Ca-Eskola incorporation in clinopyroxene: limitations and petrological implications for eclogites and related rocks

Abstract

Clinopyroxene is an essential mineral in eclogitic rocks. It commonly contains minor amounts of the defect-bearing Ca-Eskola (CaEs, Ca0.5□0.5AlSi2O6) component, with higher concentrations generally considered to indicate a high-pressure origin at least within the coesite stability field. Changes in pressure and temperature conditions can lead to exsolution of this component as a free SiO2 phase, which may have a number of petrological implications. This makes it important to understand the factors that maximize CaEs incorporation in clinopyroxene. We have undertaken a series of experiments at high pressures and temperatures (4–10 GPa and 1000–1350 °C) to further investigate the systematics of CaEs incorporation in eclogite-like clinopyroxene and the factors responsible for maximizing CaEs contents. Two simple chemical systems were chosen that allow unambiguous interpretation of the results: (1) CMAS + H2O and (2) two compositions in the NCMAS system. All experimental products contained clinopyroxene and garnet along with either a free SiO2 phase or a silicate melt. Coexisting garnet is grossular-rich, generally with X gr ≥ 0.67. Compositional variations are attributable to the presence or absence of melt and changes in modal amounts of garnet at different pressure–temperature conditions. Even small amounts of H2O lower the solidus temperature and the presence of a melt reduces the SiO2 activity, which destabilizes the CaEs component in clinopyroxene. The CaEs and the Ca-Tschermaks (CaTs, CaAl2SiO6) components in clinopyroxene decrease with increasing jadeite mole fraction, which is also a function of pressure and bulk Al content. Modeling X-ray powder diffraction data yields a molar volume for the CaEs endmember of V CaEs = 60.87(63) cm3, which reasonably agrees with a literature value that was estimated from natural samples. In the presence of coexisting coesite, the CaEs and CaTs do not vary independently of each other, being controlled by the internal equilibrium 2CaEs = CaTs + 3SiO2 (coesite). This relation, observed in simple systems (i.e., CMAS ± Na), is also obeyed by clinopyroxene in more complex, natural analog bulk compositions. An assessment of available experimental data reveals a maximum of 15–18 mol% CaEs in eclogitic clinopyroxene at conditions corresponding to 130–180 km depth. CaEs contents are maximized at high temperatures; i.e., at or near the solidus in the presence of coesite. Thus, this study supports the role of CaEs exsolution in contributing to melt generation during upwelling of eclogite bodies in the mantle, albeit with some caveats. Somewhat higher maximum CaEs contents (~20 mol%) are found in Ca and Al-rich bulk compositions, such as grospydite xenoliths. Such bulk compositions also seem to require the coexistence of kyanite. Other Ca and Al-rich rock types, like rodingites, should have the potential of containing CaEs-rich clinopyroxenes, except that they are SiO2-undersaturated. This emphasizes the further role of bulk composition, in addition to high temperatures, in achieving maximum CaEs contents in high-pressure clinopyroxene.