An enlarged and updated internally consistent thermodynamic dataset with uncertainties and correlations: the system K₂O–Na₂O–CaO–MgO–MnO–FeO–Fe₂O₃–Al₂O₃–TiO₂–SiO₂–C–H₂–O₂

TLDR

The authors present an enlarged thermodynamic dataset for the K₂O–Na₂O–CaO–MgO–MnO–FeO–Fe₂O₃–Al₂O₃–TiO₂–SiO₂–C–H₂–O₂ system and aim to maximize its utility for mineral assemblage calculations while providing a framework for uncertainty assessment. The dataset comprises 123 mineral and fluid end‑members, consistent with over 200 P–T–X CO₂–fO₂ experiments, grouped by reliability, enriched with iron‑bearing phases, modeled H₂O/CO₂ in cordierites, Landau‑theory heat‑capacity anomalies, and Tschermak‑substituted end‑members, and is used to compute complex solid‑solution compositions for invariant, univariant, and divariant assemblages. Comparison with Berman (1988) data shows substantial agreement and comparable accuracy in reproducing.

Abstract

We present, as a progress report, a revised and much enlarged version of the thermodynamic dataset given earlier (Holland & Powell, 1985). This new set includes data for 123 mineral and fluid end‐members made consistent with over 200 P–T–X CO2 – f O2 phase equilibrium experiments. Several improvements and advances have been made, in addition to the increased coverage of mineral phases: the data are now presented in three groups ranked according to reliability; a large number of iron‐bearing phases has been included through experimental and, in some cases, natural Fe:Mg partitioning data; H 2 O and CO 2 contents of cordierites are accounted for with the solution model of Kurepin (1985); simple Landau theory is used to model lambda anomalies in heat capacity and the Al/Si order–disorder behaviour in some silicates, and Tschermak‐substituted end‐members have been derived for iron and magnesium end‐members of chlorite, talc, muscovite, biotite, pyroxene and amphibole. For the subset of data which overlap those of Berman (1988), it is encouraging to find both (1) very substantial agreement between the two sets of thermodynamic data and (2) that the two sets reproduce the phase equilibrium experimental brackets to a very similar degree of accuracy. The main differences in the two datasets involve size (123 as compared to 67 end‐members), the methods used in data reduction (least squares as compared to linear programming), and the provision for estimation of uncertainties with this dataset. For calculations on mineral assemblages in rocks, we aim to maximize the information available from the dataset, by combining the equilibria from all the reactions which can be written between the end‐members in the minerals. For phase diagram calculations, we calculate the compositions of complex solid solutions (together with P and T ) involved in invariant, univariant and divariant assemblages. Moreover we strongly believe in attempting to assess the probable uncertainties in calculated equilibria and hence provide a framework for performing simple error propagation in all calculations in thermocalc, the computer program we offer for an effective use of the dataset and the calculation methods we advocate.