Effects of fluorine on dynamic reaction interfaces in hydrothermal feldspar alteration

Abstract

Fluid-induced mineral reactions exert an important control on the physico-chemical properties of the crust and hydrothermal plumbing systems. Feldspars are the most abundant minerals in the Earth's crust and a major host of the main cations found in geofluids (Na, K, Ca). In previous work, we discovered that K-feldspar-albite-sanidine zonation textures developed dynamically when sanidine ((K,Na)AlSi3O8) was reacted with NaCl or NaF in H216O- and H218O-enriched solutions at 600 °C and 2 kbar in a closed system. Based on a detailed SEM and TEM characterisation, the present study aims to constrain the reaction mechanism and the effect of fluorine on reaction kinetics and overall reaction textures in alkali feldspar replacement reaction interfaces. Replacement of high-sanidine (Sa) by albite (Ab) and/or K-feldspar (Kfs) proceeded via an interface-coupled dissolution-reprecipitation reaction, with the products preserving the crystallographic orientation of the parent Sa in both NaCl- and NaF-bearing solutions. Mineral interfaces with different micro-textures were observed depending on the nature of the interface (Ab-Sa, Kfs-Ab, Kfs-Sa) and whether the reaction occurred in NaCl-only or NaF-bearing solutions. Abundant amorphous domains (25–50 nm thick) occur both within Ab and at Ab-Sa and Kfs-Ab interfaces formed in NaF-bearing solutions. At the Kfs-Sa interface formed in NaCl-only solutions, a complex interfacial zone characterised by a high density of defects may represent sealed fluid pathways. These results reveal that the nature of the reaction interface depends on both mineral properties, in particular microtextures (i.e. polysynthetic twinning in Ab); and solution chemistry; this directly affects porosity development, the chemical environment at the interface, and chemical exchanges between the reaction front and the bulk solution. Fluorine aids the formation of amorphous layers that modify nucleation mechanisms; and facilitates element transport by forming Na-Si-Al-fluoride complexes, resulting in accelerated reaction rates relative to chloride-solutions. These nm- to μm-level processes contribute to efficient coupling between fluid-flow and mass transfer, explaining why sodic and potassic alteration associated with metal and fluid transport in some of the world's largest ore deposits can develop extensively, and subsequently access metals locked within silicate mineral assemblages.