Hydrogen has had an important and evolving role in Earth's geo- and biogeochemistry, from prebiotic to modern times. On the earliest Earth, abiotic sources of H2 were likely stronger than in the present. Volcanic out-gassing and hydrothermal circulation probably occurred at several times the modern rate, due to presumably higher heat flux. The H2 component of volcanic emissions was likely buffered close to the modern value by an approximately constant mantle oxidation state since 3.9 billion years ago, and may have been higher before that, if the early mantle was more reducing. The predominantly ultramafic character of the early, undifferentiated crust could have led to increased serpentinization and release of H2 by hydrothermal circulation, as in modern ultramafic-hosted vents. At the same time, the reactive atmospheric sink for H2 was likely weaker. Collectively, these factors suggest that steady state levels of H2 in the prebiotic atmosphere were 3-4 orders of magnitude higher than at present, and possibly higher still during transient periods following the delivery of Fe and Ni by large impact events. These elevated levels had direct or indirect impacts on the redox state of the atmosphere, the radiation budget, the production of aerosol hazes, and the genesis of biochemical precursor compounds. The early abiotic cycling of H2 helped to establish the environmental and chemical context for the origins of life on Earth. The potential for H2 to serve as a source of energy and reducing power, and to afford a means of energy storage by the establishment of proton gradients, could have afforded it a highly utilitarian role in the earliest metabolic chemistry. Some origin of life theories suggest the involvement of H2 in the first energy-generating metabolism, and the widespread and deeply-branching nature of H2-utilization in the modern tree of life suggests that it was at least a very early biochemical innovation. The abiotic production of H2 via several mechanisms of water-rock interaction could have supported an early chemosynthetic biosphere. Such processes offer the continued potential for a deep, rock-hosted biosphere on Earth or other bodies in the solar system. The continued evolution of metabolic and community-level versatility among microbes led to an expanded ability to completely exploit the energy available in complex organic matter. Under the anoxic conditions that prevailed on the early Earth, this was accomplished through the linked and sequential action of several metabolic classes of organisms. By transporting electrons between cells, H2 provides a means of linking the activities of these organisms into a highly functional and interactive network. At the same time, H2 concentrations exert a powerful thermodynamic control on many aspects of metabolism and biogeochemical function in these systems. Anaerobic communities based on the consumption of organic matter continue to play an important role in global biogeochemistry even
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