Sulfate stratospheric

Similar heterogeneous reactions also can occur, but somewhat less efticientiy, in the lower stratosphere on global sulfate clouds (ie, aerosols of sulfuric acid), which are formed by oxidation of SO2 and COS from volcanic and biological activity, respectively (80). The effect is most pronounced in the colder regions of the stratosphere at high latitudes. Indeed, the sulfate aerosols resulting from emptions of El Chicon in 1982 and Mt. Pinatubo in 1991 have been impHcated in subsequent reduced ozone concentrations (85). 

A smaller factor in ozone depletion is the rising levels of N2O in the atmosphere from combustion and the use of nitrogen-rich fertilizers, since they ate the sources of NO in the stratosphere that can destroy ozone catalyticaHy. Another concern in the depletion of ozone layer, under study by the National Aeronautics and Space Administration (NASA), is a proposed fleet of supersonic aircraft that can inject additional nitrogen oxides, as weU as sulfur dioxide and moisture, into the stratosphere via their exhaust gases (155). Although sulfate aerosols can suppress the amount of nitrogen oxides in the stratosphere... 

Heterogeneous chemistry occurring on polar stratospheric cloud particles of ice and nitric acid trihydrate has been estabUshed as a dorninant factor in the aggravated seasonal depletion of o2one observed to occur over Antarctica. Preliminary attempts have been made to parameterize this chemistry and incorporate it in models to study ozone depletion over the poles (91) as well as the potential role of sulfate particles throughout the stratosphere (92). 

There are many different types of surfaces available for reactions in the atmosphere. In the stratosphere, these include ice crystals, some containing nitric acid, liquid sulfuric acid-water mixtures, and ternary solutions of nitric and sulfuric acids and water. In the troposphere, liquid particles containing sulfate, nitrate, organics, trace metals, and carbon are common. Sea... 

Zhang, R., M.-T. Leu, and L. F. Keyser, Heterogeneous Chemistry of HONO on Liquid Sulfuric Acid A New Mechanism of Chlorine Activation on Stratospheric Sulfate Aerosols, . /. Phys. Chem., 100, 339-345 (1996). 

Figure 9.55a shows the results of single-particle analysis (see Chapter ll.B.4a) of a typical particle in the upper troposphere (Murphy et al., 1998). In the negative ion spectra, a variety of fragments due to organics are observed, along with sulfates and some halogens. In other particles, soot and minerals were also common constituents. For comparison, Fig. 9.55b shows that a typical particle in the stratosphere is primarily sulfate (see Chapter 12.C.5). 

There are several reasons for the dramatic ozone destruction (see Fig. 2.17) low temperatures may have prolonged the presence of polar stratospheric clouds, which play a key role in the ozone destruction, the polar vortex was very stable, there were increased sulfate aerosols from the 1991 Mount Pinatubo volcanic eruption, which also contribute to heterogeneous chemistry, and chlorine levels had continued to increase. These issues are treated in more detail shortly. 

Additional sulfates continue to form after the eruption as gaseous S02 is oxidized to sulfuric acid and sulfates. While we shall focus here on the effects of these sulfate particles on the heterogeneous chemistry of the stratosphere, there may be other important effects on the homogeneous chemistry as well. For example, model calculations by Bekki (1995) indicate that this oxidation of S02 by OH leads to reduced OH levels, which alters its associated chemistry. 

Although the increase in stratospheric sulfate aerosols after volcanic eruptions is dramatic, there is some evidence that these events may be superimposed on a longer term trend to increased stratospheric sulfate concentrations (Hofmann, 1990). Whether this is due to increased anthropogenic or natural sources such as COS or to an increased residual volcanic layer, i.e.,... 

There are a number of measurements documenting changes in NO and NO. in the stratosphere after the Mount Pinatubo eruption and which have been attributed to the removal of oxides of nitrogen due to reactions on aerosol particles. For example, a decrease in stratospheric NOz after the eruption followed by a return to normal levels has been reported (e.g., see Van Roozendael et al., 1997 and De Maziere et al., 1998). Similarly, NO decreases of up to 70% were reported, as well as increases in gaseous HN03 (much of that produced on the sulfate particles is released to the gas phase) (e.g., see Coffey and Mankin, 1993 Koike et al., 1993, 1994 David et al., 1994 Webster et al., 1994 and Rinsland et al., 1994). 

