Nighttime atmospheric chemistry of iodine

Abstract

Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO+HOI→IO+HNO is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260-300K and at a pressure of 1000 hPa to be k.T ) =2.7×10 (300 K/T) cm molecule s. This reaction is included in two atmospheric models, along with the known reaction between I and NO, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I, which results in the enhancement of more than 25% of nighttime ocean emissions of HOI+I and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have a considerable, so far unrecognized, impact on the reduction of the NO radical levels in the marine boundary layer (MBL) and hence upon the nocturnal oxidizing capacity of the marine atmosphere. The effect of this is exemplified by the indirect effect on dimethyl sulfide (DMS) oxidation.