海洋沉积物中氧化还原敏感元素对水体环境缺氧状况的指示作用
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摘要
近年来由于人为污染水体富营养化加剧,缺氧区面积不断增大,利用沉积物中氧化还原敏感元素反演水体缺氧情况已经发展成为海洋化学领域的热点研究方向。本文详细阐述了氧化还原敏感元素的富集机制,并总结了利用沉积物中氧化还原敏感元素在不同氧化还原条件下的富集程度反映海水缺氧程度和底质氧化还原状况的一系列指标,如Re/Mo、Cd/U、Th/U、V/Sc、V/(V+Ni)值,U—Mo共变模型,δ~(98/95)Mo,多指标微/痕量元素模型以及氧化还原敏感元素-有机质共变模型等。沉积物中Re、Mo含量、Re/Mo值、自生Mo/U值、Th/U值对上层水体缺氧和氧化条件区分良好,可定量指征上层水体的缺氧情况。沉积物中Re含量近似于1 ng/g(地壳值),Mo含量>1μg/g(地壳值),Re/Mo值接近0.3×10~(-3),Mo—U富集系数比为(0.1～0.3)×现代海水,Th/U值>2,可指示氧化环境;Re含量在10～30 ng/g,Mo含量近似于1μg/g,Re/Mo值10×10~(-3)～30×10~(-3),Mo—U富集系数比>1×现代海水,Th/U值在0～2范围内,可指示缺氧环境;Re含量>30 ng/g,Mo富集达到20～40μg/g,Re/Mo值接近0.7×10~(-3)(海水中Re/Mo值),Mo—U富集系数比为(3～10)×现代海水,可指示极度缺氧的硫化环境。Mo_(EF)—U_(EF)交会对数坐标图、氧化还原敏感元素-有机质共变模型指标可定性分析上层水体的缺氧情况;V/(V+Ni)值对于次氧化沉积物指示效果不佳;Cd/U值在次缺氧条件下的变化机制复杂,还需进一步研究。生物扰动、成岩作用、人为污染、水体局限、高有机碳通量、Fe、Mn氧化物循环等因素通过影响氧化还原敏感元素在沉积物中的富集与迁移,从而影响氧化还原敏感元素指标的应用,应剔除有机质吸附与陆源输入等非自生部分的影响,结合各种指标互相印证,综合判别水体氧化还原状态。
In recent years, due to the eutrophication of water polluted by human, the area of anoxic zone had been increasing. Using the redox sensitive elements in sediments to indicate the anoxia of water environment has become a hot research field in marine chemistry field. This paper expounded the enrichment mechanisms of redox sensitive elements in details and summarized a series of indicators reflecting the status of redox conditions of water environment, such as Re/Mo, Cd/U, Th/U, V/Sc ratio, U—Mo covariation, δ~(98/95)Mo, multi-indicator trace element model, redox sensitive elements—organic matter covariation model and so on, according to the enrichment levels of redox sensitive elements in sediments under different redox conditions. The Re, Mo content, Re/Mo ratio, authigenic Mo/U ratio, and Th/U ratio distinguish well between anoxic and oxidative conditions of the upper water, and can quantitatively indicate the redox condition of the upper water body. The Re content in the sediment with approximately 1 ng/g(the crust value), Mo content higher than 1μg/g(the crust value), Re/Mo ratio closed to 0.3×10~(-3), Mo—U enrichment coefficient ratio with(0.1～0.3) × modern seawater, Th/U ratio higher than 2, can indicate oxidation environment in overlaying water and surface sediment. The Re content about 10～30 ng/g, the Mo content with approximately 1μg/g, the Re/Mo ratio between 10×10~(-3) and 30×10~(-3), the Mo—U enrichment factor ratio higher than 1 × modern seawater, and the Th/U ratio in the range of 0～2, can indicate anoxic environment, while Re content higher than 30 ng/g, Mo enrichment reaching 20～40μg/g, Re/Mo ratio closed to 0.7×10~(-3)(Re/Mo ratio in seawater), Mo—U enrichment factor ratio about(3～10)× modern sea water, can indicate the sulfurized environment. Mo_(EF) vs. U_(EF) diagram and redox sensitive elements—organic matter covariation model indexes can be qualitatively used to analyze the anoxic condition of the upper water body, but V/(V+Ni) ratio is not suitable for the indication of sub-anoxic sediment. For Cd/U index, there are still many problems in the mechanism of Cd/U value variation under hypoxic conditions, which requires further study. The application of redox sensitive elements can be affected by the factors including biological disturbance, diagenesis, human pollution, water restriction, cycle of Fe, Mn oxides and high organic carbon flux, which influence the enrichment and migration of redox sensitive elements in sediments. Hence, the effects of non-authigenic elements such as adsorption on organic matter and terrestrial input should be eliminated, and various indicators should be used to confirm each other and to identify the redox status of the water environment.
In recent years, due to the eutrophication of water polluted by human, the area of anoxic zone had been increasing. Using the redox sensitive elements in sediments to indicate the anoxia of water environment has become a hot research field in marine chemistry field. This paper expounded the enrichment mechanisms of redox sensitive elements in details and summarized a series of indicators reflecting the status of redox conditions of water environment, such as Re/Mo, Cd/U, Th/U, V/Sc ratio, U—Mo covariation, δ~(98/95)Mo, multi-indicator trace element model, redox sensitive elements—organic matter covariation model and so on, according to the enrichment levels of redox sensitive elements in sediments under different redox conditions. The Re, Mo content, Re/Mo ratio, authigenic Mo/U ratio, and Th/U ratio distinguish well between anoxic and oxidative conditions of the upper water, and can quantitatively indicate the redox condition of the upper water body. The Re content in the sediment with approximately 1 ng/g(the crust value), Mo content higher than 1μg/g(the crust value), Re/Mo ratio closed to 0.3×10~(-3), Mo—U enrichment coefficient ratio with(0.1～0.3) × modern seawater, Th/U ratio higher than 2, can indicate oxidation environment in overlaying water and surface sediment. The Re content about 10～30 ng/g, the Mo content with approximately 1μg/g, the Re/Mo ratio between 10×10~(-3) and 30×10~(-3), the Mo—U enrichment factor ratio higher than 1 × modern seawater, and the Th/U ratio in the range of 0～2, can indicate anoxic environment, while Re content higher than 30 ng/g, Mo enrichment reaching 20～40μg/g, Re/Mo ratio closed to 0.7×10~(-3)(Re/Mo ratio in seawater), Mo—U enrichment factor ratio about(3～10)× modern sea water, can indicate the sulfurized environment. Mo_(EF) vs. U_(EF) diagram and redox sensitive elements—organic matter covariation model indexes can be qualitatively used to analyze the anoxic condition of the upper water body, but V/(V+Ni) ratio is not suitable for the indication of sub-anoxic sediment. For Cd/U index, there are still many problems in the mechanism of Cd/U value variation under hypoxic conditions, which requires further study. The application of redox sensitive elements can be affected by the factors including biological disturbance, diagenesis, human pollution, water restriction, cycle of Fe, Mn oxides and high organic carbon flux, which influence the enrichment and migration of redox sensitive elements in sediments. Hence, the effects of non-authigenic elements such as adsorption on organic matter and terrestrial input should be eliminated, and various indicators should be used to confirm each other and to identify the redox status of the water environment.
引文
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