Anaerobic Oxidation of Methane with Sulfate: on the Reversibility of the Reactions That Are Catalyzed by Enzymes Also Involved in Methanogenesis from CO2

Anaerobic oxidation of methane (AOM) with sulfate is apparently catalyzed by an association of methanotrophic archaea (ANME) and sulfate-reducing bacteria. In many habitats, the free energy change (ΔG) available through this process is only -20 kJ/mol and therefore AOM with sulfate reduction generating life-supporting ATP is predicted to operate near thermodynamic equilibrium (ΔG=0 kJ/mol). On the basis of meta-genome sequencing and enzyme studies, it has been proposed that AOM in ANME is catalyzed by the same enzymes that catalyze CO2 reduction to CH4 in methanogenic archaea. Here, this proposal is reviewed and evaluated in terms of the process thermodynamics, kinetics, and enzyme reversibilities. Currently, there is no evidence for the presence of the gene that encodes methylene-tetrahydromethanopterin reductase in ANME, one of the central enzymes in the CO2 to CH4 pathway. However, all of the remaining enzymes do appear to be present and, with the exception of a coenzyme M-S-S-coenzyme B heterodisulfide reductase, all of these enzymes have been confirmed to catalyze reversible reactions.