Microbial contribution to the formation of the Carboniferous sedimentary manganese deposits in northwestern China

[Display omitted] •Cyclicicites of biogenic minerals were identified by Raman spectroscopy.•Primary accumulation and diagenetic transformation of Mn were microbially mediated.•Decomposition of cells and EPS contributed to the formation of accessory minerals. There is an increasing consensus that mic...

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Published inOre geology reviews Vol. 170; p. 106124
Main Authors Dong, Zhi-Guo, Zhang, Bang-Lu, Gyollai, Ildikó, Fintor, Krisztián, Szabó, Máté, Kovács, Ivett, Gao, Jun, Zhang, Lian-Chang, Polgári, Márta, Wang, Chang-Le
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LanguageEnglish
Published Elsevier B.V 01.07.2024
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Abstract [Display omitted] •Cyclicicites of biogenic minerals were identified by Raman spectroscopy.•Primary accumulation and diagenetic transformation of Mn were microbially mediated.•Decomposition of cells and EPS contributed to the formation of accessory minerals. There is an increasing consensus that microbes play a critical role in the genesis of sedimentary manganese (Mn) carbonate deposits. However, compelling evidence for the microbial involvement during sedimentary Mn metallogenesis remains insufficient, and the specific effects of microbial mediation need to be further elucidated. To advance our understanding of the microbial Mn metallogenesis, multi-scale petrographic observations and high-resolution mineralogical analyses (mainly based on Fourier transform infrared spectrometer and Raman spectroscopy) were conducted on the Carboniferous black shale-hosted Malkansu and limestone-hosted Zhaosu Mn ore deposits in northwestern China. Results show that the Mn ore samples are characterized by finely laminated texture with μm-scale cyclic variations of microbe-associated minerals including rhodochrosite, apatite, quartz, and organic matter as well. These features indicate the ubiquity of microbial mats during Mn mineralization. Microbial involvement is also supported by Mn carbonate aggregates with variable morphologies (filamentous with pearl necklace-like inner forms resembling vermiform morphologies and spheroidal, coccoid-like forms), as well as the annular organic matter that resembles bacterial cells. The cyclic occurrence of trace amounts of remnant Mn oxides verify that primary Mn accumulation took place under oxic bottom waters. The negative co-variation between Mn carbonates and organic matter on Raman profiles suggests that the former was formed during diagenesis via organic matter decomposition coupled with Mn oxide reduction. Combined with previous experimental simulations and natural observations, a two-step microbially mediated Mn metallogenic model is tentatively proposed for the studied Mn deposits: (1) Mn(II)-oxidizing bacteria effectively catalyzed the deposition of considerable Mn oxides under oxygenated bottom water columns, a process that was simultaneously sustained by oxygenic microbial mats such as cyanobacteria; (2) Buried Mn oxides were reduced by highly reactive organic matter sourced from dead biomats of Mn(II)-oxidizing bacteria and benthic phototrophs, a process mediated by Mn(IV)-reducing bacteria which not only promoted the reaction rate but also served as nucleation sites for Mn carbonate minerals. This model can also help to explain the occurrence of diverse authigenic accessory minerals (e.g., quartz, apatite, and talc) and remarkable enrichments of several specific elements (e.g., Co, Ce, and Mo) in the studied Mn ores, which were closely linked to the decomposed cells and extracellular polymeric substance (EPS). By comparing with previous microbial investigations on Mn deposits over geological history, we further highlight the fundamental role of microorganisms in regulating the formation of economic Mn carbonate deposits.
