Iodine's impact on tropospheric oxidants: a global model study in GEOS-Chem

Abstract. We present a global simulation of tropospheric iodine chemistry within the GEOS-Chem chemical transport model. This includes organic and inorganic iodine sources, standard gas-phase iodine chemistry, and simplified higher iodine oxide (I₂O_X, X = 2, 3, 4) chemistry, photolysis, deposition, and parametrized heterogeneous reactions. In comparisons with recent iodine oxide (IO) observations, the simulation shows an average bias of  ∼ +90 % with available surface observations in the marine boundary layer (outside of polar regions), and of  ∼ +73 % within the free troposphere (350 hPa  <  p  <  900 hPa) over the eastern Pacific. Iodine emissions (3.8 Tg yr⁻¹) are overwhelmingly dominated by the inorganic ocean source, with 76 % of this emission from hypoiodous acid (HOI). HOI is also found to be the dominant iodine species in terms of global tropospheric I_Y burden (contributing up to 70 %). The iodine chemistry leads to a significant global tropospheric O₃ burden decrease (9.0 %) compared to standard GEOS-Chem (v9-2). The iodine-driven O_X loss rate¹ (748 Tg O_X yr⁻¹) is due to photolysis of HOI (78 %), photolysis of OIO (21 %), and reaction between IO and BrO (1 %). Increases in global mean OH concentrations (1.8 %) by increased conversion of hydroperoxy radicals exceeds the decrease in OH primary production from the reduced O₃ concentration. We perform sensitivity studies on a range of parameters and conclude that the simulation is sensitive to choices in parametrization of heterogeneous uptake, ocean surface iodide, and I₂O_X (X = 2, 3, 4) photolysis. The new iodine chemistry combines with previously implemented bromine chemistry to yield a total bromine- and iodine-driven tropospheric O₃ burden decrease of 14.4 % compared to a simulation without iodine and bromine chemistry in the model, and a small increase in OH (1.8 %). This is a significant impact and so halogen chemistry needs to be considered in both climate and air quality models.

¹ Here O_X is defined as O₃ + NO₂ + 2NO₃ + PAN + PMN+PPN + HNO₄ + 3N₂O₅ + HNO₃ + BrO + HOBr + BrNO₂+2BrNO₃ + MPN + IO + HOI + INO₂ + 2INO₃ + 2OIO+2I₂O₂ + 3I₂O₃ + 4I₂O₄, where PAN  =  peroxyacetyl nitrate, PPN  =  peroxypropionyl nitrate, MPN  =  methyl peroxy nitrate, and MPN  =  peroxymethacryloyl nitrate.