The Diversity of Rare-Metal Pegmatites Associated with Albite-Enriched Granite in the World-Class Madeira Sn-Nb-Ta-Cryolite Deposit, Amazonas, Brazil: A Complex Magmatic-Hydrothermal Transition

This study investigates pegmatites with exceptionally rare mineralogical and chemical signatures, hosted by the 1.8 Ga peralkaline albite-enriched granite, which corresponds to the renowned Madeira Sn-Nb-Ta-F (REE, Th, U) deposit in Pitinga, Brazil. Four distinct pegmatite types are identified: border pegmatites, pegmatitic albite-enriched granite, miarolitic pegmatite, and pegmatite veins. The host rock itself has served as the source for the fluids that gave rise to all these pegmatites. Their mineral assemblages mirror the rare-metal-rich paragenesis of the host rock, including pyrochlore, cassiterite, riebeckite, polylithionite, zircon, thorite, xenotime, gagarinite-(Y), genthelvite, and cryolite. These pegmatites formed at the same crustal level as the host granite and record a progressive magmatic–hydrothermal evolution driven by various physicochemical processes, including tectonic decompressing, extreme fractionation, melt–melt immiscibility, and internal fluid exsolution. Border pegmatites crystallized early from a F-poor, K-Ca-Sr-Zr-Y-HREE-rich fluid exsolved during solidification of the pluton’s border and were emplaced in contraction fractures between the pluton and country rocks. Continued crystallization toward the pluton’s core produced a highly fractionated melt enriched in Sn, Nb, Ta, Rb, HREE, U, Th, and other HFSE, forming pegmatitic albite-enriched granite within centimetric fractures. A subsequent pressure quench—likely induced by reverse faulting—triggered the separation of a supercritical melt, further enriched in rare metals, which migrated into fractures and cavities to form amphibole-rich pegmatite veins and miarolitic pegmatites. A key process in this evolution was melt–melt immiscibility, which led to the partitioning of alkalis between two phases: a K-F-rich aluminosilicate melt (low in H2O), enriched in Y, Li, Be, and Zn; and a Na-F-rich aqueous melt (low in SiO2). These immiscible melts crystallized polylithionite-rich and cryolite-rich pegmatite veins, respectively. The magmatic–hydrothermal transition occurred independently in each pegmatite body upon H2O saturation, with the hydrothermal fluid composition controlled by the local degree of melt fractionation. These highly F-rich exsolved fluids caused intense autometasomatic alteration and secondary mineralization. The exceptional F content (up to 35 wt.% F in pegmatite veins), played a central role in concentrating strategic and critical metals such as Nb, Ta, REEs (notably HREE), Li, and Be. These findings establish the Madeira system as a reference for rare-metal magmatic–hydrothermal evolution in peralkaline granites.