AbstractList [Display omitted] •Cyclicicites of biogenic minerals were identified by Raman spectroscopy.•Primary accumulation and diagenetic transformation of Mn were microbially mediated.•Decomposition of cells and EPS contributed to the formation of accessory minerals. There is an increasing consensus that microbes play a critical role in the genesis of sedimentary manganese (Mn) carbonate deposits. However, compelling evidence for the microbial involvement during sedimentary Mn metallogenesis remains insufficient, and the specific effects of microbial mediation need to be further elucidated. To advance our understanding of the microbial Mn metallogenesis, multi-scale petrographic observations and high-resolution mineralogical analyses (mainly based on Fourier transform infrared spectrometer and Raman spectroscopy) were conducted on the Carboniferous black shale-hosted Malkansu and limestone-hosted Zhaosu Mn ore deposits in northwestern China. Results show that the Mn ore samples are characterized by finely laminated texture with μm-scale cyclic variations of microbe-associated minerals including rhodochrosite, apatite, quartz, and organic matter as well. These features indicate the ubiquity of microbial mats during Mn mineralization. Microbial involvement is also supported by Mn carbonate aggregates with variable morphologies (filamentous with pearl necklace-like inner forms resembling vermiform morphologies and spheroidal, coccoid-like forms), as well as the annular organic matter that resembles bacterial cells. The cyclic occurrence of trace amounts of remnant Mn oxides verify that primary Mn accumulation took place under oxic bottom waters. The negative co-variation between Mn carbonates and organic matter on Raman profiles suggests that the former was formed during diagenesis via organic matter decomposition coupled with Mn oxide reduction. Combined with previous experimental simulations and natural observations, a two-step microbially mediated Mn metallogenic model is tentatively proposed for the studied Mn deposits: (1) Mn(II)-oxidizing bacteria effectively catalyzed the deposition of considerable Mn oxides under oxygenated bottom water columns, a process that was simultaneously sustained by oxygenic microbial mats such as cyanobacteria; (2) Buried Mn oxides were reduced by highly reactive organic matter sourced from dead biomats of Mn(II)-oxidizing bacteria and benthic phototrophs, a process mediated by Mn(IV)-reducing bacteria which not only promoted the reaction rate but also served as nucleation sites for Mn carbonate minerals. This model can also help to explain the occurrence of diverse authigenic accessory minerals (e.g., quartz, apatite, and talc) and remarkable enrichments of several specific elements (e.g., Co, Ce, and Mo) in the studied Mn ores, which were closely linked to the decomposed cells and extracellular polymeric substance (EPS). By comparing with previous microbial investigations on Mn deposits over geological history, we further highlight the fundamental role of microorganisms in regulating the formation of economic Mn carbonate deposits.
ArticleNumber 106124
Author Polgári, Márta
Zhang, Bang-Lu
Kovács, Ivett
Dong, Zhi-Guo
Gyollai, Ildikó
Szabó, Máté
Zhang, Lian-Chang
Fintor, Krisztián
Wang, Chang-Le
Gao, Jun
Author_xml – sequence: 1
  givenname: Zhi-Guo
  surname: Dong
  fullname: Dong, Zhi-Guo
  email: dongzhiguo@mail.iggcas.ac.cn
  organization: Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
– sequence: 2
  givenname: Bang-Lu
  surname: Zhang
  fullname: Zhang, Bang-Lu
  organization: Development and Research Center, China Geological Survey, Beijing 100037, China
– sequence: 3
  givenname: Ildikó
  surname: Gyollai
  fullname: Gyollai, Ildikó
  email: gyollai.ildiko@csfk.org
  organization: Institute for Geological and Geochemical Research, HUN-REN Research Centre for Astronomy and Earth Sciences, Budapest H-1112, Hungary
– sequence: 4
  givenname: Krisztián
  surname: Fintor
  fullname: Fintor, Krisztián
  organization: Department of Mineralogy, Geochemistry and Petrology, University of Szeged, Budapest H-6722, Hungary
– sequence: 5
  givenname: Máté
  surname: Szabó
  fullname: Szabó, Máté
  email: szabo.mate@csfk.org
  organization: Institute for Geological and Geochemical Research, HUN-REN Research Centre for Astronomy and Earth Sciences, Budapest H-1112, Hungary
– sequence: 6
  givenname: Ivett
  surname: Kovács
  fullname: Kovács, Ivett
  email: kovacs.ivett@csfk.org
  organization: Institute for Geological and Geochemical Research, HUN-REN Research Centre for Astronomy and Earth Sciences, Budapest H-1112, Hungary
– sequence: 7
  givenname: Jun
  surname: Gao
  fullname: Gao, Jun
  email: gaojun@mail.iggcas.ac.cn
  organization: Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
– sequence: 8
  givenname: Lian-Chang
  surname: Zhang
  fullname: Zhang, Lian-Chang
  email: lczhang@mail.iggcas.ac.cn
  organization: Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
– sequence: 9
  givenname: Márta
  orcidid: 0000-0003-4101-5690
  surname: Polgári
  fullname: Polgári, Márta
  email: rodokrozit@gmail.com
  organization: Institute for Geological and Geochemical Research, HUN-REN Research Centre for Astronomy and Earth Sciences, Budapest H-1112, Hungary
– sequence: 10
  givenname: Chang-Le
  surname: Wang
  fullname: Wang, Chang-Le
  email: wangcl@mail.iggcas.ac.cn
  organization: Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
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Keywords Biosignatures
Microbial metallogenesis
Carboniferous
Mn carbonate deposits
Malkansu
Zhaosu
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Snippet [Display omitted] •Cyclicicites of biogenic minerals were identified by Raman spectroscopy.•Primary accumulation and diagenetic transformation of Mn were...
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StartPage 106124
SubjectTerms Biosignatures
Carboniferous
Malkansu
Microbial metallogenesis
Mn carbonate deposits
Zhaosu
Title Microbial contribution to the formation of the Carboniferous sedimentary manganese deposits in northwestern China
URI https://dx.doi.org/10.1016/j.oregeorev.2024.106124
Volume 170
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