Stability and phase relations of nonstoichiometric clinopyroxenes in the join diopside-Ca-Eskola component at high pressures

The stability of nonstoichiometric clinopyroxenes in the Di-CaEsk join was experimentally studied, and phase diagrams were constructed for this join at pressures of 2.0 and 3.0 GPa. It was found that melting in the diopside part of the join occurs at anomalously low temperatures, and nonstoichiometric clinopyroxene coexists with a phase approaching diopside in composition. Phase relations along the Di-CaEsk join can be described and consistently interpreted only assuming that the diopside phase (α-diopside) is thermodynamically stable. The following phase volumes were observed along the solidus of the join at a pressure of 3.0 GPa: Cpx, αDi+Cpx, αDi+Cpx+Qtz, αDi+Cpx+Grt+Qtz, Cpx+Grt+Qtz, Cpx+Grt+Ky+Qtz, Grt+Ky+Qtz. Melting occurs via the eutectic reaction αDi+Cpx+Grt+Qtz=L at a temperature of about 1200°C in the diopside part of the system and via the eutectic reaction Cpx+Grt+Ky+Qtz=L at a temperature of 1400°C in the calcium-rich part of the system. At a pressure of 2.0 GPa, melting occurs at temperatures of 1200–1300°C via the eutectic reaction αDi+Cpx+ An + Qtz=L. The invariant equilibrium (L, An, Cpx, Grt, αDi, Qtz) lies within the pressure range 2.0–3.0 GPa. Nonstoichiometric clinopyroxenes form complex solid solutions, the compositions of which are not strictly confined to the Di-CaEsk join and depend on temperature, pressure, and phase association. Grossular garnets coexist with nonstoichiometric clinopyroxenes and α-diopside.