Abstract. An observationally constrained photochemical box model has been developed to investigate the atmospheric chemistry of iodine in the marine boundary layer, motivated by recent measurements of the iodine monoxide (IO) radical (Allan et al., this issue). Good agreement with the time series of IO measured at a midlatitude coastal station was achieved by using a reaction scheme that included recycling of iodine through marine aerosol. The strong diurnal variation in IO observed in the subtropical Atlantic was satisfactorily modeled by assuming a constant concentration of iodocarbons that photolyzed to produce roughly 1 x 10 4 iodine atoms cm '3 s -• at midday. The significance of the occurrence of IO at concentrations of up to 4 parts per trillion in the marine boundary layer was then considered from three angles. First, the iodine-catalyzed destruction of ozone was shown to be of a magnitude similar to that caused by odd-hydrogen photochemistry, with up to 13% of the available ozone destroyed per day in a marine air mass. Second, the enrichment factor of iodine in marine aerosol compared with surface seawater was predicted to increase to values of several thousand, in sensible accord with observations. Most of the enrichment should be due to the accumulation of iodate, although other iodine species may also be present, depending on the rate of aerosol recycling. Third, the denoxification of the marine boundary layer was found to be significantly enhanced as a result of aerosol uptake of IONO2, formed from the recombination of IO with NO2.
Abstract. We report measurements of the iodine monoxide (IO) radical in the marine boundary layer at three remote sites: Mace Head (Ireland), Tenerife (Canary Islands), and Cape Grim (Tasmania). IO was observed by long-path differential optical absorption spectroscopy using the A21-13/2-fitT2I-I 3/2 electronic transition between 415 and 450 nm. The daytime IO concentration at these three locations was found to vary from below the detection limit (_<0.2 parts per trillion (ppt)) to a maximum of 4 ppt, with an average of about 1 ppt. Of particular note is that the IO observed off the north coast of Tenerife, which is probably typical of the open ocean sub-tropical North Atlantic, exhibited a distinct diurnal cycle which correlated strongly with the solar actinic flux in the near UV. IO was also observed at Cape Grim to be present at much lower levels (=0.3 ppt) in westerly air from the Southern Ocean. As is shown in the companion paper (McFiggans et al., this issue), these measurements of IO are satisfactorily reproduced by a photochemical box model incorporating the recycling of iodine through marine aerosol. This model indicates that the direct iodine-catalyzed destruction of ozone in the boundary layer may well be similar to the losses caused by odd-hydrogen photochemistry and dry deposition. The significance of this work is that IO is probably present in much of the open ocean boundary layer, at levels where it may cause significant depletion of ozone.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.