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J Geol. 2000 Jan;108(1):103-119.

An Internally Consistent Thermodynamic Model for the System CaO-MgO-Al2O3-SiO2 Derived Primarily from Phase Equilibrium Data.


An internally consistent thermodynamic model for the subsolidus system CaO-MgO-Al2O3-SiO2 (CMAS) was developed and refined using primarily data from phase equilibrium experiments. The solution properties of pyroxenes and garnet were approximated with an ionic model, with independent mixing on adjacent crystallographic sites. This approach simplified the calculation of phase relations by allowing sequential calculation of the site occupancies. Enthalpy, entropy, and volume differences, nominally at 970 K, were derived for all participating phases by matching as closely as possible the experimentally observed phase relations. Although thermochemical measurements were not used directly in the refinement, the results were continuously monitored and compared with the thermochemical data to achieve a close match. The new model can be used to calculate phase diagrams for the CMAS system and its subsystems in the whole pressure range of the upper mantle. Simple empirical corrections for the effects of Na, Fe, Cr, etc., could potentially be introduced to make the model applicable to the thermobarometry of chemically complex mantle materials. Application of the new model to garnet lherzolite xenoliths from northern Lesotho and garnet peridotites from Norway supports the proposals for higher temperatures of the continental lithosphere.

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