Geochemical behaviour of biotite during interaction with aqueous and brine fluids: Constraints from hydrothermal batch experiments

Biotite plays an important role in the geochemical cycle of Li, Rb, Cs, and Ba in the upper continental crust, as it is a significant carrier of Li and large-ion lithophile elements in felsic igneous rocks and high-grade detrital metasedimentary rocks. During its interaction with meteoric and hydrothermal fluids, biotite can be transformed into various types of clay minerals (mostly, interlayer-deficient biotite, vermiculites and smectites). These transformations can cause fractionation of the alkaline trace-element ratios Rb/Li, Cs/Li and Rb/Cs between biotite and its replacement products. This study examines the mineral transformations that occur when biotite interacts with aqueous and saline fluids and the poorly understood geochemical behaviour of the resulting phyllosilicates. For this purpose, we performed batch hydrothermal experiments of the interaction of biotite + quartz ± graphite with ultrapure H2O, and 2 M NaCl, 2 M CaCl2 and 1 M NaF brine fluids at 170 °C and 10 bar using Teflon bombs, and at 550 °C and 800 to 1400 bar using autoclave apparatus. At lower-T conditions, biotite was replaced by 2:1 trioctahedral clay minerals (interlayer-deficient biotite, smectite, vermiculite, and other phyllosilicate species with higher interlayer charge) and Fe oxy-hydroxide minerals by coupled dissolution-precipitation mechanisms. At higher-T conditions, these mechanisms caused the transformation of biotite into the mineral assemblages (quartz ± graphite): diopside + anorthite + titanite (CaCl2 brine experiments), albite + ilmenite + clay minerals (NaCl brine experiments), and cryolite + alkali feldspar with albite rimmed by K-feldspar + Fe-oxides (NaF brine experiments). Therefore, a significant reduction of the clay mineral stability in the presence of NaF and CaCl2 brine fluids is inferred. The biotite replacements by phyllosilicates were mostly controlled by the ion exchange of K+ by H+ (or its hydrate state H3O+), hydrated Na+ and Ca2+, and NaF in the interlayer site. Conservation of the total mass and the Si, Al and Mg abundances occurred in most experimental phyllosilicates. However, in the products of the low-T NaF brine ± graphite experiments, the total mass may have a gain of 5.3–11 % assuming Mg conservation. Sc, V, Nb and Ta abundances were also conserved, but a significant fractionation of the Rb/Li, Cs/Li, and Ba/Li ratios occurred in the experimental phyllosilicates. The experiments predict the generation of highly fractionated Rb/Li and Cs/Li phyllosilicates by replacement of biotite during interaction with aqueous fluids and, mostly, NaCl and NaF brine fluids at high-T and low-T conditions, respectively. This demonstrates a key role of biotite in the fractionation of Rb/Li, Cs/Li and Rb/Cs during the hydrothermal alteration of felsic igneous rocks. Conversely, a reversal in the mobility of Li with respect to Rb and Cs occurred in the phyllosilicate products when biotite interacted with NaCl or CaCl2 brine fluids at relatively low-T conditions. These experimental results highlight the key role of biotite-fluid interaction processes in controlling the budget of alkaline trace elements in the continental crust.