Geochemical and textural characterization of phosphate accessory phases in the vein assemblage and metasomatically altered Llallagua tin porphyry

Abstract

Petrographic and geochemical characterization of phosphate accessory minerals represents a powerful tool in understanding the mineralization and metasomatic history of one of the world’s biggest tin deposits, the Siglo XX mine, Salvadora stock, Llallagua, Bolivia. The Llallagua tin deposit lies in a hydrothermally altered porphyry stock that is part of the subduction-related Bolivian tin belt. Despite numerous studies, there is still a debate over the timing and characteristics of mineralization history of the deposit. Primary igneous fluorapatite and monazite (for the first time) were recognized in the altered porphyry. The igneous monazite is enriched in Th, unlike the hydrothermal monazite that is recognized for its low Th concentration. Fluorapatite, monazite, and xenotime also coexist with cassiterite within the hydrothermal vein assemblage. Fluorapatite and xenotime are essentially pristine. Monazite, however, shows various degrees of alteration in the form of regenerative mineral replacement (RMR). This exemplifies differential reactivity and selective mineral replacement/alteration of three accessory phosphate minerals, that are all important geochemical tracers of magmatic and hydrothermal processes, and which can all be used as geochronometers. Mineral textures and composition in the altered porphyry and vein assemblages have been evaluated. Monazite-xenotime geothermometry indicates monazite crystallization beginning around 550 °C. Monazite continues to grow as temperatures gradually decrease to about 300 °C, when most of cassiterite precipitation occurred in the samples studied. The primary mechanism of phosphate alteration has been identified as a coupled dissolution-reprecipitation process, which led to REE exchange in the igneous fluorapatite and hydrothermal monazite. In Type I local alteration, La and Pr-Nd show continuity across the pre- and post- alteration concentric zones indicating that they were not affected by alteration. This is an example of a selective elemental exchange during coupled dissolution-precipitation. Type II, pervasive post-growth alteration, is evident by the presence of micro-porosity and the formation of secondary, reaction induced minerals. Release of HREE from the monazite goes into the formation of void filling xenotime inclusions; the first documentation of this metasomatic alteration product in monazite. A well-documented discrepancy exists among ages determined from the zircon, fluorapatite, monazite, and altered porphyry minerals. These observations, regarding selective alteration of fluorapatite and monazite, may help to elucidate the reasons for this discrepancy.