Seasonal variations of dissolved Mn concentration in the surface water of the Changjiang River Estuary and its adjacent area
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摘要: 锰（Mn）是海洋中的生命必需痕量元素。河口位于河流和海洋的交界区域，其对Mn的改造作用会影响陆源Mn向海输送的生物地球化学过程。本研究使用自动固相萃取−电感耦合等离子体联用技术对2019年9月（秋季）、2021年3月（春季）和2021年7月（夏季）长江口及其邻近水域的表层溶解Mn浓度进行了测定和分析。结果显示，溶解Mn的平均浓度和河口行为表现出了季节性差异：夏季的溶解Mn浓度最高，表现为先移除后添加的分布特征；秋季的溶解Mn浓度次之，表现为添加型分布；春季的溶解Mn浓度最低，表现为保守型分布。显著性分析结果表明，长江携带的溶解Mn仅在淡水端元浓度值较高的季节会显著影响长江口及其邻近水域溶解Mn的分布；当长江淡水端元浓度值较低时，长江口溶解Mn则受多种生物地球化学过程的共同主导。长江口的中低盐度海水中高悬浮颗粒物浓度是造成该区域溶解Mn移除的重要因素，而高盐度海水中溶解Mn的添加机制则有待进一步研究。Abstract: Manganese (Mn) is an essential trace element for the marine ecosystem. As the transitional zone between rivers and oceans, estuaries have a significant effect on dissolved Mn and its terrigenous input. In this study, the distribution of dissolved Mn, investigated in the surface water of Changjiang River Estuary and its adjacent area during September 2019 (autumn), March 2021 (spring) and July 2021 (summer), was analyzed by automatic solid phase extraction and inductively coupled plasma mass spectrometry. The results indicated that the average concentration and estuarine behaviors of dissolved Mn showed seasonal variations between the three cruises: the maximum average concentration occurred in summer and dissolved Mn was removed firstly and then added with the increase of salinity; the medium average concentration occurred in autumn and dissolved Mn was mainly removed with the increase of salinity; the minimum average concentration occurred in spring and dissloved Mn was mainly conservative with the increase of salinity. The results of significance test indicated that only in the season when the fresh water had high concentrations, dissloved Mn carried by the Changjiang River had significant influence on the distribution of dissolved Mn in the Changjiang River Estuary and its adjacent area; the distribution of dissolved Mn was co-dominated by a variety of biogeochemical processes in the season when the concentrations were low in the fresh water. The high suspended particulate matter concentrations were the important factor of the removal of dissolved Mn in the Changjiang Estuary’s water with medium-low salinity. And the addition mechanism of dissolved Mn in water with high salinity needs further vestigation.
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图 1 长江口及其邻近水域采样站位
Fig. 1 The sampling stations in the Changjiang River Estuary and its adjacent area
图 2 长江口及其邻近水域表层水体中盐度、温度和溶解Mn浓度的分布
Fig. 2 The distributions of salinity, temperature and dissolved Mn concentration in the surface of the Changjiang River Estuary and its adjacent area
图 3 长江口及其邻近水域表层水体溶解Mn跨越盐度梯度的分布状况
Fig. 3 Distributions of dissolved Mn across salinity gradients in the surface of the Changjiang River Estuary and its adjacent area
图 4 秋季、春季、夏季溶解Mn浓度的估算相对偏差与盐度（a−c）和SPM含量（d−f）的关系
Fig. 4 Relationships between the estimated relative deviation of dissolved Mn concentrations and salinity (a−c), and SPM content (d−f) in autumn, spring and summer
图 5 3个季节整体SPM含量与盐度（a）、Mn浓度与SPM含量（b）以及Mn浓度的估算相对偏差与SPM含量（c）的关系
