Experimental study of chloritoid stability at high pressure and various fO2 conditions |
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| Authors: | Olivier Vidal Thomas Theye Christian Chopin |
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| Institution: | (1) E.N.S., Laboratoire de Géologie (URA 1316 du CNRS), 24 rue Lhomond, F-75231 Paris Cedex 05, France;(2) Institut für Mineralogie, Ruhr Universität Bochum, D-44780 Bochum 1, Germany;(3) Institut für Geowissenschaften, Abt. Mineralogie, Universität Braunschweig, Posttach 3329, D-38023 Braunschweig |
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| Abstract: | The reaction chloritoid (ctd)=almandine (alm)+diaspore+H2O (CAD) has been reversed using Fe3+-free synthetic chloritoid and almandine, under fO2 conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO2 conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO2 conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH2O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H2O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H2O bracketed on the Fe/FeO buffer and under unbuffered fO2 conditions. For fO2 buffered by the assemblage Fe/FeO, aH2O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO2 buffered by the assemblage Ni/NiO, aH2O=1. The aH2O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H2O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H
o
f,ctd and S
octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and KD=(Fe3+/Al)ctd/(Fe3+/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe3+ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl2SiO5(OH)2 formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe3+ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H2O (CQGK), calculated for intermediate Fe–Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65<(XFe)gt<0.8, CQKG calculated from FASH and MASH overlap for KD=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the KD values reported from chloritoid+garnet+quartz+kyanite natural assemblages. |
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