Seasonal variability of distribution and mixing behavior of chromophoric dissolved organic matter in the Changjiang River Estuary and adjacent areas
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摘要: 于2019年3月、7月和10月对长江口及邻近海域有色溶解有机物(CDOM)的分布及河口混合行为进行分析研究。通过对盐度、吸收光谱斜率S275～295、吸收系数aCDOM(355)以及叶绿素a的分析发现，在河口内低盐度区，7月淡水流量大，陆源输入量最大，aCDOM(355)值最高，3月CDOM来源主要受陆源输入和浮游植物生产活动的影响，aCDOM(355)值较10月高；在口外高盐度区，3月和7月的aCDOM(355)值相近，均低于10月，CDOM分布主要受浮游植物生产活动的影响。利用三维荧光光谱−平行因子分析方法共鉴定出4个荧光组分：类蛋白质组分C1(280/330 nm)、类腐殖质组分C2(300/350 nm)、类腐殖质组分C3(260/465 nm)和类腐殖质组分C4(320/410 nm)。在3月、7月及10月，4个荧光组分强度由长江口内到口外呈递减趋势，受陆源输入和浮游植物生产活动的影响，平均荧光强度的季节变化总体上来说，由大到小依次为7月、10月、3月。3个季节CDOM荧光组分均存在偏离理论稀释线的现象，说明CDOM的来源(陆源输入、沉积物再悬浮和现场生物活动)和去除(被颗粒物吸附、光降解和细菌降解)机制复杂多变，揭示了长江口区域CDOM在不同时空下的不保守混合行为。Abstract: The distribution and mixing behavior of chromophoric dissolved organic matter (CDOM) in the Changjiang River Estuary and adjacent areas were analyzed in March, July and October of 2019. Through discussing the salinity, absorption spectral slope S275-295, absorption coefficient aCDOM(355) and Chl a, it was shown that the terrestrial input and aCDOM(355) had the highest value in July; aCDOM(355) was affected by terrestrial input and phytoplankton production activities in March, and the value in March was higher than that in October in the Changjiang River Estuary low salinity area. In addition, in high-salt offshore regions, aCDOM(355) was similar in March and July, and both were lower than that in October, these distribution of CDOM was mainly influenced by phytoplankton production activities. Four fluorescent components of CDOM were identified by EEMs-PARAFAC technique: one protein-like component C1 (280/330 nm) and three humic-like components C2 (300/350 nm), C3 (260/465 nm) and C4 (320/410 nm) respectively. Four fluorescent components declined from the inside to the outside of the Changjiang River Estuary in March, July and October. Affected by terrestrial input and phytoplankton production activities, the seasonal variation of the average fluorescence intensity from large to small was July, October and March. The fluorescence components of CDOM deviated from the theoretical dilution line in these three seasons. It showed that CDOM source (terrestrial input, sediment resuspension and on-site biological activities) and sink (adsorption of particulate matter, photodegradation and bacterial degradation) were complex and variable, revealing the non-conservative mixed behavior of CDOM in the Changjiang River Estuary.
