Scandium immobilization by goethite: surface adsorption versus structural incorporation

Abstract Several recent studies have reported a strong association between Sc and goethite (α-FeOOH) in synthetic analogs and natural samples. However, the mechanism of Sc immobilization by goethite and controlling factors remain unclear. This study investigated the adsorption behavior and molecular-scale immobilization mechanisms of Sc at water/goethite interfaces through a combination of batch adsorption and desorption experiments, X-ray absorption fine structure (XAFS) analyses, and density functional theory (DFT) calculations. Results indicate that Sc is preferentially adsorbed on goethite with the formation of bidentate-binuclear inner-sphere complexes at the corner-sharing sites. Bulk Sc K-edge XAFS analyses suggest that Sc is incorporated into the goethite structure by substituting for Fe(III) within the crystal in synthetic Sc-substituted goethite, which is further confirmed in natural goethite particles in the laterite by using in situ μ-XAFS. Furthermore, we demonstrate that the adsorbed Sc on the goethite surface can be structurally incorporated into the goethite lattice in the presence of aqueous Fe(II) possibly through goethite recrystallization induced by aqueous Fe(II). This process may affect the (re)partitioning of Sc between the goethite surface and the mineral bulk, which could be used to rationally explain disparate Sc speciation in laterites from different regions. Our study elucidates the molecular-scale mechanisms underlying Sc adsorption on and structural incorporation into goethite, providing critical insights into the understanding of geochemical behavior and environmental fates of Sc.