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Thermochemistry of the tremolite-edenite amphiboles using fluorine analogues, and applications to amphibole-plagioclase-quartz equilibria

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Abstract

Heats of mixing of synthetic C2/m fluortremolite-fluoredenite amphiboles measured at 985 K show a systematic deviation from ideal mixing consistent with a subregular solution model. The deviations from ideal mixing are interpreted in terms of Na ordering in the A-site and Na-Al interactions in edenite-poor compositions. Enthalpies of ‘edenite’ substitution reactions in amphiboles and in SiO2-NaAlO2 glasses and framework silicates are comparable. Gibbs free energies of formation of fluortremolite and fluoredenite at 298K are -2,821.07±3.34 kcal mol−1 and -2,889.59±2.40 kcal mol−1 respectively. The former value is in good agreement with values calculated from both F-OH exchange experiments and from a natural fluortremolite-bearing metamorphic rock. Least-squares fitted sub-regular heat-of-mixing parameters are poorly constrained and unrealistically high, but estimated subregular mixing parameters consistent with 95% confidence interval uncertainties in the calorimetric data and with TEM constraints give activity-composition relations in good agreement with the A-site compositions of natural metamorphic and igneous hornblendes. These relations predict unmixing in edenite-rich compositions over a wide range of temperature, but lend no support to the existence of a hornblende-actinolite miscibility gap. Calibration of the reaction tremolite+ albite=edenite+4 quartz as a function ofP,T andX amphed indicates negativedP/dT slopes and a limited range of X amphed (0.3 to 0.5) in equilibrium with plagioclase and quartz over a wide range of pressure and temperature, consistent with metamorphic hornblende-plagioclase assemblages. The energetics of this reaction suggest, however, that amphibole-plagioclase disequilibrium may be common.

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Author notes

  1. Alexandra Navrotsky

    Present address: Department of Geological and Geophysical Sciences, Princeton University, Guyot Hall, 08544, Princeton, New Jersey, USA

Authors and Affiliations

  1. Department of Geology, University of Edinburgh, West Mains Road, EH 9 3JW, Edinburgh, Scotland

    Colin M. Graham

  2. Department of Chemistry, Arizona State University, 85287, Tempe, AZ, USA

    Alexandra Navrotsky

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  1. Colin M. Graham
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Graham, C.M., Navrotsky, A. Thermochemistry of the tremolite-edenite amphiboles using fluorine analogues, and applications to amphibole-plagioclase-quartz equilibria. Contr. Mineral. and Petrol. 93, 18–32 (1986). https://doi.org/10.1007/BF00963582

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