The high-pressure stability of zoisite and phase relationships of zoisite-bearing assemblages

Abstract

The fluid-absent reaction 12 zoisite = 3 lawsonite + 7 grossular + 8 kyanite + 1 coesite was experimentally reversed in the model system CaO-Al₂O₃-SiO₂-H₂O (CASH) using a multi-anvil apparatus. The upper pressure stability limit for zoisite was found to extend to 5.0 GPa at 700 °C and to 6.6 GPa at 950 °C. Additional experiments both in the H₂O-SiO₂-saturated and in the H₂O-Al₂O₃-saturated portions of CASH provide further constraints on high pressure phase relationships of lawsonite, zoisite, grossular, kyanite, coesite, and an aqueous fluid. Consistency of the present experiments with the H₂O-saturated breakdown of lawsonite is demonstrated by thermodynamic analysis using linear programming techniques. Two sets of data consistent with databases of Berman (1988) and Holland and Powell (1990) were retrieved combining experimental phase relationships, calorimetric constraints, and recently measured elastic properties of solid phases. The best fits result in G _{f ,1,298} ^∘,zoisite=−6,499,400 J and S _1,298 ^∘,zoisite=302 J/K, and G _{f ,1,298} ^{∘,lawsonite}=−4,514,600 J and S _1,298 ^{∘,lawsonite}=220 J/K for the dataset of Holland and Powell, and G _{f ,1,298} ^∘,zoisite=−6,492,120 J and S _1,298 ^∘,zoisite=304 J/K, and G _{f ,1,298} ^{∘,lawsonite}=−4,513,000 J and S _1,298 ^{∘,lawsonite}= 218 J/K for the dataset of Berman. Examples of the usage of zoisite as a geohygrometer and as a geobarometer in rocks metamorphosed at eclogite facies conditions are worked, profiting from the thermodynamic properties retrieved here.