H2 is probably the most important substrate for terrestrial subsurface lithoautotrophic microbial communities. Abiotic H2 generation is an essential component of subsurface ecosystems truly independent of surface photosynthesis.
Here we report that H2 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 H2concentrations are consistent with that predicted by radiolytic dissociation of H2O during radioactive decay of U, Th, and K in the host rock and the observed He concentrations. None of the other known H2-generating mechanisms can account for such high H2 abundance either because of the positive free energy imposed by the high H2 concentration or pH or because of the absence of required mineral phases. The radiolytic H2 is consumed by methanogens and abiotic hydrocarbon synthesis. Our calculations indicate that radiolytic H2 production is a ubiquitous and virtually limitless source of energy for deep crustal chemolithoautotrophic ecosystems.