海水痕量元素—有机配体的配分特征与影响因素研究进展

doi:10.11867/j.issn.1001-8166.2019.05.0499

地球科学进展 ›› 2019, Vol. 34 ›› Issue (5): 499 -512. doi: 10.11867/j.issn.1001-8166.2019.05.0499

泮枫敏 ^1, ^2, ³(

),袁华茂 ^1, ^2, ^3, ⁴(

),宋金明 ^1, ^2, ^3, ⁴,段丽琴 ^1, ^2, ^3, ⁴

1. 中国科学院海洋生态与环境科学重点实验室，中国科学院海洋研究所，山东青岛 266071
2. 中国科学院大学，北京 100049
3. 青岛海洋科学与技术国家实验室海洋生态与环境科学功能实验室，山东青岛 266237
4. 中国科学院海洋大科学中心，山东青岛 266071

收稿日期:2018-10-24 修回日期:2019-04-05 出版日期:2019-05-10
通讯作者: 袁华茂 E-mail:15092139387@163.com;yuanhuamao@qdio.ac.cn
基金资助:
青岛海洋科学与技术国家实验室鳌山科技创新计划项目“微/痕量元素在绿潮生消过程中的调控与反馈机制”(编号：2016ASKJ02-4);国家自然科学基金委员会—山东省人民政府联合基金项目“海洋生态环境变化的生物地球化学机制”(编号：U1606404)

The Distribution of Trace Elements-Organic Ligands in Seawater and Factors Influencing Their Complexation

Fengmin Pan ^1, ^2, ³( ),Huamao Yuan ^1, ^2, ^3, ⁴( ),Jinming Song ^1, ^2, ^3, ⁴,Liqin Duan ^1, ^2, ^3, ⁴

1. Key Laboratory of Ecology and Environmental Sciences, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. Function Laboratory of Marine Ecology and Environmental Sciences, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266237, China
4. Center for Ocean Mega-Science, Chinese Academy of Sciences, Qingdao 266071, China

Received:2018-10-24 Revised:2019-04-05 Online:2019-05-10 Published:2019-07-04
Contact: Huamao Yuan E-mail:15092139387@163.com;yuanhuamao@qdio.ac.cn
About author:Pan Fengmin (1995-), female, Zhucheng City, Shandong Province, Master student. Research areas include marine biogeochemistry. E-mail: 15092139387@163.com
Supported by:
Project supported by Aoshan Technology Innovation Program of Qingdao National Laboratory for Marine Science and Technology “Regulation and feedback mechanism of micro/trace elements in the green tide generation and elimination process”(No.2016ASKJ02-4);The National Natural Science Foundation of China and Shandong Province Joint Fund “Biogeochemical mechanism of marine ecological environment changes”(No.U1606404)

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在痕量元素的海洋生物地球化学循环过程中，有机配体直接控制痕量元素在不同形态及粒径范围内的分配，进而影响痕量元素的迁移转化过程和生物可利用性。深入研究海水中痕量元素—有机配体的配分特征及影响因素，明确有机配体分子量组分及其对痕量元素的配合作用差异，对于了解痕量元素的生物地球化学行为，评估痕量元素的生物可利用性和毒性效应均具有十分重要的意义。对海水中痕量元素—有机配体的分布规律、配分特征及盐度、pH、氧化还原条件和生物活动对配体的影响进行了系统总结。海水中的有机配体一般以低分子量部分为主体，配合能力因元素性质差异存在随分子量增加而提高或降低的不同趋势。除此之外，有机配体的结构、配合能力及分子量分布随水体各物理化学参数的变化而改变。盐度的增加会降低有机配体相邻官能团的静电排斥力从而降低配体的配合能力，还会导致高分子量金属有机配合物发生絮凝和降解而去除。pH的增加不仅可以促使有机配体离子化，还能促进部分痕量元素水解为与有机配体亲和力更高的形式，提高有机配体配合率。氧化还原环境同时影响了痕量元素的价态和有机配体的浓度，间接影响痕量元素—有机配体的配合率。浮游植物利用及微生物分解可以增加低分子量有机配体的比例，从而提高其配合能力，但当生物遭受过量金属离子的毒性胁迫时，其细胞内会释放胞内配体，将致毒元素转化为配合物并排出体外，从而增加水体中痕量元素高分子量有机配体的浓度。未来应结合有机物结构分析技术及痕量元素分离检测技术，系统研究海洋环境中不同分子量有机配体的结构及与痕量元素配合强度的相互关系，进一步揭示痕量元素的迁移转化过程与生态学意义。

