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Insight into the genesis of the Zhaosu Carboniferous Mn carbonate deposit (NW China): constraints from petrography, geochemistry, and C–Mo isotopes

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Abstract

The genesis (primary versus secondary) of Mn carbonate-rich sediments, which consist of sub-economic rocks and ore deposits, remains hotly debated. Here, we investigated the petrographic, geochemical, and C–Mo isotopic characteristics of the Zhaosu Mn carbonate deposit in northwestern China, in order to provide constraints on its origin. The Mn ores occur within a Carboniferous marine transgressive siliciclastic-carbonate succession, and are mainly comprised of Mn carbonate minerals with subordinate alabandite. Within the Mn ores, organic matter is commonly replaced by Mn carbonates, coupled with concentric Mn carbonates, suggesting that Mn carbonates formed during diagenesis. This is further supported by their negative δ13CVPDB values (from −2.4 to −10.7‰), negative δ98MoNIST+0.25 values (from −0.1 to −3.7‰), shale-normalized positive Ce anomalies (up to 1.2), and lower Y/Ho ratios (29-35) relative to seawater (~44). These all indicate that the Zhaosu Mn carbonate ores formed due to original Mn oxide reduction coupled with organic matter degradation during diagenesis. The extremely negative Mo isotopic values (as low as −3.7‰) likely resulted from a dual effect of original Mn oxide adsorption and subsequent Mo sequestration within weakly sulfidic pore waters during diagenesis. The ubiquity of alabandite in the Mn ores indicates a significant separation between Mn and Fe, and combined with the country-rock limestones with negative Ce anomalies, we infer that an oxic-suboxic stratified water column might have characterized the Zhaosu basin during Mn deposition. By compiling geochemical and isotopic features of major Mn carbonate-rich sediments in Earth’s history, we argue that ancient Mn carbonate-rich sediments, especially economic ore deposits, might result from original Mn oxide reduction during diagenesis and thus are a reliable proxy for oxic oceanic conditions.

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Fig. 1

Modified from Xiao et al. (2013) and Yang et al. (2019). b Geologic sketch map of the Zhaosu Mn deposit showing the location of major mining districts. Revised from Li (2013)

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modified from Bonatti (1975), the (Fe+Mn)/4-(Zr+Ce+Y)×100-(Cu+Ni)×15 diagram is modified from Josso et al. (2017)

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Acknowledgments

We are indebted to FengMing Li for sharing geological documents about the Zhaosu deposit, Yasheng Wu for fossil identification, as well as HongWei Li, JiangYan Yuan, LiHui Jia, Zihu Zhang, Shanke Liu, Zhidan Wang, and DingShuai Xue for laboratory assistance. We also thank associate editor Alexandre R. Cabral for handling our manuscript and Bernd Lehmann, Malcolm Hodgskiss, and two anonymous reviewers for their constructive comments.

Funding

This study was jointly supported by the National Natural Science Foundation of China (No. U1703242; 42102114), the National Key Basic Research and Development Program (No. 2018YFC0604001), and the Second Comprehensive Scientific Survey of the Qinghai-Tibet Plateau (No. 2019QZKK0802). Wang CL acknowledges additional support from the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (ZDBS-LY-DQC037), and Youth Innovation Promotion Association, Chinese Academy of Sciences. Zhang BL acknowledges additional support from the Project funded by China Postdoctoral Science Foundation (2021M703018).

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Authors and Affiliations

  1. Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, 100029, China

    ZhiGuo Dong, ZiDong Peng, ChangLe Wang, LianChang Zhang, Xin Zhang & WenJun Li

  2. Innovation Academy for Earth Science, Chinese Academy of Sciences, Beijing, 100029, China

    ZhiGuo Dong, ZiDong Peng, ChangLe Wang, LianChang Zhang, Xin Zhang & WenJun Li

  3. University of Chinese Academy of Sciences, Beijing, 100049, China

    ZhiGuo Dong, ChangLe Wang, LianChang Zhang & Xin Zhang

  4. Development and Research Center, China Geological Survey, Beijing, 100037, China

    BangLu Zhang

  5. China University of Geosciences, Beijing, 100083, China

    BangLu Zhang

  6. Mineral Exploration Technical Guidance Center, Ministry of Natural Resources of the People’s Republic of China, Beijing, 100083, China

    BangLu Zhang

  7. State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China

    Jie Li & Le Zhang

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  1. ZhiGuo Dong
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Supplementary Information

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126_2022_1105_MOESM1_ESM.pdf

Supplementary file1. Fig. A1 X-ray powder diffraction patterns of Mn carbonate ores from the Zhaosu Mn deposit. (PDF 429 KB)

126_2022_1105_MOESM2_ESM.xlsx

Supplementary file2. Table B1. Atomic percentage (At. %) of metal cations in Zhaosu Mn carbonate minerals. Table B2. EPMA data (wt. %) of alabandite in the Zhaosu Mn ores. (XLSX 14 KB)

126_2022_1105_MOESM3_ESM.xlsx

Supplementary file3. Table B3. Compilations of C isotopes, Mo isotopes and Ce anomalies for major Mn carbonate-rich sediments in Earth’s history. (XLSX 65 KB)

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Dong, Z., Peng, Z., Wang, C. et al. Insight into the genesis of the Zhaosu Carboniferous Mn carbonate deposit (NW China): constraints from petrography, geochemistry, and C–Mo isotopes. Miner Deposita 57, 1269–1289 (2022). https://doi.org/10.1007/s00126-022-01105-3

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