The thermodynamics of rare earth element liberation, mobilization and supergene enrichment during groundwater-regolith interaction

Rare earth elements (REEs) mobilize, fractionate, and are re-distributed during supergene processes, and thus provide a powerful tool with which to quantitatively reconstruct the effects of chemical weathering. Moreover, under certain conditions, the REEs can concentrate to levels in the regolith sufficient to form giant regolith-hosted REE deposits, that are now responsible for much of the World's production of heavy REEs (HREEs). Understanding the supergene behavior of the REEs is an important first step towards applying the REEs as a geochemical tool and meeting the growing global demand of the REEs. Thermodynamic calculations predict that dissolution of the main REE minerals in REE-rich protoliths, namely synchysite-(Y), gadolinite-(Y), hingganite-(Y), yttrialite-(Y), allanite-(Ce), eudialyte, chevkinite-(Ce), britholite, euxenite and loparite-(Ce), should occur spontaneously during weathering. It therefore follows that a high abundance of these minerals in the protolith implies high mobility of the REEs during weathering and consequently a high potential for the discovery of economic REE resources. Dissolution of apatite is promoted by metamictization or structural distortion and could be also important at low pH. In contrast, some LREE-fluorocarbonate minerals, notably bastnäsite-(Ce) and parisite-(Ce), and monazite-(Ce) are likely thermodynamically stable in acidic environments. Thus, they would be preserved in the regolith. Zircon, titanite, aeschynite, fergusonite, and xenotime-(Y) are resistant to acidic dissolution, consistent with their common occurrence as residual minerals. In the cases of the world-class regolith-hosted REE deposits in South China, the groundwater is mildly acidic to circumneutral and carbonate-rich. The REEs are consequently transported dominantly as hydrated cations and carbonate complexes, depending on the pH. The general inheritance of the REE pattern of the regolith groundwater in the clay-sorbed fraction in the regolith indicates that the REEs in regolith are scavenged from the regolith groundwater. Elemental anomalies of specific REEs in the clay-sorbed fraction are very likely caused by an anomalously high REECO3+ fraction in the corresponding regolith groundwater, suggesting a preferential uptake of the REECO3+ complexes by the clay minerals, feasibly by halloysite through intercalation as interlayer complexes. This reaction is expected to be particularly important for the sorption and enrichment of the HREEs in the regolith. Depending on the pH and carbonate concentration of the water, surface complexation on clay minerals or interlayer intercalation particularly in halloysite control the pattern of REE enrichment. Mixing of the regolith groundwater with the alkaline and carbonate-rich aquifer groundwater increases the pH and carbonate concentration and, in turn, affects the ability of the mixed water to transport the HREEs. Interplay of aqueous complexation with the regolith mineralogy significantly affects the REE fractionation and re-distribution during groundwater-regolith interaction.