Aerosol particles clouds

In the case of S02, oxidation in the aqueous phase, present in the atmosphere in the form of aerosol particles, clouds, and fogs, is also important. Thus S02 from the gas phase dissolves in these water droplets and may be oxidized within the droplet by such species as H202, 03, 02, and free radicals. Oxidation of S02 on the surfaces of solids either present in the air or suspended in the water droplets is also possible. On the other hand, it is believed that HN03 is formed primarily by reaction (10) in the gas phase and subsequently dissolves in droplets. 

Nitrogen oxide, formed by photofragmentation of N02 or chlorine nitrate (C10N02), hydroxyl radicals and some other reactive species are also responsible for stratospheric ozone depletion. These compounds may have both natural and anthropogenic (combustion, etc.) origin. Atmospheric chemistry also takes place in aerosol particles, cloud droplets1370 and ice crystals.1371,1372... 

Table 7-2 includes most of the main gaseous constituents of the troposphere with observed concentrations. In addition to gaseous species, the condensed phases of the atmosphere (i.e. aerosol particles and clouds) contain numerous other species. The physical characteristics and transformations of the aerosol state will be discussed later in Section 7.10. The list of major gaseous species can be organized in several different ways. In the table, it is in order of decreasing concentration. We can see that there are five approximate categories based simply on concentration ... 

Condensed phase interactions can be divided roughly into two further categories chemical and physical. The latter involves all purely physical processes such as condensation of species of low volatility onto the surfaces of aerosol particles, adsorption, and absorption into liquid cloud and rainwater. Here, the interactions may be quite complex. For example, cloud droplets require a CCN, which in many instances is a particle of sulfate produced from SO2 and gas-particle conversion. If this particle is strongly acidic (as is often the case) HNO3 will not deposit on the aerosol particle rather, it will be dissolved in liquid water in clouds and rain. Thus, even though HNO3 is not very soluble in... 

Chemical interactions also occur in the condensed phases. Some of these are expected to be quite complex, e.g., the reactions of free radicals on the surfaces of or within aerosol particles. Simpler sorts of interactions also exist. Perhaps the best understood is the acid-base relationship of NH3 with strong acids in aerosol particles and in liquid water (see Chapter 16). Often, the main strong acid in the atmosphere is H2SO4, and one may consider the nature of the system consisting of H2O (liquid), NH3, H2SO4, and CO2 under realistic atmospheric conditions. Carbon dioxide is not usually important to the acidity of atmospheric liquid water (Charlson and Rodhe, 1982) the dominant effects are due to NH3 and H2SO4. The sensitivity the pH of cloud (or rainwater produced from it) to NH3 and... 

We will illustrate the necessity of including solute from CCN by a simple calculation, recalling that pH = 5.6 is the supposed equilibrium value for water in contact with 300 ppm of CO2. (That calculation will appear later.) In clean, marine air, the concentration of submicrometer aerosol particles (by far the most numerous) is small, say 0.25 pg m . It is known from measurements that the molecular form is often NH4HSO4, and we assume it is all dissolved in 0.125 g/m of liquid water in a cloud - which is typical for fair-weather marine clouds. Thus the average concentration of sulfate ion [SO4 ], mol/L, is... 

The reflection spectrum of the atmosphere is a measure of the albedo of the planet (Figure 10.4) and, despite the strong methane absorption in the red, Titan s disc looks orange principally due to scatter from the surface of dense methane-hydrocarbon clouds. Scatter from aerosol particles within the thick clouds obscures the surface of the moon although the radar analysis reveals considerable Chapman layer structure within the atmosphere and some interesting surface features. 

Sander, R. Modeling atmospheric chemistry Interactions between gas-phase species and liquid cloud/aerosol particles, Surv. Geophys., 20, 1-31, 1999. 

Gill, P. S., T. E. Graedel, and C. J. Weschler, Organic Films on Atmospheric Aerosol Particles, Fog Droplets, Cloud Droplets, Raindrops, and Snowflakes, Rev. Geophys. Space Phys., 21, 903-920 (1983). 

