Zr-bearing minerals as indicators for the polymetamorphic evolution of the eastern, lower Austroalpine nappes (Stubenberg Granite contact aureole, Styria, Eastern Alps, Austria)

Contact metamorphism during emplacement of the Permian Stubenberg Granite has led to the formation of the assemblage forsterite + calcite + titanian clinohumite ± phlogopite ± chlorite in the adjacent marbles. During intrusion of the granite, veins, rich in Ti, Zr, REE, and actinides (U + Th) formed. These veins show a distinct mineralogical zoning-sequence with four zones. Going from the center of the vein to the margin, these zones include the assemblages (1) geikielite + baddeleyite + zirconolite + apatite + calcite + chlorite ± magnetite ± pyrrhotite assemblage, (2) calcite + chlorite, (3) forsterite + titanian clinohumite + chlorite + calcite ± phlogopite and (4) calcite ± forsterite. Baddeleyite is always replaced by zirconolite, possibly via the model reaction baddeleyite + 2 geikielite + 3 calcite + CO2 = zirconolite + 2 dolomite. Zirconolite (Zirc I) shows a strong internal oscillatory zoning and distinct overgrowths (Zirc II), which have a different chemical composition. The chemical variation between the cores (Zirc I) and the rims (Zirc II) can be explained by using the substitutions: Me5+ + Me2+ = Ti4+ + Me3+ and REE3+ + Me5+ + Me2+ = Ca2+ + 2Ti4+. In contrast to zirconolite from metacarbonates associated with contact aureoles, these analyses show elevated Nb contents of up to 4.5 wt.% Nb2O5 and unusually high W contents of 1–2 wt.% WO3. A strong Eo-Alpine metamorphic overprint led locally to the formation of the assemblage chlorite + dolomite + calcite + ilmenite ± zirconolite II ± geikielite + Fe-sulfides. Late zircon grew locally, presumably as the last Zr-bearing mineral in the carbonates which formed during Permian contact metamorphism. The Zr-mineral sequence baddeleyite–zirconolite–zircon implies an increasing a(SiO2) and fCO2 during the growth of these minerals. Electron-microprobe dating of zirconolite (Zirc I) yields a weighted average age of 263 ± 16 Ma and indicates that the HFSE-and REE-rich assemblages formed during the Permian emplacement of the Stubenberg granite. As a result of the subsequent high-P Eo-Alpine metamorphic overprint (111 ± 15 Ma), HFSE and REE were locally re-mobilized leading to dissolution of Zirc I and reprecipitation of the REE and Nb-rich overgrowths of Zirc II.