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Effect of redox on Fe–Mg–Mn exchange between olivine and melt and an oxybarometer for basalts.

Blundy, Jon and Melekhova, Elena and Ziberna, Luca and Humphreys, Madeleine C. S. and Cerantola, Valerio and Brooker, Richard A. and McCammon, Catherine A. and Pichavant, Michel and Ulmer, Peter (2020) 'Effect of redox on Fe–Mg–Mn exchange between olivine and melt and an oxybarometer for basalts.', Contributions to mineralogy and petrology., 175 (11). p. 103.


The Fe–Mg exchange coefficient between olivine (ol) and melt (m), defined as KdFeT −Mg = (Feol/Fem)·(Mgm/Mgol), with all FeT expressed as Fe2+, is one of the most widely used parameters in petrology. We explore the effect of redox conditions on KdFeT −Mg using experimental, olivine-saturated basaltic glasses with variable H2O (≤ 7 wt%) over a wide range of fO2 (ironwüstite buffer to air), pressure (≤ 1.7 GPa), temperature (1025–1425 °C) and melt composition. The ratio of Fe3+ to total Fe ( Fe3+/ΣFe), as determined by Fe K-edge μXANES and/or Synchrotron Mössbauer Source (SMS) spectroscopy, lies in the range 0–0.84. Measured Fe3+/ ΣFe is consistent (± 0.05) with published algorithms and appears insensitive to dissolved H2O. Combining our new data with published experimental data having measured glass Fe3+/ ΣFe, we show that for Fo65– 98 olivine in equilibrium with basaltic and basaltic andesite melts, KdFeT −Mg decreases linearly with Fe3+/ ΣFe with a slope and intercept of 0.3135 ± 0.0011. After accounting for non-ideal mixing of forsterite and fayalite in olivine, using a symmetrical regular solution model, the slope and intercept become 0.3642 ± 0.0011. This is the value at Fo50 olivine; at higher and lower Fo the value will be reduced by an amount related to olivine non-ideality. Our approach provides a straightforward means to determine Fe3+/ ΣFe in olivine-bearing experimental melts, from which fO2 can be calculated. In contrast to KdFeT −Mg , the Mn–Mg exchange coefficient, KdMn−Mg , is relatively constant over a wide range of P–T–fO2 conditions. We present an expression for KdMn−Mg that incorporates the effects of temperature and olivine composition using the lattice strain model. By applying our experimentally-calibrated expressions for KdFeT −Mg and KdMn−Mg to olivine-hosted melt inclusions analysed by electron microprobe it is possible to correct simultaneously for post-entrapment crystallisation (or dissolution) and calculate melt Fe3+/ ΣFe to a precision of ≤ 0.04.

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Date accepted:11 September 2020
Date deposited:28 October 2020
Date of first online publication:15 October 2020
Date first made open access:28 October 2020

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