Ozone in stratosphere

Stratospheric ozone Emission of ozone-depleting compounds (CFCs, Halons) Chemical reaction release of C1 and Br in stratosphere Catalytic destruction of ozone in stratosphere Skin and crop damage, damage to materials Ozone Depletion Potential (ODP)... 

Figure 6. Amount of ozone in stratosphere over Sacramento Peak, N. M.

Ivlev L.S., V.G. Sirota, S.N. Khvorostovsky Volcanic sulfur dioxide oxidation influencing the concentration of sulfate aerosols and ozone in stratosphere. Optics of Atmosphere 3 (1990) 37-43. 

Measurements of ozone (O3) concentrations in the atmosphere are of particular importance. Ozone absorbs strongly in the ultraviolet region and it is this absorption which protects us from a dangerously high dose of ultraviolet radiation from the sun. The vitally important ozone layer lies in the stratosphere and is typically about 10 km thick with a maximum concentration about 25 km above the surface of the earth. Extreme depletion of ozone in a localised part of the atmosphere creates what is known as an ozone hole. 

The importance of ozone in the stratosphere has been stressed in Section 9.3.8. The fact that ozone can be decomposed by the halogen monoxides CIO, BrO and 10 means that their presence in the stratosphere contributes to the depletion of the ozone layer. For example, iodine, in the form of methyl iodide, is released into the atmosphere by marine algae and is readily photolysed, by radiation from the sun, to produce iodine atoms which can react with ozone to produce 10 ... 

The presence of naturally occurring ozone in the lower stratosphere creates a potential hazard for passengers and crew members of high flying aircraft (163,164). Ozone in the inlet air to the aircraft cabin, which can reach 1.2 ppm, is destroyed catalyticaHy. 

Because of the expanded scale and need to describe additional physical and chemical processes, the development of acid deposition and regional oxidant models has lagged behind that of urban-scale photochemical models. An additional step up in scale and complexity, the development of analytical models of pollutant dynamics in the stratosphere is also behind that of ground-level oxidant models, in part because of the central role of heterogeneous chemistry in the stratospheric ozone depletion problem. In general, atmospheric Hquid-phase chemistry and especially heterogeneous chemistry are less well understood than gas-phase reactions such as those that dorninate the formation of ozone in urban areas. Development of three-dimensional models that treat both the dynamics and chemistry of the stratosphere in detail is an ongoing research problem. 

In the last decade, the refrigerant issue is extensively discussed due to the accepted hypothesis that the chlorine and bromine atoms from halocarbons released to the environment were using up ozone in the stratosphere, depleting it specially above the polar regions. Montreal Protocol and later agreements ban use of certain CFCs and halon compounds. It seems that all CFCs and most of the HCFCs will be out of produc tion by the time this text will be pubhshed. 

The other global environmental problem, stratospheric ozone depletion, was less controversial and more imminent. The U.S. Senate Committee Report supporting the Clean Air Act Amendments of 1990 states, Destruction of the ozone layer is caused primarily by the release into the atmosphere of chlorofluorocarbons (CFCs) and similar manufactured substances—persistent chemicals that rise into the stratosphere where they catalyze the destruction of stratospheric ozone. A decrease in stratospheric ozone will allow more ultraviolet (UV) radiation to reach Earth, resulting in increased rates of disease in humans, including increased incidence of skin cancer, cataracts, and, potentially, suppression of the immune system. Increased UV radiation has also been shown to damage crops and marine resources."... 

During the mid-1980s, each September scientists began to observe a decrease in ozone in the stratosphere over Antarctica. These observations are referred to as "ozone holes." In order to understand ozone holes, one needs to know how and why ozone is present in the earth s stratosphere. 

F. S. Rowland and M. Molina showed that man-made chlorofluorocarbons, CFCs, could catalytically destroy ozone in the stratosphere (Nobel Prize for Chemistry, with P. Crutzen, 1995). 

