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ENV-01 Halogens in the marine environment
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Critical Role of Iodous Acid in Neutral Iodine Oxoacid Nucleation
Rongjie Zhang* , Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China Fangfang Ma, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China Hong-Bin Xie, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China Xu-Cheng He, Institute for Atmospheric and Earth System Research/Physics, Faculty of science, University of Helsinki, Helsinki, 00014, Finland |
Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2 in iodine oxoacid nucleation remains unclear. Herein, we probe such role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n (m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2 binds more strongly with HIO3 and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2 clusters rather than for pure HIO3 or HIO2 ones. Our calculations reveal that the strong binding results from HIO2 exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)n clusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the CLOUD experiment. This study suggests that HIO2 could facilitate the nucleation of other acids beyond HIO3 in regions where base vapors such as ammonia or amines are scarce. |
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