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Mechanism of germanium enrichment in the world-class Huize MVT Pb–Zn deposit, southwestern China

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Abstract

The world-class Huize deposit hosts significant germanium (Ge) resources in the Sichuan–Yunan–Guizhou (SYG) Mississippi Valley-type (MVT) Pb–Zn province of China. The distribution and enrichment mechanism of Ge is still poorly understood. In the main ore-forming stage of Huize, we identified six sphalerite colors from C1 (black) to C6 (white) in transmitted light. Two color sequences are confirmed, including C1 → C2 → C3 → C6 and C1 → C2 → C4 → C5 → C6. We used multiple analytical methods to reveal the Ge distribution and incorporation mechanism into sphalerite and the possible enrichment factors. Our results show that Ge occurs as argutite (GeO2), and in the sphalerite crystal lattice, C1 and C3 sphalerite has up to 593 ppm Ge. Two substitution mechanisms, i.e., Ge4+ + □(vacancy) → 2Zn2+ (e.g., C1 and C2) and Ge4+  + 2Cu+ → 3Zn2+ (e.g., C2, C3, C4, and C5), are inferred from the Huize sphalerite. They show different spatial structures of sphalerite and a weak shift of the white line observed by high-resolution X-ray absorption near-edge structure (XANES) spectroscopy. The trace-element composition of sphalerite suggests that reduced sulfur content of the ore-forming fluid contributes to Ge enrichment, followed by high temperature (> 300 °C).

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Acknowledgements

We appreciate Mr. Xiao Yang, Zhu Peng, Guo Tengda and Fabrice Barou for their help during sample analyses. We acknowledge the European Synchrotron Radiation Facility for the provision of synchrotron radiation facilities during the commissioning of the BM23 beamline. The editor-in-chief (Bernd Lehmann), associate editor (Huayong Chen), Alexandre Cugerone, and the two anonymous reviewers are thanked for providing constructive comments that greatly improved the quality of the manuscript.

Funding

This study is financially supported by grants from the National Key Research and Development Program of China (2021YFC2900300), the National Natural Science Foundation of China (no. 92162323), the Fundamental Research Funds for National Universities, China University of Geosciences (Wuhan), and the program of China Scholarships Council (no. 202106410073).

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Authors and Affiliations

  1. Key Laboratory of Geological Survey and Evaluation of Ministry of Education, China University of Geosciences, Wuhan, 430074, People’s Republic of China

    Pan-Pan Niu & Shao-Yong Jiang

  2. State Key Laboratory of Geological Processes and Mineral Resources, Collaborative Innovation Center for Exploration of Strategic Mineral Resources, School of Earth Resources, China University of Geosciences, Wuhan, 430074, People’s Republic of China

    Pan-Pan Niu, Suo-Fei Xiong & Shao-Yong Jiang

  3. Geosciences Montpellier, University of Montpellier, CNRS, 34095, Montpellier, France

    Pan-Pan Niu & Manuel Muñoz

  4. European Synchrotron Radiation Facility, 38043, Grenoble, France

    Olivier Mathon

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  1. Pan-Pan Niu
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  2. Manuel Muñoz
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  3. Olivier Mathon
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  4. Suo-Fei Xiong
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Correspondence to Shao-Yong Jiang.

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Supplementary file1 (JPG 938 KB) Supplementary FIGURE 1: Histogram of exposed strata in the Huize Pb–Zn deposit.

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Supplementary file2 (JPG 843 KB) Supplementary FIGURE 2: Mineralization period and mineral paragenetic sequence and association in the Huize Pb-Zn deposit.

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Supplementary file3 (JPG 608 KB) Supplementary FIGURE 3: Selected representative area for laser ablation (LA) inductively coupled plasma (ICP) mass spectroscopy (MS) spot analysis in the sphalerite of the Huize Pb–Zn deposit, including C1 (A–C), C2 (D–F), C3 (G–I), C4 (J–L), C5 (M–O) and C6 (P–R). Abbreviations: C1- black; C2- brown-red; C3- orange-red; C4- deep yellow; C5- pale yellow; C6- white.

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Supplementary file4 (JPG 5831 KB) Supplementary FIGURE 4: Representative time-resolved laser ablation (LA) inductively coupled plasma (ICP) mass spectroscopy (MS) depth profiles for C1 (A), C2 (B), C3 (C), C4 (D), C5 (E), and C6 (F) sphalerite, with few real-time curves (G-J) slightly influenced by other mineral inclusions (e.g., Pb, Sb, Na, K, Sr, Al, Mg, and Si).

126_2023_1242_MOESM5_ESM.jpg

Supplementary file5 (JPG 3312 KB) Supplementary FIGURE 5: Principal component analysis (PCA) results of the selected elements for C1 (A, B), C2 (C, D), C3 (E, F), C4 (G, H), C5 (I, J), and C6 (K, L) sphalerite, including scree plot eigenvalues and composite scatter plots of scores and loadings.

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Supplementary file6 (JPG 337 KB) Supplementary FIGURE 6: Principal component analysis (PCA) results of six sphalerite colors (C1-C6), showing scores and 95% confidence ellipse.

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Supplementary file7 (JPG 2383 KB) Supplementary FIGURE 7: (A) The electron backscattered diffraction (EBSD) Euler color map and inverse pole figures (IPF) of (B) x, (C) y, and (D) z axes in the selected sphalerite region (the same area as Figure 8A), showing the Ge signals from element mapping.

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Supplementary file8 (JPG 924 KB) Supplementary FIGURE 8: The constructed sphalerite structures for FEFF10 software calculations: (A) One Ge atom replacing the central Zn atom as the origin; (B) One first-order adjacent Zn atom replaced by one vacancy as Ge4+ + □→2Zn2+; (C) Two first-order adjacent Zn atoms replaced by two Cu atoms as Ge4+ + 2Cu+→2Zn2+.

Supplementary file9 (DOCX 84 KB)

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Niu, PP., Muñoz, M., Mathon, O. et al. Mechanism of germanium enrichment in the world-class Huize MVT Pb–Zn deposit, southwestern China. Miner Deposita (2024). https://doi.org/10.1007/s00126-023-01242-3

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