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Wet removal of highly soluble gases
Authors:Peter Brimblecombe  G A Dawson
Institution:(1) Institute of Atmospheric Physics, The University of Arizona, 85721 Tucson, AZ, U.S.A.;(2) Present address: The School of Environmental Sciences, University of East Anglia, NR4 7TJ Norwich, Norfolk, U.K.
Abstract:Partition, not kinetics, ultimately determines the concentration of highly soluble gases in cloud droplets. Partition equations are formulated and applied to idealized air-mass thunderclouds and precipitating stratus. Contribution to aqueous concentrations from sub-cloud scavenging of highly soluble gases is estimated at between 10 and 20% under relatively unpolluted conditions. Data indicate that evaporation can produce enhancements in concentration of as much as a factor of 3. The calculations give large-scale mean coefficients of wet removal of highly soluble gases of about 2.8×10-6 s-1 (4-day residence time) for air-mass thunderclouds and precipitating stratus. Removal is so effective that the mean scale heights of these gases should be decreased to 2 km or less. The criterion of high solubility in this paper is that K H (Henry's Law coefficient) > 105 mol l-1 atm-1. Gases that are effectively highly soluble include HCl, HNO3, H2SO4, H2O2, NH3 in acid droplets, SO2 in oxidizing droplets (and probably some light amines and sulfonic acids), but not SO2 in the absence of oxidants, nor HCHO. A variation of removal coefficient and scale height with solubility is presented. A comparison of atmospheric NH3 concentrations deduced from rain NH4 + and measured directly gives reasonable agreement.
Keywords:Wet removal  soluble gases  acid rain  ammonia  Henry's Law  rainout  residence time  scavenging  vertical distribution
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