The chemistry in the midlatitude stratosphere follows that discussed throughout this chapter. As seen in the previous sections, the heterogeneous chemistry that was once thought to be unique to PSCs also occurs in and on the liquid solutions characteristic of sulfate particles distributed globally, with their relative importance being determined by the temperature, composition, and phase of the condensed phase. 

Jaegle, L., Y. L. Yung, G. C. Toon, B. Sen, and J.-F. Blavier, Balloon Observations of Organic and Inorganic Chlorine in the Stratosphere The Role of HCI04 Production on Sulfate Aerosols, Geophys. Res. Lett., 23, 1749-1752 (1996). 

Tabazadeh, A., O. B. Toon, and P. Hamill, Freezing Behavior of Stratospheric Sulfate Aerosols Inferred from Trajectory Studies, Geophys. Res. Lett., 22, 1725-1728 (1995). 

Tolbert, M. A., Sulfate Aerosols and Polar Stratospheric Cloud Formation, Science, 264, 527-528 (1994). 

Wilson, J. C M. R. Stolzenburg, W. E. Clark, M. Loewenstein, G. V. Ferry, K. R. Chan, and K. K. Kelly, Stratospheric Sulfate Aerosol in and near the Northern Hemisphere Polar Vortex The Morphology of the Sulfate Layer, Multimodal Size Distributions, and the Effect of Denitrification, J. Geophys. Res., 97, 7997-8013 (1992). 

Toumi et al. (1994) also suggested there is a feedback between reduced stratospheric ozone and particles in that the increased UV due to ozone depletion may increase sulfate particle formation by increasing the concentrations of tropospheric OH. 

Volcanic eruptions provide one test of the relationship between light scattering by sulfate particles and the resulting change in temperature, since they generate large concentrations of sulfate aerosol in the lower stratosphere and upper troposphere. These aerosol... 

Sulfur Compounds Ammonium sulfate Sulfuric acid 0.1 pm Mostly stratospheric 50% globally... 

The pattern and rate of exchange of stratospheric air with the mesosphere, with the troposphere, and between hemispheres is still poorly known. Within the stratosphere a complex pattern of eddy mixing and mean motions governs the redistribution of trace constituents. In the lower stratosphere the adsorption or attachment of trace constituents to natural sulfate particles influences their subsequent transport. Some main features in stratospheric transport processes based on tracer studies are reviewed here. 

As Martell has pointed out (30), in the region of the stratospheric large particle layer near 18-20 km. altitude, radioactive aerosol particles become attached to natural sulfate particles in the size range of about 0.1-0.4 jumeter radius. Subsequent upward transport of the radioactive aerosols is opposed by gravitational sedimentation. This combination of processes affords an explanation for the observed accumulation of 210Pb near 20 km. in the tropical stratosphere (2). At higher latitudes where slow mean motions are directed poleward and downward, no such accumulation is possible. 

The tungsten tracer observations and the excess -1(,Pb in the tropical atmosphere are explained by the competing influence of sedimentation, slow mean motions, and eddy mixing. Radioactive aerosols in the lower stratosphere become attached to the natural sulfate particles which are of sufficient size and density to oppose upward transport to levels much above 20-25 km. (30). The coefficient of meridional eddy mixing appears to increase with latitude near the equator (29), with little seasonal change (33). At higher latitudes the rate of poleward transport exhibits large seasonal variations, with a maximum in winter (33). 

CFCs) and halons over the next decade, as mandated by the Montreal Protocol for the Protection of the Ozone Layer, will affect the chlorine burden of the stratosphere. Hydrochlorofluorocarbons (HCFCs) can be used as substitutes for the CFCs for a few decades without having a substantial impact on the chlorine burden of the stratosphere because they are primarily destroyed in the troposphere by reactions with OH before they are able to deliver the chlorine to the stratosphere. The elimination of CFCs and the temporary use of HCFCs into the early part of the next century must be carefully orchestrated to minimize the peak chlorine loading and promote the most rapid reduction of the chlorine burden of the stratosphere (56, 87). Another issue is the effects that perturbations to the reactive nitrogen abundances will have on the abundances of reactive chlorine. A better understanding and clarification of the direct heterogeneous conversions of chlorine species on both PSCs and sulfate aerosols are also needed. 

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