Research progress on reconstruction method of redox conditions in submarine seafloor cold seeps
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摘要:
冷泉活动是现代深海极端环境系统之一，其在天然气水合物资源勘探、全球气候变化、极端环境生命活动等方面具有重要的科学研究意义。重建海底冷泉区氧化还原环境是研究其中生物地球化学过程、揭示甲烷渗漏活动特征的重要途径。近年来，大量矿物学及地球化学指标在冷泉系统氧化还原条件的恢复研究中获得了成功的应用。在前人研究的基础上，对自生矿物学标志、稀土元素、氧化还原敏感元素（Mo、U、Fe）和稳定同位素（钼同位素δ98Mo、铁同位素δ56Fe、硫同位素δ34S）等不同指标对氧化还原环境变化的响应机制进行了系统总结，从测试分析方法、后期成岩改造、单一指标的多解性等多个方面探讨了各指标的影响因素和当前仍存在的问题，并指出了未来该领域需进一步加强的关键研究方向。
Abstract:Cold seep is one of the seafloor extreme environmental systems, it has important scientific significance in gas hydrate exploration and global climate change for extreme environmental life activities. Reconstruction of redox conditions in cold seep is an important way to study the biogeochemical processes and reveal the characteristics of methane seepage. In recent years, many mineralogical and geochemical indicators have been successfully used in the study of the recovery of redox conditions in cold seep systems. Based on previous studies, the responding mechanisms of different redox indicators were summarized, such as autogenetic mineralogical characteristics, rare earth elements, redox sensitive elements (Mo, U, and Fe), and stable isotopes (δ98Mo, δ56Fe, and δ34S). The influencing factors and existing issues of each index were discussed from the aspects of test and analysis methods, diagenetic alteration, and non-uniqueness in using a single index. At last, the key research direction in this field in the future was proposed.
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Key words:
- cold seep /
- redox /
- authigenic mineral /
- geochemical proxy /
- environmental reconstruction
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表 1 不同指标指示的沉积环境和影响因素
Table 1. Sedimentary environment indicated by different indices and their influencing factors
指标 沉积环境 影响因素 矿物学标志 碳酸盐矿物 偏氧化环境：文石
还原环境：方解石、白云石只能对氧化还原环境进行粗略的重建；受是否为原位埋藏、后期氧化、重结晶、二次生长、成岩蚀变等因素影响 草莓状黄铁矿 氧化-次氧化环境：平均粒径为（7.7±4.1） µm，有10%～50%的粒径超过10 µm
硫化环境：平均粒径为（5.0±1.7） µm，并且其中
仅约4%的黄铁矿粒径可以长到10 µm以上稀土元素 Ce异常 氧化环境：Ce负异常
缺氧环境：无Ce异常或Ce正异常容易受到成岩作用的影响；测试分析过程中容易与陆源碎屑物质的稀土元素发生混染；此外，富含有机质的高碱度流体也可以产生Ce负异常，造成多解性 氧化还原
敏感元素Mo含量 有限的硫化环境：2～25 μg/g
长期稳定的硫化环境：＞100 μg/g受有机质和铁锰氧化物的吸附作用、沉积速率、环境开放与否等因素影响 MoEF/UEF 氧化-次氧化环境：（0.1～0.3）×现代海水
缺氧环境：＞1×现代海水
硫化环境：（3～10）×现代海水受测试样品中Al元素含量的影响。异常低的Al元素含量会导致富集系数偏高 Fe的化学种 氧化环境：自生Fe以Fe3+为主
还原环境：自生Fe以Fe2+为主受Fe含量、结晶度（如是否为无定形状态）、黏土矿物含量等因素影响 稳定同位素 Mo同位素 氧化环境：同位素分馏较大
厌氧硫化环境：同位素分馏小容易受仪器测试精度影响 S同位素 厌氧硫化环境：S同位素分馏程度小，硫化物矿物
δ34S值偏高受甲烷渗漏持续时间、Fe的供给、硫的歧化作用等影响 Fe同位素 氧化条件：Fe同位素值较高
还原条件：Fe同位素值较低受Fe的瑞利分馏、不完全氧化、后期成岩作用等众多因素影响 
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表 2 沉积物中Mo含量对水体状态的指示
Table 2. Indication of water column status by Mo content in sediments
Mo含量/（μg/g） 水体状态 2～25 硫化环境，但H2S仅局限于孔隙水 25～100 复杂多变的环境 ＞100 长期稳定的硫化环境
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