The Impact of Precipitation Scavenging on the Transport of Trace Gases: A 3-Dimensional Model Sensitivity Study

With the global Chemistry-Transport model MATCHsensitivity simulations were performed to determinethe degree to which especially upward transport ofgases from the earth's surface is limited byconvective and large-scale precipitation scavenging.When only dissolution of species in the liquid phaseis taken into account, mixing ratio reductions in themiddle and upper troposphere by 10% arecalculated for gases with a Henry's Law constant H of10³ mol/l/atm. The removal increases to 50% forH = 10⁴ mol/l/atm, and to 90% for H =10⁵ mol/l/atm. We also consider scavenging by theice phase, which is generally much less efficient thanby the aqueous phase. In fact, rejection of gases fromfreezing water droplets may be a source of trace gasat higher altitudes.H₂O₂ and the strong acids (H₂SO₄,HNO₃, HCl, HBr, HI) have such large solubilitiesthat they become largely removed by precipitation.When significant concentrations of these gases andsulfate aerosol exist above the liquid water domain ofthe atmosphere, they have likely been produced thereor at higher altitudes, although some could have comefrom trace gas rejection from ice particles or fromevaporating hydrometeors. Several other gases areaffected by precipitation, but not strongly enough toprevent fractional transfer to the middle and uppertroposphere: e.g., HNO₄, HNO₂ at pH 5,CH₂O, the organic acids at pH 6,CH₃SOCH₃, HOCl, HOBr, and HOI. NH₃ islargely removed by liquid phase scavenging at pH 7 and SO₂ atpH 7. At pH less thanabout 6, upward transport of SO₂ should largelydepend on the efficiency of oxidation processes in thewater droplets by O₃ and H₂O₂.Most gases have solubilities which are too low forsignificant precipitation scavenging and aqueous phaseoxidation to occur. This holds, e.g., for O₃, CO,the hydrocarbons, NO, NO₂, HCN, CH₃CN,CH₃SCH₃, CH₃O₂H, CH₃CHOandhigher aldehydes, CH₃OH and higher alcohols,peroxyacetylnitrate (PAN), CH₃COCH₃ andother ketones (note that some of these are not listedin Table I because their solubilities are below 10mol/l/atm). Especially for the short-lived gases,transfer from the boundary layer to the middle andupper troposphere is actually promoted by the enhancedupward transport that occurs in clouds.