The role of clay minerals in the concentration and distribution of critical metals in lateritic palaeosols from NE Iberia

Abstract

The intense chemical weathering processes that lead to the formation of laterites and bauxites result in the enrichment of critical metals (Sc, V, Co, Ga, Ge, Nb, In, Hf, Ta, W, and REEs), which are of great economic interest and are directly involved in the manufacture of various devices essential for the technology transition. This work focuses on combined geochemical and scanning transmission electron microscopy (STEM) studies of lateritic palaeosols developed in continental profiles (Lower Cretaceous, NE Iberia) in order to evaluate the distribution and concentration of critical metals and their possible relationship with weathering processes. In this study, we show that during the process of laterization the highest weathering produces the highest critical metal concentrations (reaching concentrations of 1914.80 ppm in the lateritic palaeosols and 926.30 ppm in the ferruginous macropisoids). Concentrations normalized to the upper continental crust (Taylor and McLennan, 1985) indicate that both the lateritic palaeosols and the macropisoids are enriched in LREEs (256.81 and 223.01 ppm, respectively) and HREEs (107.11and 110.53, respectively). In the lateritic palaeosols, the (La/Sm)c values are higher than those of (Gd/Yb)c, indicating that the LREEs exhibit higher fractionation with weathering, whereas the opposite occurs for the macropisoids, in which the HREEs have higher fractionation. These data indicate that the HREEs are less mobile than the LREEs during laterization. The critical metals present a good positive correlation with Fe, Ti, and Al, but a good negative correlation with K. STEM images and EDS analyses allowed us to identify REE-phases (including monazite, xenotime, and La, Ce and Nd oxides) and nanoparticles of gold adsorbed on the surface of kaolinite crystals. This shows not only that during the laterization process Fe and Ti oxides act as scavengers for the critical metals, but also that kaolinite controls their distribution.