In stratospheric aerosols

If ions were, in fact, involved in stratospheric aerosol formation, a physical link between solar activity and the stratospheric aerosol layer may exist [39]. 

Various trace gases (Table 3 have already been detected using PACIMS. Particularly interesting ones are H2SO4 and HSO3, as they are involved in stratospheric aerosol formation (Fig. 10). 

Volcanic injection of large quantities of sulfate aerosol into the stratosphere offers the opportunity to examine the sensitivity of ozone depletion and species concentrations to a major perturbation in aerosol surface area (Hofmann and Solomon 1989 Johnston et al. 1992 Prather 1992 Mills et al. 1993). The increase in stratospheric aerosol surface area resulting from a major volcanic eruption can lead to profound effects on C10 -induced ozone depletion chemistry. Because the heterogeneous reaction of N205 and water on the surface of stratospheric aerosols effectively removes N02 from the active reaction system, less N02 is available to react with CIO to form the reservoir species C10N02. As a result, more CIO is present in active CIO cycles. Therefore an increase in stratospheric aerosol surface area, as from a volcanic eruption, can serve to make the chlorine present more effective at ozone depletion, even if no increases in chlorine are occurring. 

Denmark 1.5 days after the explosion. Air samples collected at Roskilde, Denmark on April 27-28, contained a mean air concentration of 241Am of 5.2 pBq/m3 (0.14 fCi/m3). In May 1986, the mean concentration was 11 pBq/m3 (0.30 fCi/m3) (Aarkrog 1988). Whereas debris from nuclear weapons testing is injected into the stratosphere, debris from Chernobyl was injected into the troposphere. As the mean residence time in the troposphere is 20-40 days, it would appear that the fallout would have decreased to very low levels by the end of 1986. However, from the levels of other radioactive elements, this was not the case. Sequential extraction studies were performed on aerosols collected in Lithuania after dust storms in September 1992 carried radioactive aerosols to the region from contaminated areas of the Ukraine and Belarus. The fraction distribution of241 Am in the aerosol samples was approximately (fraction, percent) organically-bound, 18% oxide-bound, 10% acid-soluble, 36% and residual, 32% (Lujaniene et al. 1999). Very little americium was found in the more readily extractable exchangeable and water soluble and specifically adsorbed fractions. 

CFCs. All "nonessential" uses of CFCs in aerosol propellents were banned in 1978—the first and only major control action under TSCA not specifically mandated by the statute. This action may have helped to reduce the future incidence of skin cancer by diminishing CFCs destructive effects on stratospheric ozone. Making appropriate assumptions about rates of ozone depletion and extrapolating from current disease rates, one could estimate a range of cancers avoided because of this prohibition. However, any health benefit due to the ban on aerosol CFC uses may be masked by the continued increase in non-aerosol uses. 

The chlorofluorocarbon compounds of methane and ethane are collectively known as freons. They are extremely stable, unreactlve, non-toxic, non-corrosive and easily liquefiable gases. Freon 12 (CCI2F2) Is one of the most common freons In Industrial use. It Is manufactured from tetrachloromethane by Swarts reaction. These are usually produced for aerosol propellants, refrigeration and air conditioning purposes. By 1974, total freon production In the world was about 2 billion pounds annually. Most freon, even that used In refrigeration, eventually makes Its way Into the atmosphere where It diffuses unchanged Into the stratosphere. In stratosphere, freon Is able to Initiate radical chain reactions that can upset the natural ozone balance (Unit 14, Class XI). 

Abstract Heterogeneous chemical reactions at the surface of ice and other stratospheric aerosols are now appreciated to play a critical role in atmospheric ozone depletion. A brief summary of our theoretical work on the reaction of chlorine nitrate and hydrogen chloride on ice is given to highlight the characteristics of such heterogeneous mechanisms and to emphasize the special challenges involved in the realistic theoretical treatment of such reactions. 

These aerosols play a major role in stratospheric chemistry by directly providing surfaces for heterogeneous chemistry (discussed in more detail later) as well as serving as nuclei for polar stratospheric cloud formation. Figure 12.21 schematically shows the processes believed to be involved in PSC formation. The thermodynamic stability of the various possible forms of PSCs at stratospherically relevant temperatures and the transitions between them are discussed in detail by Koop et al. (1997a). 

