Experimental determination of ferric iron partitioning between pyroxene and melt at 100KPa

preprint2020arXivOpen access

Abstract

Pyroxene is the principal host of Fe3+^{3+} in basalt source regions, hosting 79 and 81% of the Fe3+^{3+} in spinel and garnet lherzolite, respectively, with opx and cpx hosting 48% and 31%, respectively, of the total Fe3+^{3+} in spinel peridotite. To better understand partitioning of Fe3+^{3+} between pyroxene and melt we conducted experiments at 100 KPa with fO2_{O2} controlled by CO-CO2_2 gas mixes between ΔΔQFM -1.19 to +2.06 in a system containing andesitic melt saturated with opx or cpx only. To produce large (100-150 μμm), homogeneous pyroxenes, we employed a dynamic cooling technique with a 5-10°°C/h cooling rate, and initial and final dwell temperatures 5-10°°C and 20-30∘^\circC super and sub-liquidus, respectively. Resulting pyroxene crystals have absolute variation in Al2_2O3_3 and TiO2_2 <0.05 wt.% and <0.02 wt.%, respectively. Fe3+^{3+}/FeT^T in pyroxenes and quenched glass were measured by XANES. We used a newly developed XANES calibration for cpx and opx by only selecting spectra with X-ray vibrating on the optic axial plane at 50±5∘50 \pm 5^\circ to the crystallographic c axis. Values of DFe3+^{3+} cpx/melt increase from 0.03 to 0.53 as fO2 increases from ΔΔQFM -0.44 to 2.06, while DFe3+^{3+} opx/melt remains unchanged at 0.26 between ΔΔQFM -1.19 to +1.37. In comparison to natural peridotitic pyroxenes, Fe3+^{3+}/FeT in pyroxenes crystallized in this study are lower at similar fO2_{O2}, presumably owing to lower Al3+^{3+} contents. This study shows that the existing thermodynamic models implemented in pMELTS and Perple_X over-predict the stability of Fe3+^{3+} in pyroxenes, causing an anomalous reduced character to spinel peridotites at calculated conditions of MORB genesis.

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