关键词: 痕量元素, 有机配体, 分子量, 盐度, pH

Organic metal-binding ligands represent an essential role in the bioavailability of trace elements since they govern the species and sizes of those elements in seawater. The distribution and properties of organic ligands in seawater as well as the factors influencing their complexation abilities were summarized in this paper. Most organic ligands exist in the low molecular weight fraction, and their concentration nearshore is often higher than that of open ocean while the vertical distribution varies in different areas. The complexation of trace elements and organic ligands is influenced by several factors such as molecular weight of organic ligands, salinity, pH, biological activities and redox conditions. Ligand with a lower molecular weight usually represents stronger complexation ability, whereas the opposite seems to be true sometimes due to the specific affinity between some elements and ligands. Increasing salinity lowers the electrostatic repulsion among adjacent functional groups of ligands and thus decreases their complexing rate, yet increasing pH promotes the ionization of organic ligands and results in the formation of more complexes. The utilization of phytoplankton and degradation of microorganism release more low molecular weight organic ligands while more high molecular weight ligands are released from marine organisms under heavy metal stress. Therefore, sufficient significance should be attached to characterizing the structure and molecular weight of organic ligands and exploring the interaction between trace elements and organic ligands and the influence of related marine factors on their behaviors, which will certainly help us to understand the global biogeochemical cycles and ecological significance of trace elements.

Key words: Trace elements, Organic ligands, Molecular weight, Salinity, pH.

中图分类号:

P734

图1 南大洋中（0～1 000 m）溶解态铁、温度、盐度、硝酸盐、硅酸盐、荧光强度、总铁配体/强铁配体、细菌丰度的垂直分布^{[

17
]}

Fig.1 The vertical distribution of dissolved iron, temperature, salinity, nitrate, silicate, fluorescence, total iron ligands/strong iron ligands and bacterial abundance in Southern Ocean (0～1 000 m)^{[

17
]}

图2 东北太平洋中总溶解态铜，铜强配体，铜弱配体的垂直分布^{[

19
]}

Fig.2 The vertical distribution of total dissolved copper, strong copper ligands and weak copper ligands in Northeastern Pacific Ocean ^{[

19
]}

图3 溶解有机物，溶解态金属及配合物，多核金属簇，胶体，微生物的粒径分布^{[

21
]}

Fig.3 The size distribution of dissolved organic matters, dissolved metal complexes, polynuclear cluster, colloids and microorganisms ^{[

21
]}

图4 不同水体类型（河流、湖泊、海洋）中溶解有机物的分子量分布^{[

23
]}

Fig.4 The size distribution of dissolved organic matters in different aquatic environments (river, lake and ocean)^{[

23
]}

表1 不同类型溶解有机物的分子量分布 ^{[

31
]}

Table 1 The distribution of molecular weight of different dissolved organic matters ^{[

31
]}

溶解有机物类型	胡敏酸	富里酸	碳水化合物	蛋白质	脂肪酸	氨基酸
相对分子量/kDa	2～5	0.5～2	0.18～3 000	10～1 000	0.25～0.85	< 0.2

表1 不同类型溶解有机物的分子量分布 ^{[

31
]}

Table 1 The distribution of molecular weight of different dissolved organic matters ^{[

31
]}

溶解有机物类型	胡敏酸	富里酸	碳水化合物	蛋白质	脂肪酸	氨基酸
相对分子量/kDa	2～5	0.5～2	0.18～3 000	10～1 000	0.25～0.85	< 0.2

图5 与有机物分子量相关的海洋学过程^{[

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]}

Fig.5 The oceanographic processes related to the molecular weight of organic matters ^{[

54
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图6 盐度对DOM有关物理化学过程的影响^{[

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]}

Fig.6 The influence of salinity to the physiochemistry processes related to DOM ^{[

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]}

表 2 部分海区与强有机配体结合的 Cu²⁺，强有机配体以及估算不同 pH条件下自由 Cu²⁺ 的浓度 ^{[

62
]}

Table 2 The concentration of Cu²⁺ complexation with L₁,L₁ and estimated free Cu²⁺（pH=8.1, pH=7.4） ^{[

62
]}

海区	与强有机配体结合的铜/（nmol/L）	强有机配体/（nmol/L）	Cu²⁺/（pmol/L，pH=8.1）	Cu²⁺/（pmol/L，pH=7.4）
东北太平洋	0.59	1.6	1.1	1.7
印度洋	1.7	3.1	0.42	1.2
南大西洋	2.3	11	0.17	0.24
比斯坎湾	2.7	5.1	1.1	2.4
纳拉甘西特湾	21	35	0.7	1.9

表 2 部分海区与强有机配体结合的 Cu²⁺，强有机配体以及估算不同 pH条件下自由 Cu²⁺ 的浓度 ^{[

62
]}

Table 2 The concentration of Cu²⁺ complexation with L₁,L₁ and estimated free Cu²⁺（pH=8.1, pH=7.4） ^{[

62
]}

海区	与强有机配体结合的铜/（nmol/L）	强有机配体/（nmol/L）	Cu²⁺/（pmol/L，pH=8.1）	Cu²⁺/（pmol/L，pH=7.4）
东北太平洋	0.59	1.6	1.1	1.7
印度洋	1.7	3.1	0.42	1.2
南大西洋	2.3	11	0.17	0.24
比斯坎湾	2.7	5.1	1.1	2.4
纳拉甘西特湾	21	35	0.7	1.9

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