Sulfur oxidation in the troposphere

(O)
H2S, SO2 > H2SO4
Annual Fluxes
Sulfur sources
(Tg S y-1)

fossil fuel combustion:

67
biomass burining:
2.5

total anthropogenic
69.5
biogenic reduced sulfur (land)
0.35
biogenic reduced sulfur (ocean)
17
volcanic emissions
7.5

total natural
24.9

Oxidation of SO2 to sulfuric acid:

1. Dry air mechanism (clear sky conditions):

2. Aqueous-phase mechanism (humid conditions):

a. dissolution of SO2 into cloud water droplets:
SO2(g) + H2O

H2SO3(aq)

b. SO2 oxidation:
reaction with H2O2(aq):
H2SO3 + H2O2(aq) > H2O + SO42- + 2H+

reaction with O3(aq):

k1
HSO3- + O3(aq) > O2 + SO42- + H+

SO3

2-

k2
+ O3(aq) > O2 + SO42-

total rate = k1[HSO3-][O3(aq)] + k2[SO32-][O3(aq)]

By reaction with HSO3- only:
rate = k1[HSO3-][O3(aq)]

H2SO3

H+ + HSO3-

[HSO3-][H+]
Ka1 =
[H2SO3]
[HSO3-] = Ka1 [H2SO3]/[H+]
rate = k1 (Ka1 [H2SO3] / [H+]) [O3(aq)]
rate = k1 (Ka1 pSO2(g) KH-SO2 / [H+]) pO3(g)KH-O3

By reaction with SO32- only:

HSO3-

rate = k2[SO32-][O3(aq)]
H+ + SO32-

total SO2 oxidation rate by reaction with O3:

rate = k1[HSO3-][O3(aq)] + k2[SO32-][O3(aq)]
rate = {k1 (Ka1 pSO2(g) KH-SO2 / [H+])
+ k2 (Ka2 Ka1 pSO2(g) KH-SO2 / [H+]2)} pO3(g)KH-O3

SO2(g)

H2SO3(aq)

O3(g)

O3(aq)

H2SO3

HSO3- + H+

moderately fast

very fast

(O)
SO2 > H2SO4

slow