A thermodynamic assessment of the potential synthesis of condensed hydrocarbons during cooling and dilution of volcanic gases

The possibility for abiotic synthesis of condensed hydrocarbons in cooling/diluting terrestrial volcanic gases has been evaluated on the basis of the consideration of metastable chemical equilibria involving gaseous CO, CO2, H-2 and H2O. The stabilities of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) have been evaluated for several typical volcanic gas compositions under various conditions for cooling/diluting of queached volcanic gas. The modeling shows that n-alkanes and PAHs have a thermodynamic potential to form metastably from H-2 and CO below similar to 250 degrees C within the stability field of graphite. Despite the predominance of CO2 in volcanic gases, synthesis of hydrocarbons from CO2 and H-2 is less favored energetically than from CO and H-2. Both low temperature and a high H/C atomic ratio in volcanic gas generally favor stability of hydrocarbons with higher H/C ratios. PAHs are thermodynamically stable at temperatures similar to 10 degrees-50 degrees C higher than large n-alkanes; however, at lower temperatures, PAHs and n-alkanes have similar stabilities and are likely to form metastable mixtures. Both the energetic drive to form hydrocarbons and possible temperatures of formation increase as the oxidation state (fO(2)) of the volcanic gases decreases and as the cooling/dilution ratios of volcanic gases increase. Synthesis of hydrocarbons is energetically more likely in cooling trapped gases than in ashcloud eruptive columns. Mechanisms for hydrocarbon formation may include Fischer-Tropsch-type synthesis catalyzed by magnetite from solid volcanic products. On the early Earth, Mars, and Jupiter's satellite Europa, several factors would have provided more favorable conditions for hydrocarbon synthesis in volcanic gases than under current terrestrial conditions and might have contributed to the production of organic compounds required for the emergence of life.