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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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.

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