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Silver binding in argentiferous manganese oxide minerals investigated by synchrotron radiation X-ray absorption spectroscopy

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Abstract

The knowledge of the nature of silver occurrence and sites in argentiferous manganese oxides is significant for developing better process to extract silver from manganese-silver ores. Synchrotron radiation has been used to collect Ag K-edge X-ray absorption spectroscopy of three natural and five synthetic samples of silver-containing manganese oxide, basically in the phases of tunnel-type cryptomelane or todorokite and layer-type birnessite or chalcophanite. Data were also gathered on five standards including Ag foil, Ag2O, Ag2SO4, Ag2CO3, and AgNO3 to compare the local environments of Ag atoms with the samples. Ag K-edge XANES studies show that Ag is present in most of the samples in Ag+ oxidation state, except in the Ag-Tod sample through annealing step in the form of Ag0 nanoparticles which are also identified by TEM. The natural samples from Xiangguang manganese-silver ores exhibit similar coordination distances as the corresponding tunnel or layer structured synthetic samples. In the argentiferous cryptomelanes, silver cations do not occupy the tunnel centers like K+, but rather place on the common face sites of the cubic cage formed by MnO6 octahedra, coordinated with about four oxygen anions at ~ 2.4 Å bond distances proved by the EXAFS results. In the silver-exchanged birnessites or natural argentiferous chalcophanite, silver cations probably occupy a tetrahedral coordination to interlayer O atoms and a position located above or below the vacant cavities in the Mn octahedra layers.

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Acknowledgements

We owe great thanks to the group members at beam line 14W1 at Shanghai Synchrotron Radiation Facility (SSRF) for the technical assistance with data collection and analyses. We gratefully acknowledge Dr. Dong Juncai at Institute of High Energy Physics Chinese Academy of Sciences and Dr. Yin Hui at Huazhong Agricultural University for their help on the XAS data processing. We greatly thank two anonymous reviewers for their suggestions. We thank the following funding agencies for supporting this work: the National Natural Science Foundation of China (Grant No. 41302030), the Fundamental Research Project of Chinese Academy of Geological Sciences (Grant No. YYWF201619), the National Key R&D Program of China (Grant No. 2016YFC0600605), and the China Geological Survey Program (DD20179152).

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Authors and Affiliations

  1. National Research Center for Geoanalysis, Beijing, 100037, People’s Republic of China

    Chenzi Fan, Binbin Chu & Guohui Lu

  2. College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430071, People’s Republic of China

    Qiaoying Li

  3. School of Earth Sciences and Resources, China University of Geosciences (Beijing), Beijing, 100083, People’s Republic of China

    Yuhong Gao & Lingxiao Xu

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  1. Chenzi Fan
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  2. Qiaoying Li
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Correspondence to Chenzi Fan.

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Fan, C., Li, Q., Chu, B. et al. Silver binding in argentiferous manganese oxide minerals investigated by synchrotron radiation X-ray absorption spectroscopy. Phys Chem Minerals 45, 679–693 (2018). https://doi.org/10.1007/s00269-018-0954-1

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