Stable Isotope Approach to Assess the Production and Consumption of Methylphosphonate and Its Contribution to Oxic Methane Formation in Surface Waters

Recent studies in aquatic environments have indicated that microbial methane production is not limited to strictly anoxic conditions and is widespread in the oxic water column. Based on recent investigations proposing linkage between the microbial turnover of methylphosphonate (MPn) and the widespread methane oversaturation in surface waters, we conducted an MPn/¹³C-MPn tracer approach that combines liquid chromatography-mass spectrometry and gas chromatography-stable isotope ratio mass spectrometry to assess concentrations of the MPn tracer and its contribution to oxic methane formation. In our study, conducted during summer 2020 in the Baltic Sea, we show that MPn is a potent methanogenic substrate in the surface water. However, we found that MPn was produced within the surface and subthermocline water bodies and that its turnover was not limited to the phosphorus-stressed and cyanobacteria-rich surface water. However, our study revealed that most of the MPn was probably degraded via alternative pathways, not releasing methane. Our assessment indicates that the contribution of the MPn degradation pathway only contributed marginally to oxic methane production at the study site in the Baltic Sea and that a variety of methanogenic pathways are probably responsible for the surface-water methane enrichments.