Dissolved methane concentrations in the ocean are close to equilibrium with the atmosphere. Because methane is only sparingly soluble in seawater, measuring it without contamination is challenging for samples collected and processed in the presence of air. Several methods for analyzing dissolved methane are described in the literature, yet none has conducted a thorough assessment of the method yield, contamination issues during collection, transport and storage, and the effect of temperature changes and preservative. Previous extraction methods transfer methane from water to gas by either a "sparge and trap" or a "headspace equilibration" technique. The gas is then analyzed for methane by gas chromatography. Here, we revisit the headspace equilibration technique and describe a simple, inexpensive, and reliable method to measure methane in fresh and seawater, regardless of concentration. Within the range of concentrations typically found in surface seawaters (2-1000 nmol L -1 ), the yield of the method nears 100% of what is expected from solubility calculation following the addition of known amount of methane. In addition to being sensitive (detection limit of 0.1 ppmv, or 0.74 nmol L -1 ), this method requires less than 10 min per sample, and does not use highly toxic chemicals. It can be conducted with minimum materials and does not require the use of a gas chromatograph at the collection site. It can therefore be used in various remote working environments and conditions.

Continued warming of the Arctic Ocean in coming decades is projected to trigger the release of teragrams (1 Tg = 10 tons) of methane from thawing subsea permafrost on shallow continental shelves and dissociation of methane hydrate on upper continental slopes. On the shallow shelves (<100 m water depth), methane released from the seafloor may reach the atmosphere and potentially amplify global warming. On the other hand, biological uptake of carbon dioxide (CO) has the potential to offset the positive warming potential of emitted methane, a process that has not received detailed consideration for these settings. Continuous sea-air gas flux data collected over a shallow ebullitive methane seep field on the Svalbard margin reveal atmospheric CO uptake rates (-33,300 ± 7,900 μmol m⋅d) twice that of surrounding waters and ∼1,900 times greater than the diffusive sea-air methane efflux (17.3 ± 4.8 μmol m⋅d). The negative radiative forcing expected from this CO uptake is up to 231 times greater than the positive radiative forcing from the methane emissions. Surface water characteristics (e.g., high dissolved oxygen, high pH, and enrichment of C in CO) indicate that upwelling of cold, nutrient-rich water from near the seafloor accompanies methane emissions and stimulates CO consumption by photosynthesizing phytoplankton. These findings challenge the widely held perception that areas characterized by shallow-water methane seeps and/or strongly elevated sea-air methane flux always increase the global atmospheric greenhouse gas burden.

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Large-scale climatic forcing is impacting oceanic biogeochemical cycles and is expected to influence the watercolumn distribution of trace gases, including methane and nitrous oxide. Our ability as a scientific community to evaluate changes in the water-column inventories of methane and nitrous oxide depends largely on our capacity to obtain robust and accurate concentration measurements that can be validated across different laboratory groups. This study represents the first formal international intercomparison of oceanic methane and nitrous oxide measurements whereby participating laboratories received batches of seawater samples from the subtropical Pacific Ocean and the Baltic Sea. Additionally, compressed gas standards from the same calibration scale were distributed to the majority of participating laboratories to improve the analytical accuracy of the gas measurements. The computations used by each laboratory toPublished by Copernicus Publications on behalf of the European Geosciences Union. 5892 S. T. Wilson et al.: An intercomparison of oceanic methane and nitrous oxide measurements derive the dissolved gas concentrations were also evaluated for inconsistencies (e.g., pressure and temperature corrections, solubility constants). The results from the intercomparison and intercalibration provided invaluable insights into methane and nitrous oxide measurements. It was observed that analyses of seawater samples with the lowest concentrations of methane and nitrous oxide had the lowest precisions. In comparison, while the analytical precision for samples with the highest concentrations of trace gases was better, the variability between the different laboratories was higher: 36 % for methane and 27 % for nitrous oxide. In addition, the comparison of different batches of seawater samples with methane and nitrous oxide concentrations that ranged over an order of magnitude revealed the ramifications of different calibration procedures for each trace gas. Finally, this study builds upon the intercomparison results to develop recommendations for improving oceanic methane and nitrous oxide measurements, with the aim of precluding future analytical discrepancies between laboratories.