Calibration of oxygen isotope fractionation and calcite-corundum thermometry in emery at Naxos, Greece

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.