Fig. 5 The relationships between SPM content and salinity (a), Mn concentration and SPM content (b), and the estimated relative deviation of dissolved Mn concentrations and SPM content (c) in three seasons
表 1 长江口及其邻近水域表层水体的盐度、温度和溶解Mn浓度
Tab. 1 Salinity, temperature and dissolved Mn concentration in the surface of the Changjiang River Estuary and its adjacent area
季节 水域 盐度 温度/℃ 溶解Mn浓度/（nmol·L−1） 样本数 范围 均值 样本数 范围 均值 样本数 范围 均值 秋季 全水域 24 0.0～32.1 18.9 ± 11.6 21 26.4～29.5 28.0 ± 1.0 21 3.8～12.9 7.8 ± 2.5 淡水 5 0.0～0.1 0.04 ± 0.05 5 28.7～28.9 28.8 ± 0.1 5 6.2～9.7 8.0 ± 1.3 冲淡水 16 2.8～29.5 22.6 ± 7.0 14 26.4～29.5 27.7 ± 1.0 14 3.8～12.9 7.7 ± 2.9 海水 3 30.4～30.6 31.0 ± 0.8 2 27.6～29.0 28.3 ± 0.7 2 7.3～8.3 7.8 ± 0.5 春季 全水域 32 0.2～34.8 23.6 ± 13.4 32 10.1～17.0 12.8 ± 1.7 31 2.7～15.7 4.4 ± 1.0 淡水 5 0.2～0.3 0.2 ± 0.02 5 12.1～12.7 12.4 ± 0.2 5 3.1～5.5 4.5 ± 1.0 冲淡水 10 1.0～29.6 19.2 ± 11.0 10 10.1～12.3 12.3 ± 0.6 10 3.2～6.1 4.9 ± 1.0 海水 17 30.4～34.8 33.1 ± 1.4 17 11.4～17.0 13.8 ± 1.8 16 2.7～7.0 4.1 ± 0.9 夏季 全水域 24 0.1～31.4 18.5 ± 13.2 24 22.9～28.8 27.3 ± 1.8 22 2.0～20.5 9.7 ± 5.0 淡水 7 0.1～0.2 0.1 ± 0.01 7 28.4～28.6 28.5 ± 0.07 6 10.9～20.5 16.0 ± 3.7 冲淡水 14 2.8～30.0 25.0 ± 7.4 14 23.9～28.8 27.0 ± 1.7 14 2.0～15.4 7.4 ± 3.2 海水 3 30.1～31.4 30.8 ± 0.6 3 22.9～28.0 26.2 ± 2.3 2 6.9～7.7 7.3 ± 0.4 
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表 2 长江口至东海区域中表层盐度和溶解Mn浓度的历史数据对比
Tab. 2 The comparison of historical salinity and dissolved Mn concentrations in the surface from the Changjiang River Estuary to the East China Sea
研究区域 时间 纬度 经度 盐度（平均值） 溶解Mn浓度（平均值）/（nmol·L−1） 参考文献 长江口表层水 2021年3月 29°～32°N 120°～125°E 0.2～34.8
（23.6）2.7～15.7
（4.4）本研究 2021年7月 29°～32°N 120°～125°E 0.1～31.4
（18.5）2.0～20.5
（9.7）2019年9月 29°～32°N 120°～125°E 0.0～32.1
（18.9）3.8～12.9
（7.8）长江口表层水 2012年3月 29°～33°N 120°～124°E 0.2～33.9
（25.1）2.5～55.1
（11.5）文献[25] 2012年7月 29°～33°N 120°～124°E 0.1～32.3
（23.2）4.2～74.1
（16.5）长江口、东海表层水 2011年5月 23°～34°N 120°～128°E 24.4～34.6
(32.2)2.6～21.8
(7.7)文献[23] 2011年8月 27°～34°N 120°～128°E 21.5～33.8
(29.6)4.2～15.5
(9.6)2011年11月 29°～32°N 120°～128°E 24.3～33.8
(31.1)2.5～13.9
(6.5)东海表层水 2015年10月 26°～32°N 120°～128°E 20.4～34.9
（32.4）2.2～10.7
（6.1）文献[30]
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表 3 世界部分河流、河口、边缘海及大洋的表层溶解Mn浓度
Tab. 3 Surface dissolved Mn concentrations of rivers, estuaries, marginal seas and oceans in the world
类别 采样区域 溶解Mn浓度/（nmol·L−1） 参考文献 河流 长江 3.1～20.5 本研究 长江 7.2～82.9 文献[15] 哥伦比亚河 60.0～240.0 文献[7] 哈得孙河 33.0～1 460.0 文献[26] 珠江 1.5～512.3 文献[32] 河口 长江口咸水 2.0～15.4 本研究 哥伦比亚河口 12. 0～40.0 文献[33] 哈得孙河河口 33.0～1 640.0 文献[26] 杰克逊港口 24.5～1 172.7 文献[34] 长江口海水 2.7～8.3 本研究 边缘海 东海 1.5～21.8 文献[30] 南海 1.8～16.2 文献[35] 威德尔海 0.2～0.4 文献[36] 马尾藻海 0.7～4.3 文献[37] 大洋 西北太平洋 1.2～2.6 文献[38] 南大洋 0.04～0.6 文献[39]
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表 4 各季节溶解 Mn 浓度与其他环境因子的皮尔逊相关性
Tab. 4 Pearson correlation between dissolved Mn concentration and other environmental factors in different seasons
季节 盐度 温度 溶解无机氮浓度 磷酸盐浓度 硅酸盐浓度 叶绿素浓度 溶解氧浓度 悬浮颗粒物含量 春季 −0.33 −0.25 0.33 0.16 0.29 0.20 −0.12 0.38 夏季 −0.36* −0.25 0.35 0.27 0.30 0.53** −0.15 0.18 秋季 −0.74** 0.51* 0.60* 0.028 0.35 0.039 −0.57** −0.26 注：**指相关性在0.01级别上显著（双尾检验）；*指相关性在0.05级别上显著（双尾检验）。
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