The possibility of such organic films being formed on aerosol particles in the atmosphere as well as on fog, cloud, and rain droplets and snowflakes has been discussed in detail by Gill and co-workers (1983). As seen from our earlier discussions on the types of organics that have been observed in both urban and nonurban aerosols, there is no question that surface-active species... 

Quinn, P. K., D. S. Covert, T. S. Bates, V. N. Kapustin, D. C. Ranisey-Bell, and L. M. Mclnnes, Dimethylsulfide Cloud Condensation Nuclei Climate System Relevant Size-Resolved Measurements of the Chemical and Physical Properties of Atmospheric Aerosol Particles, J. Geophys. Res., 98, 10411-10427 (1993). 

The finding that the heterogeneous chemistry that occurs on polar stratospheric clouds also occurs in and on liquid solutions in the form of liquid aerosol particles and droplets in the atmosphere provided a key link in understanding the effects of volcanic eruptions on stratospheric ozone in both the polar regions and midlatitudes. As discussed herein, the liquid particles formed from volcanic emissions are typically 60-80 wt% H2S04-H20, and hence the chemistry discussed in the previous section can also occur in these particles (Hofmann and Solomon, 1989). We discuss briefly in this section the contribution of volcanic emissions to the chemistry of the stratosphere and to ozone depletion on a global scale. For a brief review of this area, see McCormick et al. (1995). 

Whether or not simultaneous changes in aerosol particles and clouds have indeed altered UV at the earth s surface is not clear. For example, Herman et al. (1996) have analyzed satellite data for ozone and reflectivity from 1979 to 1992 and conclude that over this period of time there was no significant trend in the UV albedo due to changes in clouds or aerosols. 

In addition, aerosol particles have indirect effects. The most important of these is their effect on cloud properties, since clouds obviously also have major effects on climate. In addition, since heterogeneous chemistry can occur on aerosol particles (see Chapter 5), it is possible that such chemistry can alter the concentrations of other contributors to the climate system, such as the greenhouse gases. One example is the formation of N20 from reactions of HONO on the surface of aerosol particles (see Chapter 7.C). 

The fraction of the earth that is not covered by clouds, which is where increased scattering by aerosol particles is expected to be most important (see later, however, for a brief discussion of this assumption) (1 — Av) = 0.39 with an uncertainty of a factor of 1.1, where Ac is the fraction covered by clouds. 

Effect of aerosol particles on cloud drop number concentrations and size distributions Clouds and fogs are characterized by their droplet size distribution as well as their liquid water content. Fog droplets typically have radii in the range from a few /an to 30-40 /an and liquid water contents in the range of 0.05-0.1 g m" Clouds generally have droplet radii from 5 /an up to 100 /im, with typical liquid water contents of 0.05-2.5 gin"5 (e.g., see Stephens, 1978, 1979). For a description of cloud types, mechanisms of formation, and characteristics, see Wallace and Hobbs (1977), Pruppacher (1986), Cotton and Anthes (1989), Heyms-field (1993), and Pruppacher and Klett (1997). 

There are several basic physical-chemical principles involved in the ability of aerosol particles to act as CCN and hence lead to cloud formation. These are the Kelvin effect (increased vapor pressure over a curved surface) and the lowering of vapor pressure of a solvent by a nonvolatile solute (one of the colligative properties). In Box 14.2, we briefly review these and then apply them to the development of the well-known Kohler curves that determine which particles will grow into cloud droplets by condensation of water vapor and which will not. 

As we have seen in Chapter 9, there are a variety of dissolved solutes in atmospheric particles, which will lower the vapor pressure of droplets compared to that of pure water. As a result, there is great interest in the nature and fraction of water-soluble material in atmospheric particles and their size distribution (e.g., Eichel el al., 1996 Novakov and Corrigan, 1996 Hoffmann et al., 1997). This vapor pressure lowering effect, then, works in the opposite direction to the Kelvin effect, which increases the vapor pressure over the droplet. The two effects are combined in what are known as the Kohler curves, which describe whether an aerosol particle in the atmosphere will grow into a cloud droplet or not under various conditions. 

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