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图 2 3月长江口及邻近海域温度、盐度、aCDOM(355)、Chl a浓度、S275～295的分布
Fig. 2 Distribution of temperature, salinity, aCDOM(355), Chl a concentration, S275～295 of the Changjiang River Estuary and adjacent areas in March
图 3 7月长江口及邻近海域温度、盐度、aCDOM(355)、Chl a浓度、S275～295的分布
Fig. 3 Distribution of temperature, salinity, aCDOM(355), Chl a concentration, S275～295 of the Changjiang River Estuary and adjacent areas in July
图 4 10月长江口及邻近海域温度、盐度、aCDOM(355)、Chl a浓度、S275～295的分布
Fig. 4 Distribution of temperature, salinity, aCDOM(355), Chl a concentration, S275～295 of the Changjiang River Estuary and adjacent areas in October
图 5 用PARAFAC鉴别出CDOM的4个荧光组分
Fig. 5 Four fluorescent components of CDOM identified by PARAFAC model
图 6 3月长江口及邻近海域4个荧光组分以及TFI的分布
Fig. 6 Distributions of four fluorescent components and total fluorescence intensity of the Changjiang River Estuary and adjacent areas in March
图 8 10月长江口及邻近海域4个荧光组分以及TFI的分布
Fig. 8 Distributions of four fluorescent components and total fluorescence intensity of the Changjiang River Estuary and adjacent areas in October
图 7 7月长江口及邻近海域4个荧光组分以及TFI的分布
Fig. 7 Distributions of four fluorescent components and total fluorescence intensity of the Changjiang River Estuary and adjacent areas in July
图 9 3月、7月及10月长江口及邻近海域4个荧光组分随盐度的变化
Fig. 9 Variation of four fluorescent components with salinity site of the Changjiang River Estuary and adjacent areas in March, July and October
表 1 3月长江口及邻近海域温度、aCDOM(355)、Chl a浓度以及S275～295的值
Tab. 1 The value of temperature, aCDOM(355), Chl a concentration and S275～295 of the Changjiang River Estuary and adjacent areas in March
参数 盐度分区 温度/℃ aCDOM(355)/m−1 Chl a浓度/(μg.L−1) S275～295/nm−1 范围 平均值 范围 平均值 范围 平均值 范围 平均值 表层 0.13～7.65（盐度小于10） 8.35～8.87 8.58 1.37～2.27 1.85 0.85～3.12 2.2 0.014～0.018 0.016 10.4～34.4（盐度大于10） 7.84～14.6 11.2 0.08～3.13 0.45 0.18～2.39 0.8 0.012～0.033 0.019 中层 0.14～0.15（盐度小于10） 8.52～8.62 8.57 1.85～2.00 1.91 2.18～3.59 2.7 0.015～0.016 0.015 26.1～34.3（盐度大于10） 8.06～13.9 11.2 0.019～0.5 0.31 0.17～1.52 0.6 0.015～0.024 0.019 底层 0.13～8.63（盐度小于10） 8.33～9.00 8.61 1.25～2.43 1.93 1.02～3.30 2.1 0.014～0.017 0.016 13.6～34.3（盐度大于10） 7.82～14.0 11.2 0.03～1.21 0.39 0.12～2.55 0.9 0.002～0.037 0.017 
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表 2 7月长江口及邻近海域温度、aCDOM(355)、Chl a浓度以及S275～295的值
Tab. 2 The value of temperature, aCDOM(355), Chl a concentration and S275～295 of the Changjiang River Estuary and adjacent areas in July
参数 盐度分区 温度/℃ aCDOM(355)/m−1 Chl a 浓度/(μg.L−1) S275～295/nm−1 范围 平均值 范围 平均值 范围 平均值 范围 平均值 表层 0.13～0.15（盐度小于10） 26.2～27.0 26.7 0.92～3.52 2.22 0.61～1.75 0.80 0.004～0.018 0.016 16.8～32.6（盐度大于10） 22.1～26.4 24.6 0.24～0.85 0.47 0.18～4.51 1.85 0.014～0.022 0.018 中层 0.14～0.15（盐度小于10） 26.4～27.0 26.7 2.19～2.81 2.39 0.52～1.13 0.77 0.015～0.017 0.016 18.7～33.1（盐度大于10） 21.6～26.3 24.0 0.08～1.18 0.37 0.23～8.28 1.46 0.015～0.024 0.017 底层 0.13～0.15（盐度小于10） 26.5～26.9 26.7 0.83～3.40 2.37 0.17～2.19 0.81 0.013～0.019 0.016 28.1～34.5（盐度大于10） 18.4～23.3 21.7 0.01～0.97 0.37 0.07～1.64 0.55 0.012～0.032 0.017
