Abstract. 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 CS 2 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 CO 2 uptake, which is currently impeded by the inadequate quantification of atmospheric OCS sources and sinks.

Abstract. Parameterizations of surface ocean isoprene concentrations are numerous, despite the lack of source/sink process understanding. Here we present isoprene and related field measurements in the mixed layer from the Indian Ocean and the eastern Pacific Ocean to investigate the production and consumption rates in two contrasting regions, namely oligotrophic open ocean and the coastal upwelling region. Our data show that the ability of different phytoplankton functional types (PFTs) to produce isoprene seems to be mainly influenced by light, ocean temperature, and salinity.Our field measurements also demonstrate that nutrient availability seems to have a direct influence on the isoprene production. With the help of pigment data, we calculate in-field isoprene production rates for different PFTs under varying biogeochemical and physical conditions. Using these new calculated production rates, we demonstrate that an additional significant and variable loss, besides a known chemical loss and a loss due to air-sea gas exchange, is needed to explain the measured isoprene concentration. We hypothesize that this loss, with a lifetime for isoprene between 10 and 100 days depending on the ocean region, is potentially due to degradation or consumption by bacteria.

Abstract. 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.

<p><strong>Abstract.</strong> 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-<i>a</i> concentrations to parameterize isoprene with a constant chl-<i>a</i> 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 one 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 influencing the atmospheric concentrations and, therefore, effecting the importance of marine derived isoprene as a precursor to remote marine boundary layer particle formation.</p>

Abstract. Carbonyl sulfide (OCS) and carbon disulfide (CS2) are volatile sulfur gases that are naturally formed in seawater and exchanged with the atmosphere. OCS is the most abundant sulfur gas in the atmosphere, and CS2 is its most important precursor. They have attracted increased interest due to their direct (OCS) or indirect (CS2 via oxidation to OCS) contribution to the stratospheric sulfate aerosol layer. Furthermore, OCS serves as a proxy to constrain terrestrial CO2 uptake by vegetation. Oceanic emissions of both gases contribute a major part to their atmospheric concentration. Here we present a database of previously published and unpublished (mainly shipborne) measurements in seawater and the marine boundary layer for both gases, available at https://doi.org/10.1594/PANGAEA.905430 (Lennartz et al., 2019). The database contains original measurements as well as data digitalized from figures in publications from 42 measurement campaigns, i.e., cruises or time series stations, ranging from 1982 to 2019. OCS data cover all ocean basins except for the Arctic Ocean, as well as all months of the year, while the CS2 dataset shows large gaps in spatial and temporal coverage. Concentrations are consistent across different sampling and analysis techniques for OCS. The database is intended to support the identification of global spatial and temporal patterns and to facilitate the evaluation of model simulations.