We have calculated the behavior of hydrogen and deuterium during the magma ocean and subsequent water ocean epochs to determine the extent to which hydrogen isotopes reflect the evolution of this early epoch. In analogy with modern silicate Earth, the magma ocean-primordial atmosphere system is often assumed to be chemically oxidized (logfO2~QFM) with H2O and CO2 the dominant atmospheric species. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also be much more reducing (logfO2~IW-2) such that equilibrium with the overlying atmosphere makes H2 and CO the dominant H- and C-bearing species [5]. This variable - the redox state of the magma ocean - is critical to the evolution of the early (Hadean) Earth but has not been previously constrained.
Figure 2 Schematic evolution of the behavior of water and hydrogen during and immediately after
the magma ocean. Solidification leads to outgassing of terrestrial volatiles, whose evolution generates
the earliest oceans and atmosphere. The deuterium content of the oceans reflects the chemical composition
(e.g., H2/H2O) of the primordial atmosphere. From [6]. We have identified the hydrogen
isotopic composition of the terrestrial and Martian hydrospheres as tracers of early atmospheric processes [6,7].
We have found that the redox state of the magma ocean controls not only the chemical composition of the primordial
atmosphere but also the hydrogen isotopic composition of the hydrosphere following primordial atmospheric escape.
Water concentrates deuterium and, to the extent that H2 was a significant species in a primordial
atmosphere, significant deuterium-enrichment in the planetary hydrosphere would have been generated. The
Earth-chondrite "match" in D/H (to within ~10-20%) constrains the amount of H2 in the Hadean atmosphere
to < 10 bars [6], providing novel evidence that Earth's earliest outgassed atmosphere was a steam atmosphere.
By contrast, the 2-3x D/H enrichment observed in aqueous alteration products from the Martian crust relative to
the mantle is reproduced if the primordial Martian atmosphere contained > 10 bars H2 [7]. In this
way, the D/H of planetary hydrospheres is an oxybarometer for primordial outgassing and constitute empirical
constraints on the primordial composition of the terrestrial and Martian atmospheres.
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