Abstract
Magma ocean crystallization models that track fO2 evolution can
reproduce the D/H ratios of both the Earth and Mars without the need for
exogenous processes. Fractional crystallization leads to compositional
evolution of the bulk oxide components. Metal-saturated magma oceans
have long been thought to contain negligible ferric iron oxide
(Fe3+O1.5), but recent work suggests they may contain near-present-day
Fe3+ concentrations. We model the fractional crystallization of Earth
and Mars, including Fe2+ and Fe3+ as separate components. We use two
independent equations of state (Deng, Armstrong EOS) to calculate Fe3+
partition coefficients for lower mantle minerals and compare results of
fractional crystallization for different magma ocean configurations for
both Earth and Mars. We calculate the oxygen fugacity (fO2) at the
surface as the systems evolve and compare them to constraints on the fO2
of the last magma ocean atmosphere from D/H ratios. For Earth, we find
that Fe3+ must behave incompatibly in the lower mantle to match the D/H
constraint for whole mantle models, but shallow magma ocean models also
provide reasonable matches to the constraints. For Mars, both EOSs
produce near identical results but cannot match the D/H constraints on
last fO2 unless the magma ocean begins with less than 50% of the
predicted Fe3+. This model shows that Fe3+ partitioning has a measurable
effect on magma ocean atmosphere redox state, which is not a static
quantity but evolves throughout the magma ocean’s lifetime. We highlight
the need for additional experimental constraints on ferric iron
partitioning.