Experimental Na-K distribution between amphiboles and aqueous chloride solutions, and a mixing model along the richterite – K-richterite join

Abstract

The cation exchange equilibrium

has been investigated by hydrothermal experiments at 700 and 800°C at 200 MPa. To avoid equilibration problems of conventional exchange experiments, we synthesized amphiboles with an excess fluid allowing exchange between solid and fluid during the experiment. The exchangeable cations Na and K were provided as excess 1 to 2n chloridic solution. These exchange syntheses can be described by the reaction equation

with ^(aq) for hydroxides and chlorides in aqueous solutions and _{( s )} and _{( p )} = start and product fluid. The amphiboles grew in presence of the exchange fluid and adjusted their stoichiometry in equilibrium with the fluid phase. The solid products consist of more than 99% amphibole (Na,K-richterite_ss) with traces of diopside and quartz. The amphiboles are up to 1 mm long and often ≈ 40 μm thick. Detailed EMP- and HRTEM-observations show that they are chemically homogeneous and structurally wellordered. The experimental results give consistent phase relations in the reciprocal ternary system Na-richterite–K-richterite–NaCl–KCl. We analysed the product fluid with AAS- and ICP-methods. The Na-K distribution coefficients between fluid and amphiboles of the richterite–K-richterite join are close to unity at 700°C and 800°C at 200 MPa. Small systematic deviations are explained by a symmetric solution model for the A-position of the amphiboles. Using ideal mixing for H₂O-NaCl-KCl fluids, a mixing model for the system richterite–K-richterite is presented. We suggest that the composition of richterite solid solutions can be used as a sensor for NaCl/KCl-ratios in metamorphic fluids.