Origin of carbonatite-related niobium deposits: Insights from pyrochlore geochemistry

Abstract

The carbonatite-related Nb deposits of the Alto Paranaíba Igneous Province (APIP) in central Brazil, currently account for ∼92 % of the global Nb production. In the APIP, pyrochlore is abundant in magnetite–apatite–tetraferriphlogopite ± carbonate rocks or phoscorites, occurring as interbedded layers with carbonatites in the lower hypogene zone, feeding dike swarms of phoscorite and calcite carbonatite, and late-stage carbothermal veins in the upper hypogene zone. The origin of the phoscorite-carbonatite association can be explained by three hypotheses: (1) crystal segregation from fractional crystallization, (2) liquid immiscibility, and/or (3) phoscoritic magma formation after basement metasomatism (fenitization). However, it is not well understood whether pyrochlore formation is limited to a carbonatitic event, carbohydrothermal, or both, and this gap of knowledge is addressed in this work. To investigate the petrogenesis of pyrochlore-rich phoscorite, cathodoluminescence (CL) images, chemical maps, and LA-ICP-MS data were acquired of pyrochlore crystals from magmatic and carbothermal rocks from the Boa Vista Nb mine, Catalão II Complex. In the Boa Vista mine, oscillatory and patchy zoning were identified as primary pyrochlore textures commonly recorded at the lower hypogene zone, while secondary dissolution, skeletal and zonation-free textures are registered at shallower depths in the upper hypogene zone. Calciopyrochlore is the dominant Nb phase at the Boa Vista mine, with only two kenopyrochlore outliers. The pyrochlore CI chondrite-normalized REE distribution is consistent with geochemical results of the carbonatite and phoscorite rocks, indicating a magmatic origin for pyrochlore and the presence of pyrochlore antecrysts in carbothermal veins. The Sr/Y vs La and Na vs Ce diagrams in pyrochlore indicate a continuous fractionation pattern, with some mixtures of antecrysts and primary phases. An examination of intercumulus calcite using CL provide evidence of carbonatitic magma residues within tetraferriphlogopite phoscorite dikes and suggests that alkaline–carbonate-rich fluids played a role in transporting heavy minerals (i.e., magnetite, apatite, pyrochlore). Consequently, the textural and chemical evidence in the Boa Vista Nb mine indicates that the origin of pyrochlore-rich phoscorites is the result of physical segregation of heavy minerals from a carbonatite magma by fractional crystallization, leading to the emplacement of pyrochlore-rich carbonatite and phoscorite dikes. The implications at Catalão II may extend to other APIP alkaline-carbonatite complexes, as they share a genetic connection, and should motivate further studies focusing on pyrochlore geochemistry in other carbonatite-related Nb deposits, which will be crucial for advancing our knowledge of global Nb metallogenesis.