Zoisite- and clinozoisite-segregations in metabasites (Tauern Window, Austria) as evidence for high-pressure fluid–rock interaction

High-pressure zoisite- and clinozoisite-bearing segregations are common in garnet- and albite-bearing amphibolites of the Palaeozoic part of the Lower Schieferhülle, south-central Tauern Window, Austria. The zoisite segregations (primary assemblage: Zo+Qtz+Cal) formed during an early to pre-Hercynian high-pressure event (P≫0.6 GPa, T =500–550 °C) by hydrofracturing as a result of protolith dehydration. Zoisite is growth zoned from Fe³⁺-poor cores (Al₂Fe=9 mol%) to Fe³⁺-rich rims (17 mol%), and has high Sr, Pb and Ga contents and LREE-enriched REE patterns, controlling the trace element budget of the segregations. Hercynian deformation at c. 0.7 GPa/600 °C kinked and cracked primary zoisite and enhanced breakdown into secondary zoisite (13 mol% Al₂Fe), clinozoisite (40–55 mol% Al₂Fe), albite (an_<20), calcite and white mica during an Eoalpine high-pressure event at 0.9–1.2 GPa/400–500 °C. The clinozoisite segregations (primary assemblage: Czo+Qtz+Omp+Ttn+Chl+Cal) are mm- to cm-wide, vein-like bodies, cross-cutting fabric elements of the host garnet amphibolite. They formed during the Eoalpine high-pressure event at 0.9–1.2 GPa/400–500 °C. During Alpine exhumation, omphacite was pseudomorphed by amphibole, albite, quartz and clinozoisite. Oxygen isotope data suggest equilibrium between host metabasite and zoisite segregations and indicate an internal fluid source and fluid buffering by the protolith. Mobility of P, Nb and LREE changed the protolith’s trace element composition in the vicinity of the zoisite segregations: Mobilization of LREE is evidenced by decreasing modal amounts of LREE-rich epidote and decreasing LREE contents in LREE-rich epidote towards the segregations, changing the REE patterns of the host metabasite from LREE-enriched to LREE-depleted. Tectonic discrimination diagrams, based on the trace element content of metabasites, should be applied with extreme caution.     

Experimental investigation of zoisite–clinozoisite phase equilibria in the system CaO–Fe2O3–Al2O3–SiO2–H2O

The system Ca₂Al₃Si₃O₁₁(O/OH)-Ca₂Al₂FeSi₃O₁₁(O/OH), with emphasis on the Al-rich portion, was investigated by synthesis experiments at 0.5 and 2.0 GPa, 500-800 °C, using the technique of producing overgrowths on natural seed crystals. Electron microprobe analyses of overgrowths up to >100 µm wide have located the phase transition from clinozoisite to zoisite as a function of P-T-X_ps and a miscibility gap in the clinozoisite solid solution. The experiments confirm a narrow, steep zoisite-clinozoisite two-phase loop in T-X_ps section. Maximum and minimum iron contents in coexisting zoisite and clinozoisite are given by X_ps^zo (max) = 1.9*10 ^{- 4} T+ 3.1*10 ^{- 2} P - 5.36*10 ^{- 2}{\rm X}_{{\rm ps}}^{{\rm zo}} {\rm (max) = 1}{\rm .9*10}^{ - 4} T{\rm + 3}{\rm .1*10}^{ - 2} P - {\rm 5}{\rm .36*10}^{ - 2} and X_ps^czo (min) = (4.6 * 10 ^{- 4} - 4 * 10 ^{- 5} P)T + 3.82 * 10 ^{- 2} P - 8.76 * 10 ^{- 2}{\rm X}_{{\rm ps}}^{{\rm czo}} {\rm (min)} = {\rm (4}{\rm .6} * {\rm 10}^{ - {\rm 4}} - 4 * {\rm 10}^{ - {\rm 5}} P{\rm )}T + {\rm 3}{\rm .82} * {\rm 10}^{ - {\rm 2}} P - {\rm 8}{\rm .76} * {\rm 10}^{ - {\rm 2}} (P in GPa, T in °C). The iron-free end member reaction clinozoisite = zoisite has equilibrium temperatures of 185ᇆ °C at 0.5 GPa and 0ᇆ °C at 2.0 GPa, with (H_r⁰=2.8ǃ.3 kJ/mol and (S_r⁰=4.5ǃ.4 J/mol2K. At 0.5 GPa, two clinozoisite modifications exist, which have compositions of clinozoisite I ~0.15 to 0.25 X_ps and clinozoisite II >0.55 X_ps. The upper thermal stability of clinozoisite I at 0.5 GPa lies slightly above 600 °C, whereas Fe-rich clinozoisite II is stable at 650 °C. The schematic phase relations between epidote minerals, grossular-andradite solid solutions and other phases in the system CaO-Al₂O₃-Fe₂O₃-SiO₂-H₂O are shown.