Direct field evidence of autocatalytic iodine release from atmospheric aerosol

Significance Recycling of reactive iodine from heterogeneous processes on sea-salt aerosol was hypothesized over two decades ago to play an important role in the atmospheric cleansing capacity. However, the understanding of this mechanism has been limited to laboratory studies and has not been confirmed in the atmosphere until now. We present atmospheric measurement of gas-phase iodine interhalogen species and show that their production via heterogeneous processing on marine aerosols is remarkably fast. These observations reveal that the atmospheric recycling of atomic iodine through photolysis of iodine interhalogen species is more efficient than previously thought, which is ultimately expected to lead to higher ozone loss and faster new particle formation in the marine environment.
Reactive iodine plays a key role in determining the oxidation capacity, or cleansing capacity, of the atmosphere in addition to being implicated in the formation of new particles in the marine boundary layer. The postulation that heterogeneous cycling of reactive iodine on aerosols may significantly influence the lifetime of ozone in the troposphere not only remains poorly understood but also heretofore has never been observed or quantified in the field. Here, we report direct ambient observations of hypoiodous acid (HOI) and heterogeneous recycling of interhalogen product species (i.e., iodine monochloride [ICl] and iodine monobromide [IBr]) in a midlatitude coastal environment. Significant levels of ICl and IBr with mean daily maxima of 4.3 and 3.0 parts per trillion by volume (1-min average), respectively, have been observed throughout the campaign. We show that the heterogeneous reaction of HOI on marine aerosol and subsequent production of iodine interhalogens are much faster than previously thought. These results indicate that the fast formation of iodine interhalogens, together with their rapid photolysis, results in more efficient recycling of atomic iodine than currently considered in models. Photolysis of the observed ICl and IBr leads to a 32% increase in the daytime average of atomic iodine production rate, thereby enhancing the average daytime iodine-catalyzed ozone loss rate by 10 to 20%. Our findings provide direct field evidence that the autocatalytic mechanism of iodine release from marine aerosol is important in the atmosphere and can have significant impacts on atmospheric oxidation capacity.