Troposphere sulfate oxidation

The primary sources that are responsible for the presence of this family of compounds in the atmosphere emit NH3, N20, and NO to the troposphere, the lowest level of the atmosphere, which extends to approximately 10 km from the earth s surface. NH3 seems to undergo very little chemistry in the atmosphere except for the formation of aerosols, including ammonium nitrate and sulfates. NH3 and the aerosols are highly soluble and are thus rapidly removed by precipitation and deposition to surfaces. N20 is unreactive in the troposphere. On a time scale of decades it is transported to the stratosphere, the next higher atmospheric layer, which extends to about 50 km. Here N20 either is photodissociated or reacts with excited oxygen atoms, O (lD). The final products from these processes are primarily unreactive N2 and 02, but about 10% NO is also produced. The product NO is the principal source of reactive oxidized nitrogen species in the stratosphere. 

Based on the use of the NARCM regional model of climate and formation of the field of concentration and size distribution of aerosol, Munoz-Alpizar et al. (2003) calculated the transport, diffusion, and deposition of sulfate aerosol using an approximate model of the processes of sulfur oxidation that does not take the chemical processes in urban air into account. However, the 3-D evolution of microphysical and optical characteristics of aerosol was discussed in detail. The results of numerical modeling were compared with observational data near the surface and in the free troposphere carried out on March 2, 4, and 14, 1997. Analysis of the time series of observations at the airport in Mexico City revealed low values of visibility in the morning due to the small thickness of the ABL, and the subsequent improvement of visibility as ABL thickness increased. Estimates of visibility revealed its strong dependence on wind direction and aerosol size distribution. Calculations have shown that increased detail in size distribution presentation promotes a more reliable simulation of the coagulation processes and a more realistic size distribution characterized by the presence of the accumulation mode of aerosol with the size of particles 0.3 pm. In this case, the results of visibility calculations become more reliable, too. 

Biogenic Sulfur Emissions from the Ocean. The ocean is a source of many reduced sulfur compounds to the atmosphere. These include dimethylsulfide (DMS) (2.4.51. carbon disulfide (CS2) (28). hydrogen sulfide (H2S) (291. carbonyl sulfide (OCS) (30.311. and methyl mercaptan (CH3SH) ( ). The oxidation of DMS leads to sulfate formation. CS2 and OCS are relatively unreactive in the troposphere and are transported to the stratosphere where they undergo photochemical oxidation (22). Marine H2S and CH3SH probably contribute to sulfate formation over the remote oceans, yet the sea-air transfer of these compounds is only a few percent that of DMS (2). 

Atmospheric Oxidation of DMS. DMS reacts fairly rapidly in the atmosphere to produce either SO% which is further oxidized to sulfate, or methane sulfonate (CH3SO3 ) (Figure 1). The relative abundances of the products in the remote troposphere suggest that sulfate is the major atmospheric end product (4 ), although methane sulfonate has been identified under laboratory conditions as a dominant end product (46.47). 

Carbonyl sulfide is also the most abundant reduced sulfur gas in Earth s troposphere, but for completely different reasons. Volcanic sources of OCS are negligible by comparison with biogenic emissions, which are important sources of several reduced sulfur gases (e.g., OCS, H2S, (CH3)2S, (CH3)2S2, and CH3SH) in the terrestrial troposphere. Many of these gases are ultimately converted into sulfate aerosols in the troposphere, but OCS is mainly lost by transport into the stratosphere, where it is photochemically oxidized to SO2 and then to sulfuric acid aerosols, which form the Junge layer at —20 km in Earth s stratosphere. 

This oxidation is of third order and its reaction rate is independent of the temperature. Using reaction rate values measured under laboratory conditions and the concentrations of M and O for different levels of the atmosphere, Cadle and Powers calculated that this process can be significant only above 10 km if the S02 concentration is 1 /ig m 3 STP. The residence time of sulfur dioxide molecules is estimated to be 103 hr at an altitude of 10 km, while at 30 km the corresponding figure ranges from 5 hr to 10 hr. Hence it seems probable that this reaction is not important in the troposphere. However, it may play an important role in the formation of the stratospheric sulfate layer (Subsection 4.4.3). 

The nitrate radical (NO3) which is present in the troposphere primarily during nighttime is also a powerful oxidant, and reacts efficiently with many organic compounds (nonmethane hydrocarbons, DMS, etc.). Hydrogen peroxide (H2O2) is a major oxidant for SO2 inside water droplets, and contributes to the formation of sulfate aerosols. 

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