Anaerobic oxidation of methane (AOM) by sulfate has been recognized as a critical process to maintain this greenhouse gas stability by limiting methane flux to the atmosphere. We show geochemical evidence for AOM in deep lake sediments and demonstrate that AOM is likely driven by iron (Fe) reduction. Pore-water profiles from Lake Kinneret (Sea of Galilee, Israel) show that this sink for methane is located below the 20-cm depth in the sediment, which is well below the depths at which nitrate and sulfate are completely exhausted, as well as below the zone of methanogenesis. Iron-dependant AOM was verified by Fe(III)-amended mesocosm studies using intact sediment cores, and native iron oxides were detectable throughout the sediments. Because anaerobic Fe(III) respiration is thermodynamically more favorable than both sulfate-dependent methanotrophy and methanogenesis, its occurrence below the zone of methane production supports the idea that reduction of sedimentary iron oxides is kinetically or biologically limited. Similar conditions are likely to prevail in other incompletely pyritized aquatic sediments, indicating that AOM with Fe(III) is an important global sink for methane.

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We use the carbon isotopic composition (δ13C) of the dissolved inorganic carbon (DIC) of pore fluids from Leg 175 of the Ocean Drilling Program (ODP) along the West African Margin to quantify rates of methane production (methanogenesis) and destruction via oxidation (methanotrophy) in deep‐sea sediments. Results from a model of diffusion and reaction in the sedimentary column show that anaerobic methane oxidation (AOM) occurs in the transition zone between the presence of sulfate and methane, and methanogenesis occurs below these depths in a narrow confined zone that ends at about 250 m below the sea‐sediments surface in all sediment profiles. Our model suggests that the rates of methanogenesis and AOM range between 6 · 10−8 and 1 · 10−10 mol cm−3 year−1 at all sites, with higher rates at sites where sulfate is depleted in shallower depths. Our AOM rates agree with those based solely on sulfate concentration profiles, but are much lower than those calculated from experiments of sulfate reduction through AOM done under laboratory conditions. At sites where the total organic carbon (TOC) is less than 5% of the total sediment, we calculate that AOM is the main pathway for sulfate reduction. We calculate that higher rates of AOM are associated with increased recrystallization rates of carbonate minerals. We do not find a correlation between methanogenesis rates and the content of carbonate or TOC in the sediments, porosity, sedimentation rate, or the C:N ratio, and the cause of lack of methanogenesis below a certain depth is not clear. There does, however, appear to be an association between the rates of methanogenesis and the location of the site in the upwelling system, suggesting that some variable such as the type of the organic matter or the nature of the microbiological community may be important.

Anaerobic oxidation of methane (AOM) was shown to reduce methane emissions by over 50% in freshwater systems, its main natural contributor to the atmosphere. In these environments iron oxides can become main agents for AOM, but the underlying mechanism for this process has remained enigmatic. By conducting anoxic slurry incubations with lake sediments amended with C-labeled methane and naturally abundant iron oxides the process was evidenced by significantC-enrichment of the dissolved inorganic carbon pool and most pronounced when poorly reactive iron minerals such as magnetite and hematite were applied. Methane incorporation into biomass was apparent by strong uptake of C into fatty acids indicative of methanotrophic bacteria, associated with increasing copy numbers of the functional methane monooxygenase pmoA gene. Archaea were not directly involved in full methane oxidation, but their crucial participation, likely being mediators in electron transfer, was indicated by specific inhibition of their activity that fully stopped iron-coupled AOM. By contrast, inhibition of sulfur cycling increasedC-methane turnover, pointing to sulfur species involvement in a competing process. Our findings suggest that the mechanism of iron-coupled AOM is accomplished by a complex microbe-mineral reaction network, being likely representative of many similar but hidden interactions sustaining life under highly reducing low energy conditions.

The competition between sulfate reducing bacteria and methanogens over common substrates has been proposed as a critical control for methane production. In this study, we examined the co-existence of methanogenesis and sulfate reduction with shared substrates over a large range of sulfate concentrations and rates of sulfate reduction in estuarine systems, where these processes are the key terminal sink for organic carbon. Incubation experiments were carried out with sediment samples from the sulfate-methane transition zone of the Yarqon (Israel) estuary with different substrates and inhibitors along a sulfate concentrations gradient from 1 to 10 mM. The results show that methanogenesis and sulfate reduction can co-exist while the microbes share substrates over the tested range of sulfate concentrations and at sulfate reduction rates up to 680 μmol L-1 day-1. Rates of methanogenesis were two orders of magnitude lower than rates of sulfate reduction in incubations with acetate and lactate, suggesting a higher affinity of sulfate reducing bacteria for the available substrates. The co-existence of both processes was also confirmed by the isotopic signatures of δ34S in the residual sulfate and that of δ13C of methane and dissolved inorganic carbon. Copy numbers of dsrA and mcrA genes supported the dominance of sulfate reduction over methanogenesis, while showing also the ability of methanogens to grow under high sulfate concentration and in the presence of active sulfate reduction.