Abstract. Shipboard measurements of eddy covariance dimethylsulfide (DMS) air–sea fluxes and seawater concentration were carried out in the North Atlantic bloom region in June/July 2011. Gas transfer coefficients (k660) show a linear dependence on mean horizontal wind speed at wind speeds up to 11 m s−1. At higher wind speeds the relationship between k660 and wind speed weakens. At high winds, measured DMS fluxes were lower than predicted based on the linear relationship between wind speed and interfacial stress extrapolated from low to intermediate wind speeds. In contrast, the transfer coefficient for sensible heat did not exhibit this effect. The apparent suppression of air–sea gas flux at higher wind speeds appears to be related to sea state, as determined from shipboard wave measurements. These observations are consistent with the idea that long waves suppress near-surface water-side turbulence, and decrease interfacial gas transfer. This effect may be more easily observed for DMS than for less soluble gases, such as CO2, because the air–sea exchange of DMS is controlled by interfacial rather than bubble-mediated gas transfer under high wind speed conditions.

Abstract. Air–sea dimethylsulfide (DMS) fluxes and bulk air–sea gradients were measured over the Southern Ocean in February–March 2012 during the Surface Ocean Aerosol Production (SOAP) study. The cruise encountered three distinct phytoplankton bloom regions, consisting of two blooms with moderate DMS levels, and a high biomass, dinoflagellate-dominated bloom with high seawater DMS levels (> 15 nM). Gas transfer coefficients were considerably scattered at wind speeds above 5 m s−1. Bin averaging the data resulted in a linear relationship between wind speed and mean gas transfer velocity consistent with that previously observed. However, the wind-speed-binned gas transfer data distribution at all wind speeds is positively skewed. The flux and seawater DMS distributions were also positively skewed, which suggests that eddy covariance-derived gas transfer velocities are consistently influenced by additional, log-normal noise. A flux footprint analysis was conducted during a transect into the prevailing wind and through elevated DMS levels in the dinoflagellate bloom. Accounting for the temporal/spatial separation between flux and seawater concentration significantly reduces the scatter in computed transfer velocity. The SOAP gas transfer velocity data show no obvious modification of the gas transfer–wind speed relationship by biological activity or waves. This study highlights the challenges associated with eddy covariance gas transfer measurements in biologically active and heterogeneous bloom environments.

Acetone is one of the most abundant oxygenated volatile organic compounds (VOCs) in the atmosphere. The oceans impose a strong control on atmospheric acetone, yet the oceanic fluxes of acetone remain poorly constrained. In this work, the global budget of acetone is evaluated using two global models: CAM‐chem and GEOS‐Chem. CAM‐chem uses an online air‐sea exchange framework to calculate the bidirectional oceanic acetone fluxes, which is coupled to a data‐oriented machine‐learning approach. The machine‐learning algorithm is trained using a global suite of seawater acetone measurements. GEOS‐Chem uses a fixed surface seawater concentration of acetone to calculate the oceanic fluxes. Both model simulations are compared to airborne observations from a recent global‐scale, multiseasonal campaign, the NASA Atmospheric Tomography Mission (ATom). We find that both CAM‐chem and GEOS‐Chem capture the measured acetone vertical distributions in the remote atmosphere reasonably well. The combined observational and modeling analysis suggests that (i) the ocean strongly regulates the atmospheric budget of acetone. The tropical and subtropical oceans are mostly a net source of acetone, while the high‐latitude oceans are a net sink. (ii) CMIP6 anthropogenic emission inventory may underestimate acetone and/or its precursors in the Northern Hemisphere. (iii) The MEGAN biogenic emissions model may overestimate acetone and/or its precursors, and/or the biogenic oxidation mechanisms may overestimate the acetone yields. (iv) The models consistently overestimate acetone in the upper troposphere‐lower stratosphere over the Southern Ocean in austral winter. (v) Acetone contributes up to 30–40% of hydroxyl radical production in the tropical upper troposphere/lower stratosphere.

Shipboard measurements of eddy covariance DMS air/sea fluxes and seawater concentration were carried out in the North Atlantic bloom region in June/July 2011. Gas transfer coefficients (k₆₆₀) show a linear dependence on mean horizontal wind speed at wind speeds up to 11 m s⁻¹. At higher wind speeds the relationship between k₆₆₀ and wind speed weakens. At high winds, measured DMS fluxes were lower than predicted based on the linear relationship between wind speed and interfacial stress extrapolated from low to intermediate wind speeds. In contrast, the transfer coefficient for sensible heat did not exhibit this effect. The apparent suppression of air/sea gas flux at higher wind speeds appears to be related to sea state, as determined from shipboard wave measurements. These observations are consistent with the idea that long waves suppress near surface water side turbulence, and decrease interfacial gas transfer. This effect may be more easily observed for DMS than for less soluble gases, such as CO₂, because the air/sea exchange of DMS is controlled by interfacial rather than bubble-mediated gas transfer under high wind speed conditions

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Abstract. Deposition to the sea surface is a major atmospheric loss pathway for many important trace gases, such as sulfur dioxide, (SO 2 ). The air/sea transfer of SO 2 is controlled entirely on the atmospheric side of the air/sea interface due to high effective solubility and other physical/chemical properties. There have been few direct field measurements of such fluxes due to the challenges associated with making fast response measurements of highly soluble trace gases at very low ambient levels.In this study, we report direct eddy covariance air/sea flux measurements of SO 2 , sensible heat, water vapor, and momentum. 5The measurements were made over shallow coastal waters from the Scripps Pier, La Jolla, CA using negative ion chemical ionization mass spectrometry as the SO 2 sensor. The observed transfer velocities for SO 2 , sensible heat, water vapor, and momentum and their wind speed-dependences indicate that SO 2 fluxes can be reliably measured using this approach. As expected, the transfer velocities for SO 2 , sensible heat, and water vapor are smaller than that for momentum, demonstrating the contribution of molecular diffusion to the overall air-side resistance to gas transfer. Furthermore, transfer velocities of SO 2 10 were smaller than those of sensible heat and water vapor when observed simultaneously. This result is attributable to diffusive behavior in the interfacial layer of the air/sea interface.Copyright statement.