Marine organohalogens in the atmosphere over the Atlantic and Southern Oceans

Abstract

Reactive halogen species (RHS) such as the halogen oxide radicals IO and BrO influence tropospheric oxidation processes in both polar and temperate regions. Oceanic photolabile halocarbons have been shown to be strong sources of RHS in midlatitudes. However, the global source strengths of these halocarbon precursors and the relative importance of the coastal and pelagic oceans on their concentrations are highly uncertain. Here we present atmospheric measurements of the reactive organic halogens CH3I, CH2I2, CH2ClI, CH2IBr, CHIBr2, CHBr3, CH2Br2, and CHBr2Cl made at Mace Head, Ireland, during the Particle Formation and Fate in the Coastal Environment campaign in September 1998 and at Cape Grim, Tasmania, during the Southern Ocean Atmospheric Photochemistry Experiment 2 campaign in January/February 1999. Mace Head is strongly influenced by local macroalgae, whereas Cape Grim, owing to its cliff‐top location, suffers much less impact from seaweeds. The very reactive halocarbons CH2I2, CH2IBr, and CHIBr2 observed at Mace Head were below detection limits at Cape Grim, although CH2ClI was detected at both locations. Mixing ratios of CH3I, CH2ClI, CHBr3, CHBr2Cl, and CH2Br2 at Cape Grim were on average 25–50% of those at Mace Head. Concentrations of the polybromomethanes correlated well at both sites. Using these correlations, we estimate molar source strengths of CHBr2Cl and CH2Br2 to be between 3 and 6% and between 15 and 25% of the global CHBr3 flux, respectively. These values fall within ranges estimated independently from concentration and lifetime data.