Generation of methane in the Earth's mantle: in situ high pressure-temperature measurements of carbonate reduction.

We present in situ observations of hydrocarbon formation via carbonate reduction at upper mantle pressures and temperatures. Methane was formed from FeO, CaCO(3)-calcite, and water at pressures between 5 and 11 GPa and temperatures ranging from 500 degrees C to 1,500 degrees 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]  W. M. Howard,et al.  The equation of state of supercritical HF, HCl, and reactive supercritical mixtures containing the elements H, C, F, and Cl , 1999 .

[2]  B. Wood,et al.  Experimental measurements of the graphite C−O equilibrium and CO2 fugacities at high temperature and pressure , 1995 .

[3]  The evolution of multicomponent systems at high pressures: VI. The thermodynamic stability of the hydrogen–carbon system: The genesis of hydrocarbons and the origin of petroleum , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[4]  J. Horita,et al.  Abiogenic methane formation and isotopic fractionation under hydrothermal conditions , 1999, Science.

[5]  J. W. Shaner,et al.  Specific volume measurements of Cu, Mo, Pd, and Ag and calibration of the ruby R1 fluorescence pressure gauge from 0.06 to 1 Mbar , 1978 .

[6]  Polian,et al.  Optical studies of methane under high pressure. , 1987, Physical review. B, Condensed matter.

[7]  Martin Schoell,et al.  300-Myr-old magmatic CO2 in natural gas reservoirs of the west Texas Permian basin , 2001, Nature.

[8]  I. Chou,et al.  A new diamond anvil cell for hydrothermal studies to 2.5 GPa and from −190 to 1200 °C , 1993 .

[9]  S. Jakobsson,et al.  Crystal-liquid experiments in the presence of a C-O-H fluid buffered by graphite+iron+wustite : experimental method and near-liquidus relations in basanite , 1986 .

[10]  H. Mao,et al.  Two-dimensional energy dispersive x-ray diffraction at high pressures and temperatures , 2001 .

[11]  J. Holloway Graphite-CH4-H2O-CO2 equilibria at low-grade metamorphic conditions , 1984 .

[12]  Thomas Gold,et al.  The deep, hot biosphere. , 1998, Proceedings of the National Academy of Sciences of the United States of America.

[13]  F. Mauer,et al.  Raman and x‐ray investigations of ice VII to 36.0 GPa , 1982 .

[14]  B. French Some geological implications of equilibrium between graphite and a C‐H‐O gas phase at high temperatures and pressures , 1966 .

[15]  J. Ward,et al.  Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs , 2002, Nature.

[16]  W. Seyfried,et al.  Hydrocarbons in Hydrothermal Vent Fluids: The Role of Chromium-Bearing Catalysts , 2004, Science.

[17]  Jan Marten Huizenga,et al.  Thermodynamic modelling of C O H fluids , 2001 .

[18]  Zhenhao Duan,et al.  Accurate prediction of the thermodynamic properties of fluids in the system H2O–CO2–CH4–N2 up to 2000 K and 100 kbar from a corresponding states/one fluid equation of state , 2000 .

[19]  Thomas M. McCollom,et al.  Experimental constraints on the hydrothermal reactivity of organic acids and acid anions: I. Formic acid and formate , 2003 .

[20]  Laurence E. Fried,et al.  Explicit Gibbs free energy equation of state applied to the carbon phase diagram , 2000 .

[21]  F. Ree A statistical mechanical theory of chemically reacting multiphase mixtures: Application to the detonation properties of PETN , 1984 .