Interpretation of vertical migration and enrichment processes of rare earth elements (REEs) in ion-adsorption-type mineralization in Japan based on REE speciation analyses

Nagasawa, Makoto*; Shimizu, Yusuke*; Yamaguchi, Akiko  ; Tokunaga, Kohei   ; Mukai, Hiroki*; Aoyagi, Noboru   ; Mei, H.  ; Takahashi, Yoshio*

Typical vertical profiles of ion-adsorption type rare earth element deposits (REE-IADs) discovered in the central Japan were studied by various speciation analyses including X-ray absorption fine structure (XAFS) and laser-induced fluorescence (LIF) spectroscopy combined with transmission electron microscope (TEM) and adsorption/desorption experiments. The results revealed that REE speciation, migration and enrichment in the weathered granite is largely controlled by soil pH which control the variable charges of kaolinite as the REE host phase. The distribution coefficient Kd, together with the soil pH, increases as the depth increase, resulting in (i) REE dissolution and migration in upper layers near the surface acidic environment where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a lesser degree and (ii) REE accumulation in relatively high pH environment below the surface where hydroxyls of kaolinite basal surfaces and edges deprotonated to a larger degree to produce variable charges as adsorption sites for REEs. The increase of soil pH above 6 in deeper layers promotes inner-sphere complexation of REEs. The inner-sphere complexation inhibits the ion-exchange extraction of REEs, but the inner-sphere complexes can be still extracted by lowering the pH, which suggests the adsorption of inner- and outer-sphere complexes is reversible. This fact is important both from (i) understanding of vertical profile of REE with variation of pH and (ii) effective recovery of REE from weathered granite at all the depths in the enriched layer.