Quantitative Analysis of Coenzyme F430 in Environmental Samples: A New Diagnostic Tool for Methanogenesis and Anaerobic Methane Oxidation

Coenzyme F430 is a nickel hydrocorphinoid and is the prosthetic group of methyl–coenzyme M reductase that catalyzes the last step of the methanogenic reaction sequence and its reversed reaction for anaerobic methane oxidation by ANME. As such, function-specific compound analysis has the potential to reveal the microbial distribution and activity associated with methane production and consumption in natural environments and, in particular, in deep subsurface sediments where microbiological and geochemical techniques are restricted. Herein, we report the development of a technique for high-sensitivity analysis of F430 in environmental samples, including paddy soils, marine sediments, microbial mats, and an anaerobic groundwater. The lower detection limit of F430 analysis by liquid chromatography/mass spectrometry is 0.1 femto mol, which corresponds to 6 × 10<sup>2</sup> to 1 × 10<sup>4</sup> cells of methanogens. F430 concentrations in these natural environmental samples range from 63 × 10<sup>–6</sup> to 44 nmol g<sup>–1</sup> and are consistent with the methanogenic archaeal biomass estimated by microbiological analyses.