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表 3 10月温度、aCDOM(355)、Chl a浓度以及S275～295的值
Tab. 3 The value of temperature, aCDOM(355), Chl a concentration and S275～295 of the Changjiang River Estuary and adjacent areas in October
参数 盐度分区 温度/℃ aCDOM(355)/m−1 Chl a 浓度/(μg.L−1) S275～295/nm−1 范围 平均值 范围 平均值 范围 平均值 范围 平均值 表层 0.16～6.43（盐度小于10） 21.1～22.7 22.2 1.49～2.33 1.75 0.52～2.87 1.28 0.015～0.018 0.017 11.0～34.5（盐度大于10） 21.2～24.2 22.8 0.07～2.08 0.65 0.52～5.87 1.85 0.009～0.033 0.016 中层 0.16～0.24（盐度小于10） 22.1～22.6 22.4 1.64～1.84 1.70 0.84～1.30 1.01 0.016～0.018 0.017 23.5～35.5（盐度大于10） 22.4～24.0 23.3 0.04～1.31 0.44 0.29～4.44 1.75 0.011～0.036 0.017 底层 0.16～3.66（盐度小于10） 21.9～22.5 22.3 1.60～2.70 1.82 0.62～1.36 1.08 0.014～0.017 0.017 12.0～34.3（盐度大于10） 21.5～33.6 23.4 0.09～1.33 0.58 0.53～3.39 1.42 0.005～0.020 0.015
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表 4 近岸海域的吸收系数值对比
Tab. 4 Comparison of absorption coefficients in coastal waters
海区 采样时间 盐度范围 站位类型 吸收系数(m−1)/波长(nm) 参考文献 南波罗的海 1994年 2.0～8.0 低盐度 （1.2～12）/355 [23] Funka湾 2000年10月至2001年11月 31.6～33.8 高盐度 （0.022～0.14）/440 [24] 阿拉伯海 1994年 36.2～36.9 高盐度 （0.03～0.106）/375 [25] 九龙口 2005年4月 0.11～5.92 低盐度 （2.25～3.32）/355 [16] 10.2～27.08 高盐度 （0.47～1.92）/355 2003年8月 0～5.41 低盐度 （2.3～3.11）/355 [16] 10.14～29.86 高盐度 （0.7～2.26）/355 2005年11月 0.22～9.11 低盐度 （1.54～2.76）/355 [16] 14.4～29.26 高盐度 （0.64～1.41）/355 长江口 2003年8月 0.21～7.89 低盐度 （1.75～2.42）/355 [16] 10～30.91 高盐度 （0.46～1.8）/355
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表 5 长江口及邻近海域CDOM的主要荧光组分
Tab. 5 Principle fluorescent component of CDOM in the Changjiang River Estuary and adjacent areas
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表 6 3月、7月及10月长江口及邻近海域CDOM各组分荧光强度
Tab. 6 Fluorescent intensity of CDOM component of the Changjiang River Estuary and adjacent areas in March, July and October
季节 荧光组分 表层荧光强度/RU 表层平均荧光强度/RU 中层荧光强度/RU 中层平均荧光强度/RU 底层荧光强度/RU 底层平均荧光强度/RU 3月 C1 0.005 9～0.130 0.036 0.005 3～0.078 0.028 0.008 3～0.130 0.034 C2 0.003 5～0.097 0.024 0.003 3～0.050 0.017 0.005 1～0.085 0.023 C3 0.004 3～0.068 0.027 0.003 6～0.055 0.020 0.005 2～0.060 0.027 C4 0.004 9～0.151 0.036 0.004 3～0.084 0.022 0.006 4～0.094 0.036 7月 C1 0.018 3～0.108 0.037 0.013 0～0.088 0.034 0.010 5～0.101 0.036 C2 0.005 0～0.090 0.046 0.002 7～0.309 0.045 0.004 2～0.346 0.057 C3 0.008 5～0.082 0.036 0.007 0～0.082 0.030 0.006 4～0.087 0.031 C4 0.007 0～0.117 0.047 0.007 0～0.113 0.040 0.005 5～0.126 0.042 10月 C1 0.001 6～0.249 0.033 0.005 0～0.081 0.024 0.008 7～0.229 0.034 C2 0.006 9～0.110 0.027 0.006 4～0.060 0.022 0.006 2～0.113 0.029 C3 0.002 0～0.094 0.031 0.006 8～0.096 0.028 0.001 2～0.092 0.035 C4 0.007 6～0.141 0.042 0.009 1～0.098 0.034 0.007 6～0.109 0.044
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