A numerical experiment on the relative importance of H2O2 O3 in aqueous conversion of SO2 to SO42-

The importance of the three major aqueous reactions thought to be responsible for the in-cloud conversion of SO₂ to SO₄^2- was studied using the acidic deposition and oxidants model by supressing each reaction individually and all reactions simultaneously. The reactions are the oxidation of SO₂ by H₂O₂, or O₃ and catalytic oxidation by O₂ in the presence of Fe and Mn. The model simulations were 19–24 April 1981. It was found that SO₄^2- precipitation concentrations were generally more sensitive to H₂O₂ oxidation than to O₃ oxidation. The contribution of catalytic oxidation of SO₂ in the presence of Fe and Mn is insignificant everywhere and at all times. The contributions of H₂O₂ oxidation to SO₄^2- in precipitation is strongest in light precipitation areas while O₃ oxidation can be greater than H₂O₂ oxidation in heavy precipitation areas. The effect of supressing one reaction is mitigated by compensation through another mechanism. This is seem from the significant difference observed in the effects when individual suppressions were added together and when all reactions were suppressed simultaneously. From this, it is estimated that the contribution of aqueous oxidation of SO₂ to SO₄^2- in precipitation is approximately 50–80 per cent. Further simulations show that the relationship between SO₂ emissions and SO₄^2- production in the aqueous-phase through the oxidation reaction with O₃ is always non-linear in view of the pH dependence of the reaction rates.