Energetic constraints on H2-dependent terminal electron accepting processes in anoxic environments: a review of...

Microbially mediated terminal electron accepting processes (TEAPs) to a large extent control the fate of redox reactive elements and associated reactions in anoxic soils, sediments, and aquifers. This review focuses on thermodynamic controls and regulation of H2-dependent TEAPs, case studies illustrating this concept, and the quantitative description of thermodynamic controls in modeling. Other electron transfer processes are considered where appropriate. The work reviewed shows that thermodynamics and microbial kinetics are connected near thermodynamic equilibrium. Free energy thresholds for terminal respiration are physiologically based and often near -20 kJ mol(-1), depending on the mechanism of ATP generation; more positive free energy values have been reported under "starvation conditions" for methanogenesis and lower values for TEAPs that provide more energy. H2-dependent methanogenesis and sulfate reduction are under direct thermodynamic control in soils and sediments and generally approach theoretical minimum energy thresholds. If H2 concentrations are lowered by thermodynamically more potent TEAPs, these processes are inhibited. This principle is also valid for TEAPS providing more free energy, such as denitrification and arsenate reduction, but electron donor concentration cannot be lowered so that the processes reach theoretical energy thresholds. Thermodynamics and kinetics have been integrated by combining traditional descriptions of microbial kinetics with the equilibrium constant K and reaction quotient Q of a process, taking into account process-specific threshold energies. This approach is dynamically evolving toward a general concept of microbially driven electron transfer in anoxic environments and has been used successfully in applications ranging from bioreactor regulation to groundwater and sediment biogeochemistry.