The climate active trace-gas carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere. A missing source in its atmospheric budget is currently suggested, resulting from an upward revision of the vegetation sink. Tropical oceanic emissions have been proposed to close the resulting gap in the atmospheric budget. We present a bottom-up approach including (i) new observations of OCS in surface waters of the tropical Atlantic, Pacific and Indian oceans and (ii) a further improved global box model to show that direct OCS emissions are unlikely to account for the missing source. The box model suggests an undersaturation of the surface water with respect to OCS integrated over the entire tropical ocean area and, further, global annual direct emissions of OCS well below that suggested by top-down estimates. In addition, we discuss the potential of indirect emission from CS₂ and dimethylsulfide (DMS) to account for the gap in the atmospheric budget. This bottom-up estimate of oceanic emissions has implications for using OCS as a proxy for global terrestrial CO₂ uptake, which is currently impeded by the inadequate quantification of atmospheric OCS sources and sinks.

In this study, direct measurements of the air/sea flux of acetone were made over the North Pacific Ocean. The results demonstrate that the net flux of acetone is into, rather than out of the oceans. The extrapolated global ocean uptake of 48 Tg yr⁻¹ requires a major revision of the atmospheric acetone budget. This result is consistent with a recent reevaluation of acetone photodissociation quantum yields.

A system for the shipboard measurement of air‐sea CO₂ fluxes by eddy covariance was developed and tested. The system was designed to reduce two major sources of experimental uncertainty previously reported. First, the correction for in situ water vapor fluctuations (the “Webb” correction) was reduced by 97% by drying the air sample stream. Second, motion sensitivity of the gas analyzer was reduced by using an open‐path type sensor that was converted to a closed‐path configuration to facilitate drying of the air stream. High‐quality CO₂ fluxes were obtained during 429 14 min flux intervals during two cruises in the North Atlantic. The results suggest that the gas analyzer resolved atmospheric CO₂ fluctuations well below its RMS noise level. This noise was uncorrelated with the vertical wind and therefore filtered out by the flux calculation. Using climatological data, we estimate that the techniques reported here could enable high‐quality measurements of air‐sea CO₂ flux over much of the world oceans.

Shipboard measurements of air/sea fluxes and sea surface concentrations of dimethylsulfide (DMS) were made over the tropical and midlatitude North Pacific Ocean. Atmospheric pressure chemical ionization mass spectrometry was used to measure DMS levels in ambient air and in air equilibrated with surface seawater drawn from a depth of 5 m. Air/sea fluxes were obtained using eddy covariance. Corrections and uncertainties involved in the calculation of fluxes from shipboard data are discussed. The surface ocean DMS concentrations measured during this study ranged from 1 to 10 nM, and atmospheric mixing ratios ranged from 20 to 1000 ppt. Air/sea fluxes ranged from 0.47 to 39 μmol m⁻² d⁻¹. Most of the variance in the fluxes can be accounted for by variations in sea surface concentration (37%) and wind speed (19%). Gas transfer coefficients derived from the measurements are generally consistent with those derived from deliberate inert gas tracer experiments and eddy covariance measurements of CO₂. The gas transfer coefficients exhibit wind speed dependence, but the variance in the data is sufficiently large that they do not constrain the functionality of the wind speed dependence of gas exchange.

We use isoprene and related field measurements from three different ocean data sets together with remotely sensed satellite data to model global marine isoprene emissions. We show that using monthly mean satellite-derived chl a concentrations to parameterize isoprene with a constant chl a normalized isoprene production rate underpredicts the measured oceanic isoprene concentration by a mean factor of 19 ± 12. Improving the model by using phytoplankton functional type dependent production values and by decreasing the bacterial degradation rate of isoprene in the water column results in only a slight underestimation (factor 1.7 ± 1.2). We calculate global isoprene emissions of 0.21 Tg C for 2014 using this improved model, which is twice the value calculated using the original model. Nonetheless, the sea-to-air fluxes have to be at least 1 order of magnitude higher to account for measured atmospheric isoprene mixing ratios. These findings suggest that there is at least one missing oceanic source of isoprene and, possibly, other unknown factors in the ocean or atmosphere influencing the atmospheric values. The discrepancy between calculated fluxes and atmospheric observations must be reconciled in order to fully understand the importance of marine-derived isoprene as a precursor to remote marine boundary layer particle formation.

Air/sea fluxes of dimethylsulfide (DMS) were measured by eddy correlation over the Eastern South Pacific Ocean during January 2006. The cruise track extended from Manzanillo, Mexico, along 110° W, to Punta Arenas, Chile. Bulk air and surface ocean DMS levels were also measured and gas transfer coefficients (k_DMS) were computed. Air and seawater DMS measurements were made using chemical ionization mass spectrometry (API-CIMS) and a gas/liquid membrane equilibrator. Mean surface seawater DMS concentrations were 3.8±2.2 nM and atmospheric mixing ratios were 340±370 ppt. The air/sea flux of DMS was uniformly out of the ocean, with an average value of 12±15 μmol m⁻² d⁻¹. Sea surface concentration and flux were highest around 15° S, in a region influenced by shelf waters and lowest around 25° S, in low chlorophyll gyre waters. The DMS gas transfer coefficient exhibited a linear wind speed-dependence over the wind speed range of 1 to 9 m s⁻¹. This relationship is compared with previously measured estimates of k from DMS, CO₂, and dual tracer data from the Atlantic and Pacific Ocean, and with the NOAA/COARE gas transfer model. The model generated slope of k vs. wind speed is at the low end of those observed in previous DMS field studies.