水成型铁锰成矿的纳米成因研究进展
收稿日期: 2023-07-03
修回日期: 2023-08-02
网络出版日期: 2023-09-25
基金资助
国家自然科学基金项目(91428207);国家重点基础研究发展计划(2012CB417300)
Research Progress on the Nanogenesis of Hydrogenetic Fe-Mn Mineralization
Received date: 2023-07-03
Revised date: 2023-08-02
Online published: 2023-09-25
Supported by
the National Natural Science Foundation of China(91428207);The Major State Basic Research Development Program of China(2012CB417300)
新生代深海铁锰矿床的大规模成矿是地质历史上特有的现象，其形成的海底铁锰结核/结壳因富含巨量的有用金属而备受关注。水成型铁锰成矿的胶体成因模型自20世纪90年代中期提出以来已被广泛接受并采用。随着近20年来纳米地球科学的迅速发展，人们意识到纳米颗粒作为胶体的最小部分，能够以其独特的性质显著影响铁锰成矿过程。通过总结已有研究，发现铁氧化物与锰氧化物会以纳米颗粒的形式普遍共存于多种表生地质环境，还证实了水成型铁锰结核/结壳中的主要铁锰矿物（如水羟锰矿和水铁矿）都是纳米颗粒。铁氧化物纳米颗粒对二价锰［Mn（II）］的表面催化氧化可能是水成型铁锰矿物通常在纳米尺度密切共生的原因。此外，在铁锰结壳中还观测到大量在以往研究中被普遍忽视的三价锰［Mn（III）］矿物，其含量在结壳顶部最高，随深度增加逐渐下降，四价锰［Mn（IV）］矿物的含量则呈相反的变化趋势。不同价态锰氧化物纳米颗粒的表面能差异导致Mn（III）矿物在Mn（II）的氧化过程中最先沉淀，并可能在沉淀之后逐渐转化为Mn（IV）矿物。相信随着纳米地球科学与高精度原位实验技术的发展，必将不断深化对海水铁锰循环及海底铁锰成矿的认识。
关键词： 水成型铁锰结核/结壳; 胶体成因模型; 纳米颗粒; 铁锰氧化物; 表面催化氧化
张维石 , 周怀阳 . 水成型铁锰成矿的纳米成因研究进展[J]. 地球科学进展, 2023 , 38(9) : 904 -915 . DOI: 10.11867/j.issn.1001-8166.2023.054
The extensive mineralization of Cenozoic deep-sea ferromanganese deposits is a unique phenomenon in geological history. Ferromanganese nodules/crusts have attracted considerable attention owing to their enrichment in critical metals. The colloidal genetic model of hydrogenetic Fe-Mn mineralization has been widely accepted and applied since it was first proposed in the mid-1990s. With the rapid development of nanogeoscience over the past two decades, it has become clear that nanoparticles, as the smallest part of colloids, can significantly affect the Fe-Mn mineralization process owing to their unique properties. It has not only been discovered that iron and manganese oxides generally coexist as nanoparticles in various supergene geological environments, but it has also been verified that the primary Fe-Mn minerals, such as vernadite and ferrihydrite, in hydrogenetic ferromanganese nodules/crusts are nanoparticles. Iron oxide nanoparticles can catalyze the surface oxidation of Mn(II), thereby potentially explaining why hydrogenetic Fe-Mn minerals are usually symbiotic even at the nanoscale. In addition, Mn(III) minerals, which have generally been neglected in previous research, have been abundantly observed in ferromanganese crusts. The Mn(III) fraction is highest near the surface of the crust and gradually decreases with increasing depth, whereas the Mn(IV) fraction shows the opposite trend. The surface energy variation among manganese oxide nanoparticles with different valence states induces the initial precipitation of Mn(III) minerals during Mn(II) oxidation, which may eventually be converted to Mn(IV) minerals over geological timescales. Further progress in comprehending the Fe-Mn cycle in seawater and Fe-Mn mineralization on the seafloor through the advancement of nanogeoscience and high-resolution in situ experimental techniques is expected in the near future.
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