In-situ trace element and Li-isotope study of zinnwaldite from the Degana tungsten deposit, India: Implications for hydrothermal tungsten mineralization

Abstract

Zinnwaldite, a Li, Rb-mica is a common magmatic or hydrothermal mineral in many tungsten deposits. In this study, we use the trace element and Li-isotope composition of zinnwaldite from Degana, the largest tungsten deposit of India, to constrain the source and evolution of the ore fluid, the precipitation mechanism of W and the roles of fractional crystallization, fluid exsolution and fluid-rock interaction in the mineralization process. Textural evidence suggests that the mineralization in the Degana rocks involved at least two stages of fluid infiltration. The earlier of the two was multi-pulsed and responsible for the primary tungsten and zinnwaldite mineralization. The second hydrothermal stage caused partial dissolution and reprecipitation of both wolframite as well as zinnwaldite, reflected in the patchy zones that replace both minerals. The ore fluid had high concentration of Li, Rb, Cs, Nb, and Ta as evident from zinnwaldite chemistry. The δ7Li of the ore fluid (+14 to +19 ‰), estimated from the Li-isotope composition of zinnwaldite in mineralized veins (δ7Li = +12 to +17‰), is significantly heavier compared to upper/middle continental crust, ruling out the possibility of a metamorphic fluid source. The high concentration of incompatible elements including Cs, extremely low K/Rb (10–15), is best explained by its growth from fluids exsolved from an enriched, late-fractionated granitic melt. Alteration of the host granite, formation of greisen, large-scale albitization and muscovitization are indicative of fluid-rock interaction, which might have increased the fluid pH, destabilizing fluoride complexes of W, resulting in the precipitation of wolframite. The shift in the chemical and Li-isotope composition from the early mica to late altered ones in the greisen indicates interaction of the hydrothermal fluid with the host rocks. A U-Pb Concordia age of 838 ± 9 Ma retrieved from magmatic domains of zircon from the Degana granite dates it emplacement and represents the maximum age of the W-mineralization.