The contribution of oceanic halocarbons to marine and free troposphere air over the tropical West Pacific

Emissions of halogenated very short lived substances (VSLS) from the tropical 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 in particular on ship and aircraft measurements of the VSLS bromoform, dibromomethane and methyl iodide and meteorological parameters 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 of 19.9 (2.80–136.91) pmol L−1 for bromoform, 5.0 (2.43–21.82) pmol L−1 for dibromomethane and 3.8 (0.55–18.83) pmol L−1 for methyl iodide in particular close to Singapore and at the coast of Borneo with high corresponding oceanic emissions of 1486 ± 1718 pmol m−2 h−1 for bromoform, 405 ± 349 pmol m−2 h−1 for dibromomethane and 433 ± 482 pmol m−2 h−1 for methyl iodide characterize this tropical region as a strong source of these compounds. Unexpectedly atmospheric mixing ratios in the MABL were relatively low with 2.08 ± 2.08 ppt for bromoform, 1.17 ± 1.17 ppt for dibromomethane and 0.39 ± 0.09 ppt for methyl iodide. We use meteorological and chemical ship and aircraft observations, FLEXPART trajectory calculations and source-loss estimates to identify the oceanic VSLS contribution to the MABL and to the FT. Our results show that a convective, well-ventilated MABL and intense convection led to the low atmospheric mixing ratios in the MABL despite the high oceanic emissions in coastal areas of the South-China and Sulu Seas. While the accumulated bromoform in the FT above the region origins almost entirely from the local South China Sea area, dibromomethane is largely advected from distant source regions. The accumulated FT mixing ratio of methyl iodide is higher than can be explained with the local oceanic or MABL contributions. Possible reasons, uncertainties and consequences of our observations and model estimates are discussed.