Closed system fluid-mineral-mediated trace element behaviour in peralkaline rare metal pegmatites: Evidence from Strange Lake

Abstract

Large peralkaline complexes are ‘factories’ that have produced a variety of ‘exotic’ minerals including high field strength element minerals. In most cases, these minerals are secondary and crystallise in a hydrothermal paragenesis that is extremely difficult to decipher due to the complexity of the textural relationships. The Strange Lake pluton is one of these complexes, and contains 37 exotic minerals, most of which are secondary. Adding to the difficulty in establishing a comprehensive paragenesis for these minerals and an alteration/precipitation path for the pluton is the fact that there were several stages of crystallisation of the same exotic and common secondary minerals, e.g., bastnäsite, fluocerite, gadolinite, aegirine, fluorite, and zircon.In this paper, we present a model, which describes a detailed path for the alteration and precipitation of minerals in the closed hydrothermal system of a peralkaline granitic pegmatite, based on direct measurements of the evolving composition of the aqueous fluid that exsolved from the late-stage magma crystallising rare-metal pegmatites in the Strange Lake pluton. The driving force for this evolution was cooling-induced oxidation that ultimately transformed the CH4-H2 gas in this fluid to CO2. This led to a large drop in the pH, which was a major control on the composition of the fluid and the crystallisation of secondary minerals.Although large numbers of minerals formed and were replaced during the different stages of fluid evolution, the changing chemistry of the fluid was largely a response to the alteration of four minerals, namely arfvedsonite, elpidite, narsarsukite and fluorite. The earliest stage of alteration, which took place at ~360 °C, was marked by the replacement of arfvedsonite by aegirine. This alteration decreased salinity and released K, Li, and Rb to the fluid, causing K-metasomatism. At ~300 °C, CH4 and higher hydrocarbons reacted to produce CO2. This caused a massive drop in pH from a value > 10 to a value of ~3 and intense alteration, which included the dissolution of fluorite, the breakdown of elpidite to zircon and quartz and the replacement of narsarsukite by titanite. With ongoing dissolution of fluorite, Ca activity reached a level sufficient to promote the alteration of elpidite to armstrongite or gittinsite. This was accompanied by alteration of arfvedsonite to ferroceladonite and microcline to Al-phyllosilicates, enriching the fluid in Na, Fe and F. Soon after, there was a near total loss of CO2 (at ~230 °C). This loss was catastrophic and was focused along conical fractures (these developed as a result of the collapse of the roof of the pluton), with resultant fragmentation of the rocks along the fluid path. Alteration to phyllosilicates continued after the loss of CO2, as the system cooled to ~190 °C. This marked the beginning of the final stage of alteration, which involved the replacement of arfvedsonite by aegirine and hematite. It also coincided with large scale hematisation within the pluton. Finally, it led to the cementation of the fragments along the fluid path to form the fluorite-hematite ring breccia that is now evident at the margins of the pluton.The model of fluid evolution presented here is potentially applicable to many other peralkaline complexes. The only requirements are that the system was closed until a relatively late stage and that the exsolved fluid was saline and contained a reduced carbonic component. This is a feature of many peralkaline complexes, most notably, the Khibiny and Lovozero complexes in Russia, and Ilímaussaq in Greenland.