We collected Arctic Ocean water column samples for methane (CH4) and nitrous oxide (N2O) analysis on three separate cruises in the summer and fall of 2015, covering a ∼10,000 km transect from the Bering Sea to Baffin Bay. This provided a three‐dimensional view of CH4 and N2O distributions across contrasting hydrographic environments, from the oligotrophic waters of the deep Canada Basin and Baffin Bay, to the productive shelves of the Bering and Chukchi Seas. Percent saturation relative to atmospheric equilibrium ranged from 30 to 800% for CH4 and 75 to 145% for N2O, with the highest concentrations of both gases occurring in the northern Chukchi Sea. Nitrogen cycling in the shelf sediments of the Bering and Chukchi Seas likely constituted the major source of N2O to the water column, and the resulting high N2O concentrations were transported across the Arctic Ocean in eastward‐flowing water masses. Methane concentrations were more spatially heterogeneous, reflecting a variety of localized inputs, including likely sources from sedimentary methanogenesis and sea ice processes. Unlike N2O, CH4 was rapidly consumed through microbial oxidation in the water column, as shown by the 13C enrichment of CH4 with decreasing concentrations. For both CH4 and N2O, sea‐air fluxes were close to neutral, indicating that our sampling region was neither a major source nor sink of these gases. Our results provide insight into the factors controlling the distribution of CH4 and N2O in the North American Arctic Ocean, and an important baseline data set against which future changes can be assessed.

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.

Abstract. Large scale climatic forcing is impacting oceanic biogeochemical cycles and is 41expected to influence the water-column distribution of trace gases including methane and nitrous 42 oxide. Our ability as a scientific community to evaluate changes in the water-column inventories 43 of methane and nitrous oxide depends largely on our capacity to obtain robust and accurate 63Biogeosciences Discuss., https://doi

Between 2015 and 2018, we collected approximately 2,000 water column measurements of methane (CH4) and nitrous oxide (N2O) concentrations in the North American Arctic Ocean during summer and early fall. We also obtained 25 measurements of CH4 and N2O concentrations in rivers along the Northwest Passage and Ellesmere Island in midsummer 2017–2019. Our results show that N2O is generated in the highly productive Bering and Chukchi Seas and transported northeastward, producing a persistent subsurface N2O peak in the Beaufort Sea. The Chukchi and Beaufort Sea sediments are a significant source of CH4 to the water column. These sedimentary sources and associated water column consumption display significant spatial gradients and interannual variability. CH4 isotope data demonstrate the importance of CH4 oxidation across the study region. We find that rivers are not a significant source of CH4 or N2O to the Arctic Ocean at the time of year sampled. The estimated annual sea‐air flux across the study region (2.3 million km2) had a median (first quartile, third quartile) of 0.009 (0.002, 0.023) Tg CH4 y−1 and −0.003 (−0.013, 0.010) Tg N y−1. These results suggest that the North American Arctic Ocean currently plays a negligible role in global CH4 and N2O budgets. Our expansive data set, with observations at many repeat stations, provides a synopsis of present‐day Arctic CH4 and N2O distributions and their range of variability, as well as a benchmark against which future climate‐dependent changes can be evaluated.

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