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

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Abstract. Ambient concentrations of four marine-derived halocarbons (methyl iodide, ethyl iodide, bromoform and dibromomethane) and two man-made halocarbons (trichloroethylene and tetrachloroethylene) were measured during western Pacific cruises and east and southeast Asian cruises. Ethyl iodide was detected in the atmosphere for the first time and was identified as an atmospheric iodine source compound. Bromoform concentrations were positively correlated with those of dibromomethane, and methyl iodide showed variations similar to those of ethyl iodide. However, there was no correlation between the bromocarbons and the iodocarbons. The concentrations of methyl iodide and ethyl iodide changed more markedly, possibly owing to higher rates of photodecomposition of iodocarbons.