Description: Bromoform (CHBr3) is one important precursor of atmospheric reactive bromine species that are involved in ozone depletion in the troposphere and stratosphere. In the open ocean bromoform production is linked to phytoplankton that contains the enzyme bromoperoxidase. Coastal sources of bromoform are higher than open ocean sources. However, open ocean emissions are important because the transfer of tracers into higher altitude in the air, i.e. into the ozone layer, strongly depends on the location of emissions. For example, emissions in the tropics are more rapidly transported into the upper atmosphere than emissions from higher latitudes. Global spatio-temporal features of bromoform emissions are poorly constrained. Here, a global three-dimensional ocean biogeochemistry model (MPIOM-HAMOCC) is used to simulate bromoform cycling in the ocean and emissions into the atmosphere using recently published data of global atmospheric concentrations (Ziska et al., 2013) as upper boundary conditions. Our simulated surface concentrations of CHBr3 match the observations well. Simulated global annual emissions based on monthly mean model output are lower than previous estimates, including the estimate by Ziska et al. (2013), because the gas exchange reverses when less bromoform is produced in non-blooming seasons. This is the case for higher latitudes, i.e. the polar regions and northern North Atlantic. Further model experiments show that future model studies may need to distinguish different bromoform-producing phytoplankton species and reveal that the transport of CHBr3 from the coast considerably alters open ocean bromoform concentrations, in particular in the northern sub-polar and polar regions.

Description: Production pathways of the prominent volatile organic halogen compound methyl iodide (CH3I) are not fully understood. Based on observations, production of CH3I via photochemical degradation of organic material or via phytoplankton production has been proposed. Additional insights could not be gained from correlations between observed biological and environmental variables or from biogeochemical modeling to identify unambiguously the source of methyl iodide. In this study, we aim to address this question of source mechanisms with a three-dimensional global ocean general circulation model including biogeochemistry (MPIOM-HAMOCC (MPIOM - Max Planck Institute Ocean Model HAMOCC - HAMburg Ocean Carbon Cycle model)) by carrying out a series of sensitivity experiments. The simulated fields are compared with a newly available global data set. Simulated distribution patterns and emissions of CH3I differ largely for the two different production pathways. The evaluation of our model results with observations shows that, on the global scale, observed surface concentrations of CH3I can be best explained by the photochemical production pathway. Our results further emphasize that correlations between CH3I and abiotic or biotic factors do not necessarily provide meaningful insights concerning the source of origin. Overall, we find a net global annual CH3I air-sea flux that ranges between 70 and 260 Gg/yr. On the global scale, the ocean acts as a net source of methyl iodide for the atmosphere, though in some regions in boreal winter, fluxes are of the opposite direction (from the atmosphere to the ocean).