Adsorption of REEs to Kaolinite via Ion Exchange and Surface Complexation as a Function of Water Chemistry

Ramazanova, Elmira; Sharma, Neha; Flynn, Elaine D.; Stagg, Olwen; Catalano, Jeffrey G.; Giammar, Daniel E.

doi:10.1021/acsearthspacechem.4c00389

Adsorption of REEs to Kaolinite via Ion Exchange and Surface Complexation as a Function of Water Chemistry

Journal Article · Mon May 19 04:00:00 EDT 2025 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.4c00389· OSTI ID:2570436

Ramazanova, Elmira ^[1]; ^[1]; ^[1]; Stagg, Olwen ^[1]; ^[1]; ^[1]

Washington Univ., St. Louis, MO (United States)

Rare earth elements (REEs) are critical components of modern technology behind renewable energy, transportation, and electronics but have a limited current supply. A substantial portion of global REE production relies on ion adsorption deposits. A high abundance of kaolinite in REE enrichment zones within these deposits suggests that kaolinite controls the subsurface migration of REEs. This study aimed to improve the current understanding of REE binding to kaolinite under varying water chemistry conditions. We conducted batch experiments with kaolinite (KGa-2) and three REEs (Nd, Dy, and Yb) at varying pH, electrolyte concentration, dissolved inorganic carbon (DIC), low molecular weight organic acids (citric and oxalic acids), and total REE concentration conditions. Increasing electrolyte concentration inhibits REE adsorption at pH < 7, suggesting that ion exchange contributes to adsorption at these pH values. DIC affects adsorption above pH 7–8 by forming strong aqueous complexes with heavy REEs. Citric acid decreases REE adsorption via aqueous complexation of REEs at pH > 5 but does not affect adsorption at pH < 5. The surface complexation model captures the main adsorption trends with two mechanisms: ion exchange on basal planes at pH < ∼6 and inner-sphere surface complexation to edge sites at pH > ∼6. Equilibrium constants for surface complexation increase in the order of Yb > Dy > Nd, indicating a higher strength of adsorption for heavy REEs. This study demonstrates how water chemistry conditions control the adsorption mechanisms that may determine the mobility of REEs in subsurface environments rich in kaolinite.

View Accepted Manuscript (DOE)

Research Organization:: Washington Univ., St. Louis, MO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022213; SC0022213

OSTI ID:: 2570436

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 6 Vol. 9; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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