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Germanium oxidation state and substitution mechanism in Ge-rich sphalerite from MVT deposits: Constraints from X-ray absorption fine structure (XAFS) and geometric optimization

  • Pan-Pan Niu ORCID logo , Shao-Yong Jiang ORCID logo EMAIL logo , Manuel Muñoz , Clément Bonnet , Olivier Mathon , Marie-Christine Boiron , Hai-Zhen Wei and Suo-Fei Xiong ORCID logo
Published/Copyright: September 11, 2025
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American Mineralogist
From the journal American Mineralogist Volume 110 Issue 9

Abstract

Sphalerite is a crucial host mineral for germanium (Ge) resources worldwide. However, the oxidation state (+2 or +4) of Ge and its substitution mechanism in sphalerite remain a subject of ongoing debate. The Huize and Maoping deposits are the largest and second largest Pb-Zn-Ge deposits in the Mississippi Valley Type (MVT) metallogenic province in southwest China, respectively. Four types of Ge-rich sphalerite have been identified within these two deposits: C1-Huize, C3-Huize, C1-Maoping, and C5-Maoping. This study employs synchrotron-based microscale X-ray absorption fine structure (μ-XAFS) methods, including X-ray absorption near-edge structure (μ-XANES) and extended X-ray absorption fine structure (μ-EXAFS) analyses, to investigate the Ge distribution, oxidation state, and neighboring atomic environment within the Huize and Maoping Ge-rich sphalerites. The results suggest that the incorporation of Ge4+ and Cu+ into sphalerite occurs at varying Cu/Ge molar ratios, depending on the availability/concentration of Cu in the sphalerite (i.e., Cu/Ge ≥ 2). On the other hand, Ge2+ and Ge4+ coexist when Ge and one vacancy (□) substitute for Zn in sphalerite. These different types of Ge substitutions influence the position of Zn atoms in the second neighboring atomic shell in the structure, while they have minor effects on the location of S atoms in the first neighboring atomic shell. The presence of vacancies strongly affects Zn atoms in the second neighboring atomic shell when coupled with Ge substitution in sphalerite, resulting in smaller interatomic distances and significant structural disorder (Debye-Waller factor). Additionally, two Cd2+ ions are required to co-replace two Zn2+ ions to fill the structural defects caused by vacancies. In contrast, the substitution of Cu+ and Ge4+ for two Zn ions results in a more ordered spatial structure, which is not distinctly controlled by the Fe content of sphalerite. Based on the characterization of the Ge oxidation state and local structure, we redefined the Ge substitution mechanisms inferred from element correlations: (1) Ge4+ +2Cd2++□→4Zn2+ and Ge2+→Zn2+ in C1-Huize; (2) Ge4++2Cu+→3Zn2+ in C3-Huize and C1-Maoping; and (3) 3Cu++As3++Ge4+→5Zn2+ in C5-Maoping. This study not only elucidates the distribution of Ge in different valence states but also unveils its true spatial structure in sphalerite. These findings have significant implications for investigating Ge substitution and enrichment mechanisms in sphalerite.

Keywords: Germanium; HR-XAFS; Ge-rich sphalerite; MVT deposit

Acknowledgments and Funding

This study was 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 China Scholarships Council (no. 202106410073). Thanks to Weihua Liu and three anonymous reviewers for their valuable comments, which have significantly improved the quality of this manuscript. We also acknowledge the European Synchrotron Radiation Facility for providing the synchrotron beamtime.

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Received: 2024-06-05
Accepted: 2024-12-22
Published Online: 2025-09-11
Published in Print: 2025-09-25

© 2025 Mineralogical Society of America

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Revisiting the importance of clay minerals in rock varnish
  3. Formation and transformation of clay minerals in Mars-analog rock varnish
  4. Reconstructing volatile evolution in melts using zircon-hosted apatite inclusions: Implications for the use of apatite as a fertility indicator
  5. Vesuvianite as a key tool for the reconstruction of skarn formation conditions: An example from the Sauce Chico Complex, Argentina
  6. Germanium oxidation state and substitution mechanism in Ge-rich sphalerite from MVT deposits: Constraints from X-ray absorption fine structure (XAFS) and geometric optimization
  7. Enrichment mechanism of heavy rare earth elements in magmatic-hydrothermal titanite: Insights from SXAS/XPS experiments and first-principles calculations and implications for regolith-hosted HREE deposits
  8. Thorite: An oddity in phase stability among the zircon-structured orthosilicates at high pressures
  9. High P-T single-crystal elasticity of zircon by Brillouin spectroscopy
  10. Berndlehmannite: A new V-bearing sulfide mineral from the black-shale-hosted Zhongcun vanadium deposit, South China
  11. In situ Raman spectroscopic investigation on the phase transition of grunerite at high pressures
  12. Silicate liquid immiscibility in the Chang’e 5 lunar mare magmas: Constraints on the petrogenesis of lunar granitic rocks
  13. The high-pressure, vacancy-stabilized component in clinopyroxenes
  14. Lianbinite, (NH4)(C2H3O3)(C2H4O3), a new glycolate mineral from the Santa Catalina Mountains, Tucson, Arizona, U.S.A
  15. Mariakrite, [Ca4Al2(OH)12(H2O)4][Fe2S4]: A new mineral and the first layered double hydroxide intercalated with dithioferrate (iron disulfide) chains
  16. New Mineral Names
  17. Book Review
  18. Book Review: Rings of Fire: How an Unlikely Team of Scientists, Ex-Cons, Women, and Native Americans helped win World War II
https://doi.org/10.2138/am-2024-9485
Keywords for this article
Germanium; HR-XAFS; Ge-rich sphalerite; MVT deposit

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Revisiting the importance of clay minerals in rock varnish
  3. Formation and transformation of clay minerals in Mars-analog rock varnish
  4. Reconstructing volatile evolution in melts using zircon-hosted apatite inclusions: Implications for the use of apatite as a fertility indicator
  5. Vesuvianite as a key tool for the reconstruction of skarn formation conditions: An example from the Sauce Chico Complex, Argentina
  6. Germanium oxidation state and substitution mechanism in Ge-rich sphalerite from MVT deposits: Constraints from X-ray absorption fine structure (XAFS) and geometric optimization
  7. Enrichment mechanism of heavy rare earth elements in magmatic-hydrothermal titanite: Insights from SXAS/XPS experiments and first-principles calculations and implications for regolith-hosted HREE deposits
  8. Thorite: An oddity in phase stability among the zircon-structured orthosilicates at high pressures
  9. High P-T single-crystal elasticity of zircon by Brillouin spectroscopy
  10. Berndlehmannite: A new V-bearing sulfide mineral from the black-shale-hosted Zhongcun vanadium deposit, South China
  11. In situ Raman spectroscopic investigation on the phase transition of grunerite at high pressures
  12. Silicate liquid immiscibility in the Chang’e 5 lunar mare magmas: Constraints on the petrogenesis of lunar granitic rocks
  13. The high-pressure, vacancy-stabilized component in clinopyroxenes
  14. Lianbinite, (NH4)(C2H3O3)(C2H4O3), a new glycolate mineral from the Santa Catalina Mountains, Tucson, Arizona, U.S.A
  15. Mariakrite, [Ca4Al2(OH)12(H2O)4][Fe2S4]: A new mineral and the first layered double hydroxide intercalated with dithioferrate (iron disulfide) chains
  16. New Mineral Names
  17. Book Review
  18. Book Review: Rings of Fire: How an Unlikely Team of Scientists, Ex-Cons, Women, and Native Americans helped win World War II
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