河口水体溶解性有机质与重金属的相互作用研究进展

Research progress on the interaction between dissolved organic matter and heavy metals in estuarine waters

  • 摘要: 河口是陆源物质进入海洋前发生混合、转化、截留和再分配的关键界面,也是溶解性有机质(Dissolved organic matter, DOM)与重金属发生强烈相互作用的生物地球化学反应器。河口水体DOM具有来源复杂、组成异质、分子量连续分布和活性官能团丰富等特点,可通过络合、吸附、絮凝、氧化还原等过程调控重金属在溶解态、胶体态、颗粒态和沉积相之间的分配与转化,并驱动其在多介质界面间的迁移行为。近年来,紫外-可见吸收光谱、三维荧光光谱、尺寸排阻色谱、粒级分离技术、高分辨质谱等表征手段的发展,显著推动了河口DOM的来源解析、组成识别和分子结构表征及其与重金属相互作用机制研究。河口水体DOM的数量和性质受河流输入、工业污水排放、浮游植物和微生物内源生产以及沉积物释放等多源过程共同控制,同时,盐度梯度、离子强度、pH等环境因子可进一步改变DOM的组成、结构和重金属结合能力。DOM与重金属的相互作用机制与其分子量、芳香性、官能团等特征及环境因子密切相关。本文系统综述了河口水体DOM的来源、组成与表征方法,重点阐明DOM与重金属的作用机制、关键影响因素及对重金属的调控;在此基础上,提出未来应加强多尺度表征技术联用、活性配体定量识别、多相耦合过程解析和极端事件响应等方面的研究,以期为河口重金属污染风险评估、水质基准修正和生态环境管理提供科学支撑。

     

    Abstract: Estuaries serve as critical interfaces where terrestrial materials undergo mixing, transformation, retention, and redistribution before entering the ocean. They also function as biogeochemical reactors in which dissolved organic matter (DOM) interacts strongly with heavy metals. Estuarine DOM is characterized by complex sources, heterogeneous composition, continuous molecular-weight distribution, and abundant reactive functional groups. Through processes including complexation, adsorption, flocculation, and redox reactions, DOM modulates the partitioning and transformation of heavy metals among dissolved fraction, colloidal fraction, particulate fraction, and sedimentary phase, thereby driving their migration across multi-medium interfaces. In recent years, advances in characterization techniques—such as ultraviolet-visible absorption spectroscopy, three-dimensional excitation-emission matrix fluorescence spectroscopy, size-exclusion chromatography, size-fractionation techniques, and high-resolution mass spectrometry—have significantly promoted research on the source apportionment, compositional identification, molecular structural characterization of estuarine DOM, and its interaction mechanisms with heavy metals. The quantity and properties of estuarine DOM are co-regulated by multi-source processes including riverine input, industrial wastewater discharge, autochthonous production by phytoplankton and microorganisms, and sediment release. Meanwhile, environmental factors such as salinity gradients, ionic strength, and pH can further modify the composition, structure, and heavy metal-binding capacity of DOM. The interaction mechanisms between DOM and heavy metals are closely linked to DOM characteristics (e.g., molecular weight, aromaticity, functional groups) and environmental conditions. This review systematically summarizes the sources, composition, and characterization methods of estuarine DOM, with emphasis on the interaction mechanisms between DOM and heavy metals, the key influencing factors, and the regulatory effects of DOM on heavy metals. On this basis, future research should focus on the integrated application of multi-scale characterization techniques, quantitative identification of reactive ligands, analysis of multi-phase coupling processes, and responses to extreme events, with the aim of providing scientific support for heavy metal pollution risk assessment, water quality criteria revision, and ecological environmental management in estuarine systems.

     

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