An experimental study of rare earth element partitioning between a shergottite melt and pigeonite: implications for the oxygen fugacity of the martian interior

A series of experiments on a synthetic, pigeonite-saturated, basaltic shergottite were carried out to constrain the variation of D(Eu/Gd)(pigeonite/melt) and D(Eu/Sm)(pigeonite/melt) with oxygen fugacity (f(O2)). The experiments have been run Under both dry and hydrous conditions. The shergottite was doped with 0.1, 0.5, and 1.0 wt.% Eu. Gd, and Sin oxides in different experiments and was equilibrated at liquidus conditions for 24 hours. D(Eu/Gd)(pigeonite/melt) in dry melts ranges from 0. 156 +/- 0.014 (f(O2) = IW - 1) to 0.630 +/- 0.102 (IW + 3.5). D(Eu/Sm)(pigeonite/melts) in dry melts ranges from 0.279 +/- 0.021 (IW - 1) to 1.114 +/- 0.072 (IW + 3.5). Due to difficulties with low-f(O2) experiments, hydrous distribution coefficients were measured, but were not used in the calibration of the Eu-oxybarometers. These two Eu-oxybarometers provide ail accurate way to measure f(O2) recorded during pigeonite crystallization, thereby yielding a record of f(O2) during the earliest period of Martian meteorite parent magma crystallization history. Using this new calibration, Martian meteorite pigeonite cores record f(O2) values of IW - 0.6 (+/-0.3) (QUE94201) to IW + 1.9 (+/-0.6) (Shergotty). These new values differ in magnitude, but not trend, from previously published data. The pigeonite Eu-oxybarometer yields f(O2) range in the basaltic shergottites of 2 to 3 orders of magnitude. Several processes have been proposed to explain the origin of fO2 range, the majority of which rely on assimilation of an oxidized source. A potential correlation between this new pigeonite data and recent Fe-Ti oxide data, however, is consistent with intrinsic f(O2) differences in the magma source region being responsible for the measured variations. This implies that the Martian meteorite source region. the mantle or lithosphere, may he heterogeneous in nature. However, the process of assimilation cannot be completely ruled Out ill that an assimilation event that took place before crystallization commenced would result in the overprinting of the Source re ion signature. Copyright (C) 2004 Elsevier Ltd.