We present in situ observations of hydrocarbon formation via carbonate reduction at upper mantle pressures and temperatures. Methane was formed from FeO, CaCO3-calcite, and water at pressures between 5 and 11 GPa and temperatures ranging from 500°C to 1,500°C. The results are shown to be consistent with multiphase thermodynamic calculations based on the statistical mechanics of soft particle mixtures. The study demonstrates the existence of abiogenic pathways for the formation of hydrocarbons in the Earth's interior and suggests that the hydrocarbon budget of the bulk Earth may be larger than conventionally assumed.

[1] We have carried out nuclear resonant scattering measurements on 57 Fe-enriched Fe 3 C between 1 bar and 50 GPa at 300 K. Synchrotron Mössbauer spectra reveal a pressure-induced magnetic transition in Fe 3 C between 4.3 and 6.5 GPa. On the basis of our nuclear resonant inelastic X-ray scattering spectra and existing equation-of-state data, we have derived the compressional wave velocity V P and shear wave velocity V S for the high-pressure nonmagnetic phase, which can be expressed as functions of density (r):) and V S (km/s) = 1.45 + 0.24r(g/cm 3

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The bulk modulus of scheelite-structured ZrSiO(4) is 301.4+/-12.5 GPa, as derived from static compression experiments to 52.5 GPa. It is as stiff as the most incompressible known silicate, SiO(2) stishovite. This high incompressibility indicates that octahedrally coordinated silicon is not required to generate ultrastiff silicates: ZrSiO(4) scheelite is the most incompressible material containing SiO(4) tetrahedra. Its incompressibility is in accord with a semitheoretical relation we derive for the bulk modulus of scheelite-structured materials. Based upon correlations between incompressibility and hardness, scheelite-structured oxides may thus represent a new family of ultrahard materials.

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