Oxic lake surface waters are frequently oversaturated with methane (CH4). The contribution to the global CH4 cycle is significant, thus leading to an increasing number of studies and stimulating debates. Here we show, using a mass balance, on a temperate, mesotrophic lake, that ~90% of CH4 emissions to the atmosphere is due to CH4 produced within the oxic surface mixed layer (SML) during the stratified period, while the often observed CH4 maximum at the thermocline represents only a physically driven accumulation. Negligible surface CH4 oxidation suggests that the produced 110 ± 60 nmol CH4 L−1 d−1 efficiently escapes to the atmosphere. Stable carbon isotope ratios indicate that CH4 in the SML is distinct from sedimentary CH4 production, suggesting alternative pathways and precursors. Our approach reveals CH4 production in the epilimnion that is currently overlooked, and that research on possible mechanisms behind the methane paradox should additionally focus on the lake surface layer.

Recent discovery of oxic methane production in sea and lake waters, as well as wetlands, demands re-thinking of the global methane cycle and re-assessment of the contribution of oxic waters to atmospheric methane emission. Here we analysed system-wide sources and sinks of surface-water methane in a temperate lake. Using a mass balance analysis, we show that internal methane production in well-oxygenated surface water is an important source for surface-water methane during the stratified period. Combining our results and literature reports, oxic methane contribution to emission follows a predictive function of littoral sediment area and surface mixed layer volume. The contribution of oxic methane source(s) is predicted to increase with lake size, accounting for the majority (>50%) of surface methane emission for lakes with surface areas >1 km 2 .

Methane (CH4), a potent greenhouse gas, is produced in and emitted from lakes at globally significant rates. The drivers controlling the proportion of produced CH4 that will reach the atmosphere, however, are still not well understood. We sampled a small eutrophic lake (Soppensee, Switzerland) in 2016–2017 for CH4 concentrations profiles and emissions, combined with water column hydrodynamics to investigate the fate of CH4 produced in hypolimnetic sediments. Using a mass balance approach for the periods between April and October of both years, net CH4 production rates in hypolimnetic sediments ranged between 11.4 and 17.7 mmol m−2 d−1, of which 66–88% was stored in the hypolimnion, 13–27% was diffused to the epilimnion, and 6–7% left the sediments via ebullition. Combining these results with a process‐based model we show that water column turbulent diffusivity (K z) had a major influence on the fate of produced CH4 in the sediments, where higher K z values potentially lead to greater proportion being oxidized and lower K z lead to a greater proportion being stored. During fall when the water column mixes, we found that a greater proportion of stored CH4 is emitted if the lake mixes rapidly, whereas a greater proportion will be oxidized if the water column mixes more gradually. This work highlights the central role of lake hydrodynamics in regulating CH4 dynamics and further suggests the potential for CH4 production and emissions to be sensitive to climate‐driven alterations in lake mixing regimes and stratification.

[1] Eddy correlation (EC) measurements in the benthic boundary layer (BBL) allow estimating benthic O 2 uptake from a point distant to the sediment surface. This noninvasive approach has clear advantages as it does not disturb natural hydrodynamic conditions, integrates the flux over a large foot-print area and allows many repetitive flux measurements. A drawback is, however, that the measured flux in the bottom water is not necessarily equal to the flux across the sediment-water interface. A fundamental assumption of the EC technique is that mean current velocities and mean O 2 concentrations in the bottom water are in steady state, which is seldom the case in highly dynamic environments like coastal waters. Therefore, it is of great importance to estimate the error introduced by nonsteady state conditions. We investigated two cases of transient conditions. First, the case of transient O 2 concentrations was examined using the theory of shear flow dispersion.

Atmospheric methane (CH 4 ) concentrations have more than doubled in the past~250 yr, although the sources of this potent greenhouse gas remain poorly constrained. Freshwaters contribute~20% of natural CH 4 emissions, about half attributed to ebullition. Estimates remain uncertain as ebullition is stochastic, making measurements difficult, time consuming, and costly with current methods (e.g., floating chambers, funnel gas traps, and hydroacoustics). We present a novel approach to quantify basin-wide hypolimnetic CH 4 fluxes at the sediment level based on measurements of bubble gas content and modeling of dissolved pore-water gases. We show that the relative ebullition flux pathway can be resolved by knowledge of only bubble gas content. As sediment CH 4 production, diffusion, and ebullition are interrelated, the addition of a second observation allows closing the entire sediment CH 4 balance. Such measurements could include bubble formation depth, sediment diffusive fluxes, ebullition, sediment CH 4 production, or the hypolimnetic CH 4 mass balance. The measurement of bubble gas content is particularly useful for identifying local ebullitive hotspots and integrating spatial heterogeneity of CH 4 fluxes. Our results further revealed the crucial effect of water column depth, production rates, and hypolimnetic dissolved CH 4 concentrations on sediment CH 4 dynamics. Although we apply the model to cohesive sediments in an anoxic hypolimnion, the model can be applied to shallow, oxic settings by altering the CH 4 production rate curve to account for oxidation. Utilizing our approach will provide a deeper understanding of in-lake CH 4 budgets, and thus improve CH 4 emission estimates from inland freshwaters at the regional and global scales.