南华系锰的生物化学成矿作用
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本文为国家重点研发计划课题(编号2022YFC2903404)和中国冶金地质总局地质综合研究项目(编号 中冶地\[2022\]CMGBDZYJ001)联合资助的成果


Biochemical mineralization of manganese in the Nanhua System
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    摘要:

    本次工作在湘黔地区南华系锰矿的采矿巷道以及钻孔中采集了碳酸锰矿石样品,用于开展扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)分析,结果显示矿石内碳酸锰普遍交代氧化锰,两者形成的多层微米级微古生物化石构成矿层主体。本研究通过观察矿石显微结构,总结锰矿层和锰结核内微古生物化石的发现及前人微生物代谢模拟实验成果,分析微生物的生理特征对锰质沉积的控制作用机理,证实生物化学作用是锰大规模成矿的关键。我国南华系海相沉积型锰矿产出于湘黔渝地区大塘坡组下段,各矿区锰矿层由赋存于微古生物化石内的菱锰矿物结晶集合体组成。在成矿期,蓝细菌cyanobacteria主导的微生物席生态系统在华南洋陆棚区的底水环境广泛繁育,席内蓝细菌与好氧异养细菌(AHB)、硫酸盐还原细菌(SRB)等微生物互利共生,控制了锰的沉淀以及氧化锰向碳酸锰的转化,矿物悬浮微粒或被存活微生物的表面位点吸附,或自吸附于死亡自溶菌体的空间。海水的锰通量影响微生物席,沉积了菱锰矿工业矿层及其顶底板黑色页岩。本次研究揭示,本质上是微生物席维持自身生存的生命活动促进了锰矿物的沉淀和转化:① 与锰结核相同,异养细菌的酶促反应主动沉淀氧化锰,降解有机质的代谢副产物被动还原氧化锰;② 蓝细菌主动调节EPS的微环境为弱碱性- 弱还原,调控异养细菌提升微环境中Mn2+离子的浓度,被动连续沉淀碳酸锰矿物;③ 碳酸锰和氧化锰同时沉淀于微生物细胞外,其沉积能力不受菌体吸收锰质的速度和容量的限制,能够将充足的锰质供给转化成巨量的锰矿物沉积;④ 微生物的生命周期就是碳酸锰和氧化锰的“脉动式”沉积周期,世代生长使锰矿物层层堆叠,形成了特征性的微米级矿物结构。本次工作构建了南华系海相沉积型锰矿的生物化学“外生”成矿模式,丰富了锰的“内源外生”成矿学说。

    Abstract:

    Manganese carbonate ore samples from Nanhua System deposits (Hunan- Guizhou region) were collected from mining tunnels and drill cores for analysis by SEM, TEM, and XPS. Analytical results indicate pervasive replacement of manganese oxide by manganese carbonate within the ore, with both minerals forming multilayered, micrometer- scale microfossils that make up the bulk of the ore layers. Based on microstructural observations, the discovery of microfossils within manganese layers and nodules, and previous experimental simulations of microbial metabolism, this study analyzes the mechanisms by which microbial physiology controlled manganese deposition. The findings confirm that biochemical processes were fundamental to large- scale manganese mineralization. The marine sedimentary manganese deposits of the Nanhua System occur within the lower member of the Datangpo Formation in the Hunan- Guizhou- Chongqing region. The manganese ore layers across all mining districts consist of crystalline aggregates of rhodochrosite hosted within microbial fossils. During the metallogenic period, cyanobacteria- dominated microbial mat ecosystems proliferated extensively in the bottom- water environments of the South China Ocean shelf. Within these mats, cyanobacteria interacted with aerobic heterotrophic bacteria (AHB) and sulfate- reducing bacteria (SRB) through mutualistic symbiosis, controlling manganese precipitation and the transformation of manganese oxides to carbonates. Suspended mineral particles were either adsorbed onto surface sites of living microorganisms or self- aggregated within the spaces of autolytic dead cells. Manganese fluxes in seawater influenced microbial mats to deposit industrial- grade rhodochrosite ore layers intercalated with black shales. This study reveals that the biological activities through which microbial mats promoted the precipitation and transformation of manganese minerals were essentially survival mechanisms: ① analogous to modern manganese nodules, heterotrophic bacteria actively precipitate manganese oxides through enzymatic reactions while passively reducing manganese oxides through the metabolic byproducts of organic matter degradation; ② cyanobacteria actively regulated EPS microenvironments to maintain weakly alkaline and weakly reducing conditions while enhancing Mn2+ concentrations through heterotroph regulation, thereby enabling continuous passive precipitation of manganese carbonate minerals; ③ manganese carbonates and oxides precipitate simultaneously outside microbial cells, meaning deposition capacity is not constrained by the rate or capacity of cellular manganese absorption, enabling the transformation of abundant manganese supplies into massive mineral deposits; ④ the microbial life cycle represents a “pulsed” deposition cycle of manganese carbonates and oxides, where generational growth causes manganese minerals to stack layer upon layer, forming characteristic micrometer- scale mineral structures. This work establishes a biochemical “exogenic mineralization model” for marine sedimentary manganese deposits of the Nanhua System, advancing the “Endogenous Origin and Exogenous Mineralization” metallogenic theory of manganese.

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陈旭,田郁溟,高宝龙,王哲,王华青,黄飞,刘东升,肖德长.2026.南华系锰的生物化学成矿作用[J].地质学报,100(2):484-509.
CHEN Xu, TIAN Yuming, GAO Baolong, WANG Zhe, WANG Huaqing, HUANG Fei, LIU Dongsheng, XIAO Dechang.2026. Biochemical mineralization of manganese in the Nanhua System[J]. Acta Geologica Sinica,100(2):484-509.

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  • 收稿日期:2025-11-26
  • 最后修改日期:2025-12-21
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  • 在线发布日期: 2026-02-12
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