Supersilicic clinopyroxene and silica exsolution in UHPM eclogite and pelitic gneiss from the Kokchetav massif, Kazakhstan

Abundant exsolved quartz rods occur in matrix clinopyroxene of eclogite from the Kokchetav massif, Kazakhstan. These rocks are diamond-grade, ultrahigh-pressure (UHP) metamorphic rocks that recrystallized at P > 6 GPa and T > 1000 °C, Zircon is an excellent container, which effectively protects peak UHP metamorphic phases from retrogression. Therefore, to ascertain the pre-exsolution composition of the clinopyroxene, we analyzed clinopyroxene inclusions in zircon of the eclogite and a diamond-bearing biotite gneiss. Clinopyroxene in zircon has an excess of Fe³⁺ + (VI)Al over (IV)Al + Na + K, and calculated cation totals significantly less than 4.0 per six O atoms. The stoichiometry of these pyroxenes can be reconciled if the Ca-Eskola end-member (Ca_0.5[ ]_0.5AlSi₂O₆) is considered. The zircon-hosted clinopyroxene in the eclogite contains up to 9.6 mol% of the Ca-Eskola component, and in the biotite gneiss up to 18.2 mol%, whereas the matrix clinopyroxene contains much less (1.3 mol%, on average). Recalculation of the composition of the matrix clinopyroxene prior to exsolution of quartz rods yields 6.8 mol% Ca-Eskola component, which is consistent with the composition of the clinopyroxene inclusions in zircon. We conclude that the Ca-Eskola component in the peak metamorphic clinopyroxenes broke down by a retrograde reaction: 2 Ca_0.5[ ]_0.5AlSi₂O₆ → CaAl₂SiO₆ + 3 SiO₂ resulting in exsolution of the quartz rods in the matrix clinopyroxene. Subducted crustal and supracrustal rocks from the Ca-Eskola clinopyroxene at high pressures and temperatures. The vacancy-containing clinopyroxene may have an important bearing on the physico-chemical properties of the subducted slab at upper mantle depth.