Figure 12.28 shows the particle surface area size distribution before the Mount Pinatubo eruption (Fig. 12.28a), inside the main aerosol layer several months after the eruption (Fig. 12.28b), and almost two years after the eruption (Fig. 12.28c). (See Chapter 9.A.2 for a description of how particle size distributions are normally characterized.) Prior to the eruption, the surface area distribution is unimodal, with typical radii of 0.05-0.09 /xrn and a number concentration of l-20 particles cm 1. In the main stratospheric aerosol layer formed after the eruption, the distribution is bimodal...

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). 

Measurements of the solubility of HBr in sulfuric acid at 220 K gave Henry s law constants from 8.5 X 103 M atm-1 for 72 wt% H2S04 to 1.5 X 107 M atm-1 for 54 wt% H2S04 (Williams et al., 1995 Abbatt, 1995). Application of these values to stratospheric aerosol particles typical of midlatitude conditions gives very small equilibrium concentrations of dissolved HBr i.e., most of the HBr will remain in the gas phase. 

Stone, R. S., J. R. Key, and E. G. Duton, Properties and Decay of Stratospheric Aerosols in the Arctic Following the 1991 Eruptions of Mount Pinatubo, Geophys. Res. Lett., 20, 2359-2362 (1993). Strand, A, and 0. Hov, The Impact of Man-Made and Natural NOA. Emissions on Upper Tropospheric Ozone A Two-Dimensional Model Study, Atmos. Enriron., 30, 1291-1303 (1996). 

Wilson, J. C., The Stratospheric Aerosol and Its Impact on Stratospheric Chemistry, in Perspectives in Environmental Chemistry (D. L. Macalady, Ed.), pp. 344-368, Oxford Univ. Press, New York, 1998. 

Zawodny, J. M., and M. P. McCormick, Stratospheric Aerosol and Gas Experiment II Measurements of the Quasi-Biennial Oscillations in Ozone and Nitrogen Dioxide, J. Geophys. Res., 96, 9371-9377 (1991). 

At Arosa, Switzerland, where there are records back to 1926 (the longest data record available), the trend in annual mean 03 has been determined to be —(2.3 + 0.6)% per decade. When contributions due to the solar cycle, temperature, and stratospheric aerosol concentrations are taken into account, the trend is —(1.9 0.6)% per decade. However, the total measured column 03 includes both stratospheric and a smaller tropospheric contribution, and the latter has been increasing (see Chapters 14 and 16). This would tend to mask part of a decrease in stratospheric 03. Applying an estimate of the increase in tropospheric ozone gives a trend in stratospheric 03 of - (3.0 + 0.6)% per decade at Arosa (Staehelin et al., 1998b). 

Cunnold, D. M H. Wang, W. P. Chu, and L. Froidevaux, Comparisons between Stratospheric Aerosol and Gas Experiment II and Microwave Limb Sounder Ozone Measurements and Aliasing of SAGE II Ozone Trends in the Lower Stratosphere, J. Geophys. Res., 101, 10061-10075 (1996). 

Grams, G. W., 1981. In-situ measurements of scattering phase functions of stratospheric aerosol particles in Alaska during July 1979, Geophys. Res. Lett., 8, 13-14. 

Mechanisms and rates of transport of nuclear test debris in the upper and lower atmosphere are considered. For the lower thermosphere vertical eddy diffusion coefficients of 3-6 X 106 cm.2 sec. 1 are estimated from twilight lithium enhancement observations. Radiochemical evidence for samples from 23 to 37 km. altitude at 31° N indicate pole-ward mean motion in this layer. Large increases in stratospheric debris in the southern hemisphere in 1963 and 1964 are attributed to debris from Soviet tests, transported via the mesosphere and the Antarctic stratosphere. Most of the carbon-14 remains behind in the Arctic stratosphere. 210Bi/ 210Pb ratios indicate aerosol residence times of only a few days at tropospheric levels and only several weeks in the lower stratosphere. Implications for the inventory and distribution of radioactive fallout are discussed. 

The atmospheric concentration of natural and bomb-produced radionuclides has been measured at ground level for several years at three locations throughout the world. The manner in which the concentration decreased suggested a half-residence time for stratospheric aerosols of 11.8 months at 46°N latitude. The annual spring concentration maximum occurred one to four months earlier at 71°N than at 46°N. Cosmogenic 7Be attained a maximum concentration before the bomb-produced radionuclides at 71° N and later than the bomb-produced isotopes at 46°N. The rate of increase toward the annual peak concentration for most radionuclides could be approximated by an exponential in which the concentration doubled every 60 days likewise, the rate of decrease from the maximum concentration could be approximated by an exponential with a half-time of about 40 days for most radionuclides except 7Be at 46°N, which shows a half-time of about 60 days. 

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