Iodine chemistry in the tropical and remote open ocean marine boundary layer

Abstract

<p>Iodine chemistry plays an essential role in controlling the radiation budget by changing various atmospheric parameters. Iodine in the atmosphere is known to cause depletion of ozone via catalytic reaction cycles. It alters the atmospheric oxidation capacity, and lead to ultrafine particle formation that acts as potential cloud condensation nuclei. The ocean is the primary source of iodine; it enters the atmosphere through fluxes of gaseous reactive iodine species. At the ocean surface, seawater iodide reacts with tropospheric ozone (gas) to form inorganic iodine species in gaseous form. These species namely, hypoiodous acid (HOI) and molecular iodine (I<sub>2</sub>) quickly photolyse to release reactive iodine (I) in the atmosphere. This process acts as a significant sink for tropospheric ozone contributing to ~16% ozone loss throughout the troposphere. Reactive iodine released in the atmosphere undergoes the formation of iodine monoxide (IO) or higher oxides of iodine (I<sub>x</sub>O<sub>x</sub>) via self-recombination reactions. It is known that inorganic iodine fluxes (HOI and I<sub>2</sub>) contribute to 75% of the detected IO over the Atlantic Ocean. However, we did not observe this from ship-based MAX-DOAS studies between 2014-2017. At present, there are no direct observations of inorganic iodine (HOI; few for I<sub>2</sub>) and are estimated via empirical methods derived from the interfacial kinetic model by Carpenter et al. in 2013. Based on the kinetic model, estimation of HOI and I<sub>2</sub> fluxes depends on three parameters, namely, ozone concentration, surface iodide concentration, and the wind speed. This parameterisation for inorganic fluxes assumes a sea surface temperature (SST) of 293 K and has limiting wind speed conditions. Since the parameterisation conditions assumed SST of 293 K higher uncertainties due to errors in activation energy creeps in the estimation of HOI flux compared to I<sub>2</sub> as the flux of HOI is ~20 times greater than that of I<sub>2</sub>. For three consecutive expeditions in the Indian and Southern Ocean, we detected ~1 pptv of IO in the marine boundary layer. These levels are not explained by the calculated inorganic fluxes by using observed and predicted sea surface iodide concentrations. This method of iodine flux estimation is currently used in all global models, along with the MacDonald et al. 2014 iodide estimation method. Model output using these parameterisations have not been able to match the observed IO levels in the Indian and Southern Ocean region. This discrepancy suggests that the process of efflux of iodine to the atmosphere may not be fully understood, and the current parametrisation does not do justice to the observations. It also highlights that the flux of organic iodine may also play a role in observed IO levels, especially in the Indian Ocean region. A correlation of 0.7 was achieved above the 99% confidence limit for chlorophyll-a with observed IO concentration in this region. There is a need to carry more observations to improve the estimation technique of iodine sea-air flux thus improving model predictions of IO in the atmosphere.</p>