REE concentration processes in ion adsorption deposits: Evidence from the Ambohimirahavavy alkaline complex in Madagascar

Ion adsorption deposits, in which the rare earth elements (REE) occur adsorbed onto clay mineral surfaces, currently provide the world's dominant supply of heavy REE (Gd-Lu). Concentration of REE within ion adsorption deposits has been proposed to be a dominantly supergene process, where easily degradable REE-minerals (e.g. REE-fluorcarbonates) break down and release REE that are then adsorbed onto clay mineral surfaces in the weathered material. Here we present data from the Cenozoic Ambohimirahavavy alkaline complex in Madagascar, with the aim of further constraining controls on the formation and HREE enrichment processes in ion adsorption deposits. The laterite weathering profiles described here are developed on alkaline igneous rocks, including both SiO2-undersaturated and oversaturated lithologies. The latter group includes REE mineralised peralkaline granitic pegmatites and granitic dykelets. The weathering mineralogy includes gibbsite, clay minerals and minor Fe and Mn oxyhydroxides. X-ray diffraction and infrared spectroscopy show that the clay fraction in all sites is dominated by kaolinite and halloysite (7 Å and 10 Å). Extraction with ammonium sulfate (0.5 M (NH4)2SO4, pH = 4; removes weakly adsorbed metals retained on the solid surface and dissolves carbonates) indicates that, in the different profiles and along the same profile, the leachable REE content is heterogeneous, ranging from 5 to 2300 mg/kg total REE, with 1 to 32% heavy REE. Leaching with magnesium chloride (0.5 M MgCl2, pH = 6; removes only weakly adsorbed REE) releases similar total REE concentrations, suggesting that most of the leachable REE are adsorbed onto mineral surfaces. In most of the laterite profiles, the amount of leachable REE continuously increases with depth up to the saprock. Recovery rates depend on the REE atomic number, generally decreasing from La to Lu except for Ce which is invariably low. In the Ambohimirahavavy complex, the nature of the protolith is the main factor controlling the amount of easily leachable REE in the laterite weathering profile. Hydrology and topography are secondary factors. The most favourable protoliths include SiO2-undersaturated volcanic lithologies and altered mudstone with granitic dykelets. The main primary REE minerals include agpaitic minerals (eudialyte) and allanite-(Ce). Locally in granitic pegmatite dykes, autometasomatism by late magmatic fluids inhibits formation of ion adsorption ore by transforming easily weathered agpaitic minerals into unweatherable zircon.