could be degraded in a year. The results support the notion that combined photochemical and microbial CDOM degradation can be remarkably higher in lakes than previously thought and that humic lakes retain their color due to light absorption by ongoing CDOM input.     

太湖水华前表层水CDOM的光谱特征与来源解析

有色溶解性有机质（CDOM）是水生态系统中营养盐生物地球化学循环的重要环节,为探究太湖水华前表层水中CDOM的组分特征与来源,采用紫外-可见光谱与激发发射矩阵荧光光谱-平行因子分析（EEM-PARAFAC）技术对表层水中的CDOM组分进行了解析,结合CDOM光学参数（a₃₅₅、SUVA₂₅₄、a₂₅₀/a₃₆₅、FI、BIX和HIX）辨识其空间差异与污染来源,并与太湖CDOM组分历史数据进行了初步对比.结果表明,a₃₅₅、SUVA₂₅₄和a₂₅₀/a₃₆₅显示太湖东部表层水CDOM呈现高浓度、高芳香性和低相对分子量的特征,而北部与之相反.平行因子分析法从CDOM中分离出4个组分,类酪氨酸（C1）、两种类色氨酸（C2、C4）和类富里酸（C3）,且主要组分C1与C2和C3组分具有较强的线性关系,不同组分来自相似污染源,荧光指数显示,太湖CDOM不同区域间受内源与陆源输入影响存在差异,但整体腐殖化程度较低.这表明太湖CDOM组分以类蛋白（C1、C2和C4）为主（>85%）且以自生源为主,可生化利用性好.     

秦岭北麓河流夏季有色溶解有机物分布特征及影响因素

以秦岭北麓辋川河水体为研究对象,利用紫外可见吸收光谱、荧光光谱结合平行因子分析法解析了夏季辋川河水体有色溶解性有机质(CDOM)的组成结构,并探讨了水体有色溶解性有机质的来源,运用冗余分析法和Pearson相关性分析阐明了光学参数与水质参数的相关性.结果表明,①辋川河水体CDOM由类色氨酸组分C1(245, 300/335 nm)、短波类腐殖质组分C2(240, 320～340/405 nm)和长波类腐殖质组分C3(270, 350～370/470 nm)组成,其中组分C1与C2具有一定的同源性(r=0.859,P0.001).②CDOM吸收系数α(355)表明辋川河水体CDOM浓度处于较低水平,并且α(355)与DOC浓度相关性显著(r=0.850,P0.001),这有利于建立DOC反演模型.③水体荧光指数FI(2.36±0.20)、HIX(3.66±2.47)、BIX(1.56±0.82)和新鲜度指数(β:α)(1.33±0.62),以及光谱斜率比S_R(0.76±0.25)表明,辋川河水体CDOM呈现强自生源、低腐殖化和非陆源的特征.④冗余分析结果表明类腐殖质组分(C2、C3)受藻类代谢和微生物作用影响,而类色氨酸组分(C1)与陆源输入有关,类色氨酸组分C1与DTN呈负相关关系,类腐殖质组分C2和C3与TP、DTP和DOC呈现正相关关系.本文阐明了夏季秦岭北麓河流水体有色溶解有机质的特征及影响因素,为秦岭流域水体治理提供理论依据.     

Resolving the variability of CDOM fluorescence to differentiate the sources and fate of DOM in Lake Taihu and its tributaries

Taihu Basin is the most developed area in China, which economic development has resulted in pollutants being produced and discharged into rivers and the lake. Lake Taihu is located in the center of the basin, which is characterized by a complex network of rivers and channels. To assess the sources and fate of dissolved organic matter (DOM) in surface waters, we determined the components and abundance of chromophoric dissolved organic matter (CDOM) within Lake Taihu and 66 of its tributaries, and 22 sites along transects from two main rivers. In Lake Taihu, there was a relative less spatial variation in CDOM absorption a_CDOM(355) with a mean of 2.46 ± 0.69 m⁻¹compared to the mean of 3.36 ± 1.77 m⁻¹ in the rivers. Two autochthonous tryptophan-like components (C1 and C5), two humic-like components (C2 and C3), and one autochthonous tyrosine-like component (C4) were identified using the parallel factor analysis (PARAFAC) model. The C2 and C3 had a direct relationship with a_CDOM(355), dissolved organic carbon (DOC), and chemical oxygen demand (COD). The separation of lake samples from river samples, on both axes of the Principal Component Analysis (PCA), showed the difference in DOM fluorophores between these various environments. Components C1 and C5 concurrently showed positive factor 1 loadings, while C4 was close to the negative factor 1 axis. Components C2 and C3 showed positive second factor loadings. The major contribution of autochthonous tryptophan-like components to lake samples is due to the autochthonous production of CDOM in the lake ecosystems. The results also showed that the differences in geology and associated land use control CDOM dynamics, such as the high levels of CDOM with terrestrial characteristics in the northwestern upstream rivers and low levels of CDOM with increased microbial characteristics in the southwestern upstream rivers. Most of river samples from the downstream regions in the eastern and southeastern plains had a similar relative abundance of humic-like fluorescence, with less of the tryptophan-like and more of the tyrosine-like contributions than did samples from upstream regions.