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Potassium-bearing clinopyroxene: a review of experimental, crystal chemical and thermodynamic data with petrological applications

Published online by Cambridge University Press:  05 July 2018

O. G. Safonov
Affiliation:
Institute of Experimental Mineralogy, Russian Academy of Science, Academician Ossipian str. 4, 142432, Russia Department of Geology, University of Johannesburg, Auckland Park, Johannesburg 2006, South Africa
L. Bindi*
Affiliation:
Museo di Storia Naturale, sezione di Mineralogia, Universitá degli Studi di Firenze, Via La Pira, 4, I-50121, Florence, Italy CNR – Istituto di Geoscienze e Georisorse, sezione di Firenze, Via La Pira, 4, I-50121, Florence, Italy
V. L. Vinograd
Affiliation:
Institute of Energy and Climate Research, Forschungszentrum Jülich GmbH 1, 52425 Jülich, Germany

Abstract

Available experimental data on chemical composition and crystal structure of K-bearing clinopyroxenes are compiled together with the results of atomistic simulations and thermodynamic calculations of mineral equilibria. It is shown that the limited solubility of K2O in clinopyroxene from crustal rocks cannot be ascribed to the strong non-ideality of mixing between diopside (CaMgSi2O6) and K-jadeite (KAlSi2O6) components. The more likely reason is the instability of the potassic endmember with respect to other K-bearing phases. As the volume effects of typical K-jadeite-forming reactions are negative, the incorporation of K in the clinopyroxene structure becomes less difficult at higher pressure. Atomistic simulations predict that the thermodynamic mixing properties of diopside-K-jadeite solid-solutions at high temperature approach those of a regular mixture with a relatively small positive excess enthalpy. The standard enthalpy of formation fH° = —2932.7 kJ/mol), the standard volume (V° = 6.479 J mol–1 bar–1) and the isothermal bulk modulus (K0 = 145 GPa) of K-jadeite were calculated from first principles, and the standard entropy (S° = 141.24 J mol–1 K–1) and thermal-expansion coefficient (α = 3.3 x 1CP–5 K–1) of the K-jadeite endmember were estimated using quasi-harmonic lattice-dynamic calculations based on a force-field model. The estimated thermodynamic data are used to compute compositions of K-bearing clinopyroxenes in diverse mineral assemblages within a wide P-T interval. The review substantiates the conclusion that clinopyroxene can serve as an effective container for K at upper-mantle conditions.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2011

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