Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr₃), dibromomethane (CH₂Br₂) and methyl iodide (CH₃I). The input of marine halogens to the stratosphere has been estimated from observations and modelling studies using low-resolution oceanic emission scenarios derived from top-down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt (Halocarbons in the Ocean and Atmosphere) database (https://halocat.geomar.de/). Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1°×1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global sea-to-air concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr⁻¹ for CHBr₃, 0.78/0.98 Gmol Br yr⁻¹ for CH₂Br₂ and 1.24/1.45 Gmol Br yr⁻¹ for CH₃I (robust fit/ordinary least squares regression techniques). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic regions. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the subtropical gyre regions. Inter-annual and seasonal variation is contained within our flux calculations for all three compounds. Compared to earlier studies, our global fluxes are at the lower end of estimates, especially for bromoform. An under-representation of coastal emissions and of extreme events in our estimate might explain the mismatch between our bottom-up emission estimate and top-down approaches

Abstract. Emissions of halogenated very-short-lived substances (VSLSs) from the oceans contribute to the atmospheric halogen budget and affect tropospheric and stratospheric ozone. Here, we investigate the contribution of natural oceanic VSLS emissions to the marine atmospheric boundary layer (MABL) and their transport into the free troposphere (FT) over the tropical West Pacific. The study concentrates on bromoform, dibromomethane and methyl iodide measured on ship and aircraft during the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) campaign in the South China and Sulu seas in November 2011. Elevated oceanic concentrations for bromoform, dibromomethane and methyl iodide of on average 19.9, 5.0 and 3.8 pmol L −1 , in particular close to Singapore and to the coast of Borneo, with high corresponding oceanic emissions of 1486, 405 and 433 pmol m −2 h −1 respectively, characterise this tropical region as a strong source of these compounds. Atmospheric mixing ratios in the MABL were unexpectedly relatively low with 2.08, 1.17 and 0.39 ppt for bromoform, dibromomethane and methyl iodide. We use meteorological and chemical ship and aircraft observations, FLEX-PART trajectory calculations and source-loss estimates to identify the oceanic VSLS contribution to the MABL and to the FT. Our results show that the well-ventilated MABL and intense convection led to the low atmospheric mixing ratios in the MABL despite the high oceanic emissions. Up to 45 % of the accumulated bromoform in the FT above the region originates from the local South China Sea area, while dibromomethane is largely advected from distant source regions and the local ocean only contributes 20 %. The accumulated methyl iodide in the FT is higher than can be explained with local contributions. Possible reasons, uncertainties and consequences of our observations and model estimates are discussed.

Abstract. We investigate the contribution of oceanic methyl iodide (CH 3 I) to the stratospheric iodine budget. Based on CH 3 I measurements from three tropical ship campaigns and the Lagrangian transport model FLEXPART, we provide a detailed analysis of CH 3 I transport from the ocean surface to the cold point in the upper tropical tropopause layer (TTL). While average oceanic emissions differ by less than 50 % from campaign to campaign, the measurements show much stronger variations within each campaign. A positive correlation between the oceanic CH 3 I emissions and the efficiency of CH 3 I troposphere-stratosphere transport has been identified for some cruise sections. The mechanism of strong horizontal surface winds triggering large emissions on the one hand and being associated with tropical convective systems, such as developing typhoons, on the other hand, could explain the identified correlations. As a result of the simultaneous occurrence of large CH 3 I emissions and strong vertical uplift, localized maximum mixing ratios of 0.6 ppt CH 3 I at the cold point have been determined for observed peak emissions during the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere)-Sonne research vessel campaign in the coastal western Pacific. The other two campaigns give considerably smaller maxima of 0.1 ppt CH 3 I in the open western Pacific and 0.03 ppt in the coastal eastern Atlantic. In order to assess the representativeness of the large local mixing ratios, we use climatological emission scenarios to derive global upper air estimates of CH 3 I abundances. The model results are compared with available upper air measurements, including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the eastern Pacific region, the location of the available measurement campaigns in the upper TTL, the comparisons give a good agreement, indicating that around 0.01 to 0.02 ppt of CH 3 I enter the stratosphere. However, other tropical regions that are subject to stronger convective activity show larger CH 3 I entrainment, e.g., 0.08 ppt in the western Pacific. Overall our model results give a tropical contribution of 0.04 ppt CH 3 I to the stratospheric iodine budget. The strong variations in the geographical distribution of CH 3 I entrainment suggest that currently available upper air measurements are not representative of global estimates and further campaigns will be necessary in order to better understand the CH 3 I contribution to stratospheric iodine.