A variety of physical mechanisms are jointly responsible for facilitating air‐sea gas transfer through turbulent processes at the atmosphere‐ocean interface. The nature and relative importance of these mechanisms evolves with increasing wind speed. Theoretical and modeling approaches are advancing, but the limited quantity of observational data at high wind speeds hinders the assessment of these efforts. The HiWinGS project successfully measured gas transfer coefficients (k660) with coincident wave statistics under conditions with hourly mean wind speeds up to 24 m s−1 and significant wave heights to 8 m. Measurements of k660 for carbon dioxide (CO2) and dimethylsulfide (DMS) show an increasing trend with respect to 10 m neutral wind speed (U10N), following a power law relationship of the form: k660 CO2∼U10N1.68 and k660 dms∼U10N1.33. Among seven high wind speed events, CO2 transfer responded to the intensity of wave breaking, which depended on both wind speed and sea state in a complex manner, with k660 CO2 increasing as the wind sea approaches full development. A similar response is not observed for DMS. These results confirm the importance of breaking waves and bubble injection mechanisms in facilitating CO2 transfer. A modified version of the Coupled Ocean‐Atmosphere Response Experiment Gas transfer algorithm (COAREG ver. 3.5), incorporating a sea state‐dependent calculation of bubble‐mediated transfer, successfully reproduces the mean trend in observed k660 with wind speed for both gases. Significant suppression of gas transfer by large waves was not observed during HiWinGS, in contrast to results from two prior field programs.

Concurrent wavefield and turbulent flux measurements acquired during the Southern Ocean (SO) Gas Exchange (GasEx) and the High Wind Speed Gas Exchange Study (HiWinGS) projects permit evaluation of the dependence of the whitecap coverage W on wind speed, wave age, wave steepness, mean square slope, and wind-wave and breaking Reynolds numbers. The W was determined from over 600 high-frequency visible imagery recordings of 20 min each. Wave statistics were computed from in situ and remotely sensed data as well as from a WAVEWATCH III hindcast. The first shipborne estimates of W under sustained 10-m neutral wind speeds U10N of 25 m s−1 were obtained during HiWinGS. These measurements suggest that W levels off at high wind speed, not exceeding 10% when averaged over 20 min. Combining wind speed and wave height in the form of the wind-wave Reynolds number resulted in closely agreeing models for both datasets, individually and combined. These are also in good agreement with two previous studies. When expressing W in terms of wavefield statistics only or wave age, larger scatter is observed and/or there is little agreement between SO GasEx, HiWinGS, and previously published data. The wind speed–only parameterizations deduced from the SO GasEx and HiWinGS datasets agree closely and capture more of the observed W variability than Reynolds number parameterizations. However, these wind speed–only models do not agree as well with previous studies than the wind-wave Reynolds numbers.

Predicting future climate hinges on our understanding of and ability to quantify air‐sea gas transfer. The latter relies on parameterizations of the gas transfer velocity k, which represents physical mass transfer mechanisms and is usually parameterized as a nonlinear function of wind forcing. In an attempt to reduce uncertainties in k, this study explores empirical parameterizations that incorporate both wind speed and sea state dependence via wave‐wind and breaking Reynolds numbers, RH and RB. Analysis of concurrent eddy covariance gas transfer and measured wavefield statistics supplemented by wave model hindcasts shows for the first time that wave‐related Reynolds numbers collapse four open ocean data sets that have a wind speed dependence of CO2 transfer velocity ranging from lower than quadratic to cubic. Wave‐related Reynolds number and wind speed show comparable performance for parametrizing dimethyl sulfide (DMS) which, because of its higher solubility, is less affected by bubble‐mediated exchange associated with wave breaking.