Global resources of heavy Rare Earth Elements (REE) are dominantly sourced from Chinese regolith-hosted ion-adsorption deposits in which the REE are inferred to be weakly adsorbed onto clay minerals. Similar deposits elsewhere might provide alternative supply for these high-tech metals, but the adsorption mechanisms remain unclear and the adsorbed state of REE to clays has never been demonstrated in situ. This study compares the mineralogy and speciation of REE in economic weathering profiles from China to prospective regoliths developed on peralkaline rocks from Madagascar. We use synchrotron X-ray absorption spectroscopy to study the distribution and local bonding environment of Y and Nd, as proxies for heavy and light REE, in the deposits. Our results show that REE are truly adsorbed as easily leachable 8- to 9-coordinated outer-sphere hydrated complexes, dominantly onto kaolinite. Hence, at the atomic level, the Malagasy clays are genuine mineralogical analogues to those currently exploited in China.

Eudialyte-group minerals (EGM) are very common in highly evolved SiO₂-undersaturated syenites and are characteristic minerals of agpaitic rocks. Conversely, they are extremely rare in peralkaline granites, with only a handful of EGM occurrences reported worldwide. Here, we study two new examples of EGM occurrence in two types of peralkaline pegmatitic granites from the Cenozoic Ambohimirahavavy complex, and assess the magmatic conditions required to crystallize EGM in peralkaline SiO₂-oversaturated rocks. In the transitional granite (contains EGM as accessory minerals) EGM occur as late phases and are the only agpaitic and major rare-earth element (REE) bearing minerals. In the agpaitic granite (contains EGM as rock-forming minerals) EGM are early-magmatic phases occurring together with two other agpaitic minerals, nacareniobsite-(Ce) and turkestanite. In these granites, EGM are partly-to-completely altered and replaced by secondary assemblages consisting of zircon and quartz in the transitional granite and an unidentified Ca-Na zirconosilicate in the agpaitic granite. Ambohimirahavavy EGM, as well as those from other peralkaline granites and pegmatites, are richer inREEand poorer in Ca than EGM in nepheline syenites. We infer that magmatic EGM are rare in SiO₂-oversaturated rocks because of low Cl concentrations in these melts. At Ambohimirahavavy, contamination of the parental magma of the agpaitic granite with Ca-rich material increased the solubility of Cl in the melt promoting EGM crystallization. In both granite types, EGM were destabilized by the late exsolution of a fluid and by interaction with an external Ca-bearing fluid.