Variation characteristics and source analysis of dissolved organic matter along the river into Baiyangdian Lake
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摘要:
采用紫外-可见吸收光谱、三维荧光光谱，结合平行因子分析、主成分分析等方法，分析了白洋淀3条入淀河流（府河、孝义河、白沟引河）中发色团溶解有机物（CDOM）的光谱特征，阐释了CDOM组成、来源及对水质的影响机制。结果发现：河流CDOM平均浓度顺序为府河>孝义河>白沟引河，其中，府河CDOM的芳香性与分子量高于其他河流，白沟引河腐殖化程度高于其他河流，孝义河CDOM中内源性物质占比高于其他河流；3条河流均检出类腐殖质组分C1、C2、C3和类蛋白质组分C4，其中C1、C2、C3来源相近，且与C4异源；3条河流各组分最大荧光强度和总荧光强度的沿程变化表明，府河CDOM为点源、面源混合来源，孝义河CDOM以点源输入为主，白沟引河CDOM来自水源本身。
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关键词:
- 白洋淀 /
- 入淀河流 /
- 发色团溶解有机物（CDOM） /
- 紫外-可见吸收光谱 /
- 三维荧光光谱 /
- 平行因子分析（PARAFAC）
Abstract:The spectral characteristics of chromophoric dissolved organic matter (CDOM) in three inflow rivers of Baiyangdian Lake (Fu River, Xiaoyi River and Baigouyin River) were analyzed by UV-vis absorption spectroscopy, three-dimensional fluorescence spectroscopy, parallel factor analysis and principal component analysis, and the composition, sources and the influence mechanism of CDOM on water quality were explained. The results showed that the order of CDOM average concentration was Fu River>Xiaoyi River>Baigouyin River. The aromaticity and molecular weight of CDOM in the Fu River were higher than those in other rivers, the degree of humification in the Baigouyin River was higher than those in other rivers, and the proportion of endogenous substances in CDOM in the Xiaoyi River was higher than those in other rivers. Humic-like components C1, C2, C3 and protein-like components C4 were detected in the three rivers, among which C1, C2 and C3 were similar in origin and different from C4. The variation of maximum fluorescence intensity and total fluorescence intensity of each component in the three rivers showed that CDOM of the Fu River was from point and non-point mixed sources, CDOM of the Xiaoyi River was mainly from point sources, and CDOM of the Baigouyin River diversion was contained by the water source itself.
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图 2 3条河流不同河段的DOC浓度和光谱特征参数箱线图
Figure 2. Boxplots of DOC concentration and spectral characteristic parameters at different river sections of three rivers
图 3 3条河流不同河段的荧光参数箱线图
Figure 3. Boxplots of fluorescence parameters at different river sections of three rivers
图 4 PARAFAC模型分离的4种荧光组分及其激发/发射载荷
Figure 4. Four fluorescence components separated by PARAFAC model and their excitation/emission loads
图 5 3条河流各采样点PARAFAC组分的沿程变化
Figure 5. Variation of PARAFAC components along the river at sampling points of three rivers
图 6 光学参数和水质指标的主成分分析结果
注：椭圆表示各组采样点 95% 的置信椭圆。右轴和上轴表示图中各参数与PC1和PC2的相关性，轴上数字为相关性系数。
Figure 6. Results of principal component analysis of optical parameters and water quality indexes
表 1 紫外-可见吸收光谱参数与DOC的相关性
Table 1. Correlation between UV-vis absorption spectrum parameters and DOC
项目 a（350） SUVA254 SUVA260 E2/E3 a（350） 1 SUVA254 0.573** 1 SUVA260 0.581** 0.905** 1 E2/E3 −0.549** −0.742** −0.692** 1 注：*表示在P<0.05水平显著相关；**表示在P<0.01水平极显著相关。 
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表 2 利用PARAFAC模型识别的4个组分的光谱特性
Table 2. Spectral characteristics of four components identified by PARAFAC model
组分 (Exmax/Emmax)/
(nm/nm)传统峰 描述 分子特征 匹配
数量C1 330/410 M 类腐殖质 低分子量，微生物转化 11 C2 360/445 C 类腐殖质 芳香族，高分子量 1 C3 390~400/
400~500C 类腐殖质 高分子量，高芳香性 4 C4 285~290/320 T 类色氨酸 脂肪族，高分子量，
亲水性好5 注：Exmax和Emmax分别表示各组分的最大激发波长和发射波长的近似位置。
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表 3 PARAFAC模型中CDOM吸收系数与组分荧光强度之间的关系
Table 3. Relationship between CDOM absorption coefficient and component fluorescence intensity in PARAFAC model
河流 参数 a（350） DOC Fmax（C1） Fmax（C2） Fmax（C3） Fmax（C4） 府河 a（350） 1 DOC 0.529** 1 Fmax（C1） 0.310 0.697** 1 Fmax（C2） 0.295 0.700** 0.972** 1 Fmax（C3） 0.322* 0.733** 0.957** 0.988** 1 Fmax（C4） 0.077 0.528* 0.779** 0.631** 0.603* 1 孝义
河a（350） 1 DOC 0.680** 1 Fmax（C1） 0.550* 0.603* 1 Fmax（C2） 0.463* 0.634** 0.985** 1 Fmax（C3） 0.265 0.694** 0.966** 0.994** 1 Fmax（C4） 0.434* 0.609* 0.451* 0.311 0.255 1 白沟
引河a（350） 1 DOC 0.587** 1 Fmax（C1） 0.146 0.798** 1 Fmax（C2） 0.127 0.743** 0.988** 1 Fmax（C3） 0.126 0.853** 0.944** 0.951** 1 Fmax（C4） 0.142 0.566* 0.850** 0.807** 0.780** 1 注：同表1。
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表 4 水质参数与荧光组分的回归分析
Table 4. Regression analysis of water quality parameters and fluorescence components
河流 回归方程 决定系数（R2） 方差膨胀
系数（VIF）府河 [COD]=7.713+3.885×Fmax(C3) 0.379** 1.0 [TN]=3.720+0.533×Fmax(C2) 0.129* 1.0 孝义河 [COD]=9.710+14.518×Fmax(C2)−
25.333× F max(C3)0.950** 1.25 [NH4 +-N]=−0.049−0.045×F max(C1)+
0.008×F max(C4)+0.215×F max(C3)0.949** 1.0 [TP]=0.008+0.007×F max(C4) 0.861** 1.0 [TN]=−3.527+2.079× F max(C2)+
2.864× F max(C3)− 0.084× F max(C4)0.995* 1.07 白沟引河 [COD]=2.061+7.601×Fmax(C3) 0.698** 1.0 [NH4 +-N]=0.171−0.006×Fmax(C4) 0.190* 1.0 [TN]=6.376−2.086× F max(C4) 0.223* 1.0 3条河流
所有
采样点[COD]=5.238+5.545×Fmax(C3) 0.518** 1.0 [NH4 +-N]=0.185+0.050× F max(C1) 0.063* 1.0 [TP]=0.098+0.130× F max(C2)−0.065×
F max(C1)− 0.154× F max(C3)0.240* 1.0 [TN]=2.951+0.868× F max(C2)−
0.154× F max(C4)0.211* 1.0 注：同表1。
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