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Journal of Petrology | Volume 43 | Number 10 | Pages 1787-1814 | 2002
© Oxford University Press 2002

The Substitution of Al and F in Titanite at High Pressure and Temperature: Experimental Constraints on Phase Relations and Solid Solution Properties

PETER TROPPER1,2,*, CRAIG E. MANNING2 and ERIC J. ESSENE1

1DEPARTMENT OF GEOLOGICAL SCIENCES, UNIVERSITY OF MICHIGAN, 2534 C. C. LITTLE BUILDING, ANN ARBOR, MI 48109-1063, USA
2DEPARTMENT OF EARTH AND SPACE SCIENCES, GEOLOGY BUILDING, UNIVERSITY OF CALIFORNIA AT LOS ANGELES, LOS ANGELES, CA 90095-1567, USA

Experimental studies were carried out to evaluate phase relations involving titanite–F–Al-titanite solid solution in the system CaSiO3–Al2SiO5–TiO2–CaF2. The experiments were conducted at 900–1000°C and 1·1–4·0 GPa. The average F/Al ratio in titanite solid solution in the experimental run products is 1·01 ± 0·06, and XAl ranges from 0·33 ± 0·02 to 0·91 ± 0·05, consistent with the substitution [TiO2+]–1[AlF2+]1. Analysis of the phase relations indicates that titanite solid solutions coexisting with rutile are always low in XAl, whereas the maximum XAl of titanite solid solution occurs with fluorite and either anorthite or Al2SiO5. Reaction displacement experiments were performed by adding fluorite to the assemblage anorthite + rutile = titanite + kyanite. The reaction shifts from 1·60 GPa to 1·15 ± 0·05 GPa at 900°C, from 1·79 GPa to 1·375 ± 0·025 GPa at 1000°C, and from 1·98 GPa to 1·575 ± 0·025 GPa at 1100°C. The data show that the activity of CaTiSiO4O is very close to the ideal molecular activity model (XTi) at 1100°C, but shows a negative deviation at 1000°C and 900°C. The results constrain {Delta}G°f,298·15 of CaAlSiO4F to be -2595 ± 3 kJ/mol and S°298·15 to be in the range of 105·2–109·6 J/mol K, which in turn can be used to calculate petrogenetic grids involving titanite solid solutions in the system CaTiSiO4O–CaAlSiO4F.

KEY WORDS: F–Al-titanite; thermodynamic data; TARK; fluorite; reaction displacement


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