Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.

[1] H 2 is probably the most important substrate for terrestrial subsurface lithoautotrophic microbial communities. Abiotic H 2 generation is an essential component of subsurface ecosystems truly independent of surface photosynthesis. Here we report that H 2 concentrations in fracture water collected from deep siliclastic and volcanic rock units in the Witwatersrand Basin, South Africa, ranged up to two molar, a value far greater than observed in shallow aquifers or marine sediments. The high H 2 concentrations are consistent with that predicted by radiolytic dissociation of H 2 O during radioactive decay of U, Th, and K in the host rock and the observed He concentrations. None of the other known H 2 -generating mechanisms can account for such high H 2 abundance either because of the positive free energy imposed by the high H 2 concentration or pH or because of the absence of required mineral phases. The radiolytic H 2 is consumed by methanogens and abiotic hydrocarbon synthesis. Our calculations indicate that radiolytic H 2 production is a ubiquitous and virtually limitless source of energy for deep crustal chemolithoautotrophic ecosystems.

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