Crystallization Sequence of the Spodumene-Rich Alijó Pegmatite (Northern Portugal) and Related Metasomatism on Its Host Rock

Abstract

The Barroso–Alvão region is an excellent setting for studying Li mineralization associated with granitic pegmatites and developing Li exploration techniques. Among the distinguished pegmatite types in this pegmatite field, the spodumene-bearing dyke from Alijó is a representative example of an Iberian Li–Cs–Ta (LCT) pegmatite currently under exploitation. In this work, we examine the internal evolution of the Alijó dyke and its external metasomatic effect on the surrounding metasediments, contributing to lithium exploration techniques. Electron microprobe analyses provided clues about the crystallization conditions and the degree of differentiation of the pegmatitic melt, whereas the external metasomatism induced by the spodumene-bearing pegmatite was studied through whole-rock geochemistry. The obtained results indicate that the primary crystallization of the studied dyke likely occurred at temperatures between 450–500 °C, with emplacement at shallow crustal levels of about 2–3 kbar. The high concentrations of trace elements such as Li, Cs, Rb, Be, Sn, Nb, Ta, Ge, U, and Tl in the pegmatitic melt suggests high availability of these elements, allowing their partitioning into an early exsolved fluid phase. The exsolution of this fluid phase, subtracting components such as F and B, from the pegmatitic melt would cause a significant undercooling of the melt. Moreover, the interaction of this expelled fluid with the country rock generated a metasomatic overprint in the surrounding metasedimentary host rocks. The metasomatic effect in Alijó is strongly influenced by the nature of the host metasediments, with a significantly higher grade of metasomatism observed in pelitic (mica-rich) samples compared to psammitic (mica-poor) samples collected at same distances from the dyke. The greisen developed close to the pegmatite contact reflects this metasomatic signature, characterized by the mobilization of at least B, F, Li, Rb, Cs, Sn, Be, Nb, Ta, and Tl. We cautiously suggest that whole rock Li concentrations greater than 300 ppm, combined with a minimum value of 1000 ppm for the sum of B, F, Li, Rb, Cs, and Sn in pelitic metasediments of Barroso–Alvão, may be indicative of a mineralized pegmatite in this region.