Hydrothermal REE and Zr Ore Forming Processes in Peralkaline Granitic Systems

Abstract:

Anorogenic peralkaline igneous systems display extreme enrichment of REE and Zr with a hydrothermal overprint leading to post-magmatic metal mobilization. Strange Lake in Canada, for example, is a mid-Proterozoic peralkaline granitic intrusion and host to a world-class REE-Zr deposit with >50 Mt ore (>1.5 wt.% REE and >3 wt.% Zr). In contrast to porphyry systems, peralkaline systems are poorly understood and hydrothermal metal mobilization models are only in the early stage of their development. This is partly due to the paucity of thermodynamic data for REE-bearing minerals and aqueous species, and the complexity of the hydrothermal fluids (enrichment of F, P and Cl), which make it difficult to develop thermodynamic models of metal partitioning. This study aims to show the link between alteration stages and metal mobilization using Strange Lake as a natural laboratory and combine these observations with numerical modeling. Four types of alteration were recognized at Strange Lake: i) alkali (i.e. K and Na) metasomatism related to interaction with NaCl-bearing orthomagmatic fluids, ii) acidic alteration by HCl-HF-bearing fluids originating from the pegmatites followed by iii) aegirinization of the border of the pegmatites and surrounding granites and by iv) pervasive Ca-F-metasomatism. The acidic alteration accounts for most of the hydrothermal metal mobilization in and outward from the pegmatites, whereas the Ca-F-metasomatism led to metal deposition and resulted from interaction of an acidic F-rich fluid with a Ca-bearing fluid. Numerical simulations of fluid-rock reactions with saline HCl-HF-bearing fluids at 400 °C to 250 °C indicate that temperature, availability of F/Cl and pH limit the mobility of Zr and REE. Fluids with pH <2 led to the formation of quartz and fluorite in the core of the pegmatites and to an increase in the stability of REE chloride species favorable for REE mobilization. The mobilization of Zr was favored at low temperature with the formation of Zr hydroxyfluoride species depending on pH and competition with Al fluoride species requiring very low pH (<1) fluids for Zr transport. The key factor for hydrothermal metal mobilization in peralkaline granitic systems is the formation of a fluid-buffered subsystem providing the acids and ligands required for REE and Zr mobilization.