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Calibration of oxygen isotope fractionation and calcite-corundum thermometry in emery at Naxos,Greece
Authors:Rachelle B Turnier  Yaron Katzir  Kouki Kitajima  Ian J Orland  Michael J Spicuzza  John W Valley
Institution:1. Department of Geoscience, University of Wisconsin, Madison, Wisconsin;2. Department of Geological and Environmental Sciences, Ben Gurion University of the Negev, Be'er Sheva, Israel
Abstract:Corundum (Crn), including sapphire, occurs in emery pods surrounded by marble on the island of Naxos, Greece. The emery formed from bauxite deposited in karst that was metamorphosed to 400–700°C at 20–15 Ma. Many of these rocks initially appeared well suited for refractory accessory mineral (RAM) thermometry, which uses oxygen isotope fractionation between a RAM – corundum – and a modally dominant phase with faster diffusion of oxygen – calcite (Cc) – to determine peak metamorphic temperatures. However, previous attempts at oxygen isotope thermometry were confounded by highly variable fractionations (Δ18O) measured at mm-scale and the uncertain calibration of Δ18O(Cc-Crn) versus temperature. Secondary ion mass spectrometry (SIMS) permits in situ analysis of δ18O in corundum and calcite at the 10-μm scale in adjacent grains where textures suggest peak metamorphic equilibrium was attained. SIMS analyses of adjacent mineral pairs in eight rocks yield values of Δ(Cc-Crn) that systematically decrease from 7.2 to 2.9‰ at higher metamorphic grade. Pairing these data with independent temperature estimates from mineral isograds yields an empirical calibration of 1,000 lnα(Cc-Crn) = 2.72 ± 0.3 × 106/T2 (T in K). The new fractionations (2.7‰ at 1,000 K) are significantly smaller than those calculated from the modified increment method (6.5‰ at 1,000 K; Zheng, Geochimica et Cosmochimica Acta, 1991, 55:2299–2307; Zheng, Mineral Mag, 1994, 58A:1000–1001), which yield unreasonably high temperatures of 630 to 1,140°C when applied to the new Naxos data. The new calibration of Δ(Cc-Crn) can be combined with published fractionations to calculate A-factors for corundum versus a range of 14 other minerals. These new fractionation factors can be used for thermometry or to constrain the genesis of corundum. A compilation of gem corundum δ18O values shows that many igneous sapphires, including important deposits of basalt-associated sapphire, are mildly elevated in δ18O relative to the calculated range in equilibrium with mantle values (4.4–5.7‰) and formed from evolved magmas.
Keywords:calcite  corundum  oxygen isotope fractionation  SIMS  thermometry
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