Abstract

Methane is the second most important greenhouse gas on earth. It is produced by methanogenic archaea, which play an important role in the global carbon cycle. Three main methanogenesis pathways are known: in the hydrogenotrophic pathway H2 and carbon dioxide are used for methane production, whereas in the methylotrophic pathway small methylated carbon compounds like methanol and methylated amines are used. In the aceticlastic pathway, acetate is disproportionated to methane and carbon dioxide. However, next to these conventional substrates, further methanogenic substrates and pathways have been discovered. Several phylogenetically distinct methanogenic lineages (Methanosphaera, Methanimicrococcus, Methanomassiliicoccus, Methanonatronarchaeum) have evolved hydrogen-dependent methylotrophic methanogenesis without the ability to perform either hydrogenotrophic or methylotrophic methanogenesis. Genome analysis of the deep branching Methanonatronarchaeum revealed an interesting membrane-bound hydrogenase complex affiliated with the hardly described class 4 g of multisubunit hydrogenases possibly providing reducing equivalents for anabolism. Furthermore, methylated sulfur compounds such as methanethiol, dimethyl sulfide, and methylmercaptopropionate were described to be converted into adapted methylotrophic methanogenesis pathways of Methanosarcinales strains. Moreover, recently it has been shown that the methanogen Methermicoccus shengliensis can use methoxylated aromatic compounds in methanogenesis. Also, tertiary amines like choline (N,N,N-trimethylethanolamine) or betaine (N,N,N-trimethylglycine) have been described as substrates for methane production in Methanococcoides and Methanolobus strains. This review article will provide in-depth information on genome-guided metabolic reconstructions, physiology, and biochemistry of these unusual methanogenesis pathways.Key points• Newly discovered methanogenic substrates and pathways are reviewed for the first time.• The review provides an in-depth analysis of unusual methanogenesis pathways.• The hydrogenase complex of the deep branching Methanonatronarchaeum is analyzed.

Highlights

  • Methane is an important greenhouse gas with an atmospheric budget of about 600 Tg per year (Conrad 2009)

  • About 70% of the emitted methane is produced by methanogenic archaea (Conrad 2009) underlining the importance of methanogenesis for the global carbon cycle

  • This review comprises an overview of unconventional substrates and pathways used by methanogenic archaea

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Summary

Introduction

Methane is an important greenhouse gas with an atmospheric budget of about 600 Tg per year (Conrad 2009). The methyl group from methylated compounds like methanol is channeled into the methanogenesis pathway via transfer from the substrate to coenzyme M (CoM) (Fig. 5) It has been shown for Methanosarcina barkeri, a very versatile methanogen using hydrogenotrophic, methylotrophic, and aceticlastic methanogenesis, that this organism can convert DMS and MMPA to methane when grown on acetate (Paul and Krzycki 1996; Tallant and Krzycki 1996, 1997). For this organism, it has been demonstrated that a 30-kDa corrinoid protein (MtsB) and a 41-kDa protein (MtsA), forming a 480 kDa complex, are used for coenzyme M methylation by methylated thiols (Paul and Krzycki 1996; Tallant and Krzycki 1996, 1997). Energy conservation presumably follows what is known for methylamine or methanol dependent growth, using a membrane-bound respiratory chain involving Ech + Vho or Rnf and membranebound heterodisulfide reductase HdrDE

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