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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

  • Yuzhou Feng , Huayong Chen , Huiyao Kuang , Rucao Li , Bing Xiao , Chao Wu , Hui Zheng , Renfei Feng , Mohsen Shakouri and Yuanming Pan ORCID logo EMAIL logo
Published/Copyright: September 11, 2025
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American Mineralogist
From the journal American Mineralogist Volume 110 Issue 9

Abstract

Heavy rare earth elements (HREE), as critical materials for the global transition to a low-carbon economy, are mostly supplied by regolith-hosted ion adsorption REE deposits formed from the weathering of granites. Magmatic-hydrothermal titanite of pronounced HREE enrichment in granites has been suggested to play an important role in forming HREE-dominated regolith-hosted deposits. However, the crystal-chemical mechanism and geological process responsible for HREE enrichment in titanite remain unknown. In this study, we investigated two texturally distinct types of HREE-enriched titanite (titanite I and II) in granites from the Gucheng regolith-hosted HREE deposit in South China. Secondary ion mass spectrometry (SIMS) U-Pb dating of rutile associated with titanite I and II yielded similar ages of 101.0 ± 1.7 and 97.9 ± 6.2 Ma, respectively, supporting HREE remobilization during auto-metasomatism. Microbeam synchrotron X-ray absorption spectroscopic analyses show that titanite I and II have distinct Y K-edge X-ray absorption near-edge structure spectra. The best-fit results of Y K-edge extended X-ray absorption fine structure data suggest that titanite I and II have a Y-O first shell with coordination numbers and distances of 7.8 and 7.2 Å and 2.31–2.51 Å and 2.30–2.47 Å, respectively. Measured Y 3d and Dy 3d X-ray photoelectron spectroscopic data also support different Y,HREE-O first shells between titanite I and II. These results suggest that Y3+ and REE3+ occupy the 7-coordinated Ca site via three substitutions (Y,REE)3++(Al,Fe)3+↔Ca2++Ti4+, 2(Y,REE)3++□Ca↔3Ca2+, and 2(Y,REE)3++O2−↔2Ca2+. First-principles calculations and the lattice strain model predict preferential uptakes of Y3+ and HREE3+ as the (Y,HREE)O8 polyhedra arising from the latter substitution mechanism at the Ca site in titanite. Moreover, we link the 2Y3++ O2−↔2Ca2+ substitution in titanite to highly oxidized and HREE-enriched melts/fluids originating from the subducted slab. These findings further support our previous suggestion that the crystallization of HREE-enriched titanite in granites plays an important role in forming HREE-dominated regolith-hosted deposits.

Keywords: Critical minerals; HERE-enriched titanite; synchrotron XAS; XPS; uptake mechanism; regolith-hosted REE deposit

Acknowledgments and Funding

We thank Daniel Harlov and three anonymous reviewers for insightful comments and helpful suggestions. This study was funded by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA0430301), a Natural Science and Engineering Research Council of Canada (NSERC) Discovery Grant (RGPIN 03255-2023), and the Taishan Scholar Program of Shandong Province (tsqn202312194). Yuzhou Feng is partially supported by an NSERC-CREATE INSPIRE postdoctoral fellowship. All synchrotron data were collected at the VESPERS beamline of the Canadian Light Source, a national research facility of the University of Saskatchewan, supported by the Canada Foundation for Innovation (CFI), the Natural Sciences and Engineering Research Council (NSERC), the National Research Council (NRC), Canadian Institutes of Health Research (CIHR), and Government of Saskatchewan. Hongping He and Xiaoliang Liang of the Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, are thanked for their assistance with sample collection. Shiqin Long of the Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, is thanked for her assistance with XPS data collection.

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Received: 2024-10-10
Accepted: 2025-01-18
Published Online: 2025-09-11
Published in Print: 2025-09-25

© 2025 Mineralogical Society of America

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  2. Revisiting the importance of clay minerals in rock varnish
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  4. Reconstructing volatile evolution in melts using zircon-hosted apatite inclusions: Implications for the use of apatite as a fertility indicator
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  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
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  12. Silicate liquid immiscibility in the Chang’e 5 lunar mare magmas: Constraints on the petrogenesis of lunar granitic rocks
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  14. Lianbinite, (NH4)(C2H3O3)(C2H4O3), a new glycolate mineral from the Santa Catalina Mountains, Tucson, Arizona, U.S.A
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https://doi.org/10.2138/am-2024-9645
Keywords for this article
Critical minerals; HERE-enriched titanite; synchrotron XAS; XPS; uptake mechanism; regolith-hosted REE 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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