Global sea-to-air flux climatology for bromoform, dibromomethane and methyl iodide

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 degrees x 1 degrees 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.

Past, present and future nutrient loads of the North Sea: causes and consequences

Comprehensive, aggregate nutrient budgets were established for two compartments of the North Sea, the shallow coastal and deeper open regions, and for three different periods, representing pre-eutrophication (∼1950), eutrophication (∼1990) and contemporary (∼2000) phases. The aim was to quantify the major budget components, to identify their sources of variability, to specify the anthropogenic components, and to draw implications for past and future policy. For all three periods, open North Sea budgets were dominated (75%) by fluxes from and to the North-East Atlantic; sediment exchange was of secondary importance (18%). For the coastal North Sea, fluxes during the eutrophication period were dominated by sediment exchange (49% of all inputs), followed by exchange with the open sea (21%), and anthropogenic inputs (19%). Between 1950 and 1990, N-loading of coastal waters increased by a factor of 1.62 and P-loading by 1.45. These loads declined after 1990. Interannual variability in Atlantic inflow was found to correspond to a variability of 11% in nutrient load to the open North Sea. Area-specific external loads of both the open and coastal North Sea were below Vollenweider-type critical loads when expressed relative to depth and flushing. External area-specific load of the coastal North Sea has declined since 1990 from 1.8 to about 1.4 g P m−2 y−1 in 2000, which is close to the estimate of 1.3 for 1950. N-load declined less, leading to an increase in N/P ratio.