Despite their instability (or perhaps because of it) the oxides of chlorine have been much studied and some (such as CI2O and particularly CIO2) find extensive industrial use. They have also assumed considerable importance in studies of the upper atmosphere because of the vulnerability of ozone in the stratosphere to destruction by the photolysis products of chlorofluorocarbons (p. 848). The compounds to be discussed are ... 

About 51 percent of solar energy incident at the top of the atmosphere reaches Earth s surface. Energetic solar ultraviolet radiation affects the chemistry of the atmosphere, especially the stratosphere where, through a series of photochemical reactions, it is responsible for the creation of ozone (O,). Ozone in the stratosphere absorbs most of the short-wave solar ultraviolet (UV) radiation, and some long-wave infrared radiation. Water vapor and carbon dioxide in the troposphere also absorb infrared radiation. 

In the upper atmosphere (the stratosphere), the situation is quite different. There the partial pressure of ozone goes through a maximum of about 10-5 atm at an altitude of 30 km. From 95% to 99% of sunlight in the ultraviolet region between 200 and 300 nm is absorbed by ozone in this region, commonly referred to as the "ozone layer." The mechanism by which this occurs can be represented by the following pair of equations ... 

Ever) year our planet is bombarded with enough energy from the Sun to destroy all life. Only the ozone in the stratosphere protects us from that onslaught. The ozone, though, is threatened by modern life styles. Chemicals used as coolants and propellants, such as chlorofluorocarbons (CFCs), and the nitrogen oxides in jet exhausts, have been found to create holes in Earth s protective ozone layer. Because they act as catalysts, even small amounts of these chemicals can cause large changes in the vast reaches of the stratosphere. 

Figure 4. Processes that Control Ozone in the Stratosphere.

The concentration of ozone in the stratosphere is lower than predicted from reactions 1-4. This is due to the presence of trace amounts of some reactive species known as free radicals. These species have an odd number of electrons and they can speed up reaction 4 by means of catalytic chain reactions. Nitrogen oxides, NO and NO2, which are naturally present in the stratosphere at levels of a few parts per billion (ppb), are the most important catalysts in this respect. The reactions, first suggested by Paul Crutzen (2) and by Harold Johnston (3) in the early 1970 s, are as follows ... 

It is only recently that a decrease in stratospheric ozone levels attributable to the CFCs has been observed. In spite of the relatively large natural... 

The Antarctic ozone hole is the result of anthropogenic release of trace gases into the atmosphere (CFCs in particular), causing a decrease in stratospheric ozone and a subsequent increase in solar ultraviolet radiation reaching the earth s surface. 

In summary, biomass burning is a major source of many trace gasses, especially the emissions of CO2, CH4, NMHC, NO,, HCN, CH3 CN, and CH3 Cl (73). In the tropics, these emissions lead to local increases in the production of O3. Biomass burning may also be responsible for as much as one-third of the total ozone produced in the troposphere (74). However, CH3 Cl from biomass burning is a significant source for active Cl in the stratosphere and plays a significant role in stratospheric ozone depletion (73). 

The chemistry of the stratospheric ozone will be sketched with a very broad brush in order to illustrate some of the characteristics of catalytic reactions. A model for the formation of ozone in the atmosphere was proposed by Chapman and may be represented by the following "oxygen only" mechanism (other aspects of... 

We begin our exploration of delocalized bonds with ozone, O3. As described in Chapter 7, ozone in the upper stratosphere protects plants and animals from hazardous ultraviolet radiation. Ozone has 18 valence electrons and a Lewis stmcture that appears in Figure 10-36a. Experimental measurements show that ozone is a bent molecule with a bond angle of 118°. 

Events that take place on a grand scale often can be traced to the molecular level. An excellent example is the depletion of the ozone layer in the Earth s stratosphere. The so-called ozone hole was first observed above the Antarctic in the 1980s and is now being observed above both the Arctic and Antarctic poles. The destruction of ozone in the stratosphere is caused primarily by reactions between chlorine atoms and ozone molecules, as depicted in our molecular inset view. 

Catalysts are immensely beneficial in industry, but accidental catalysis in the atmosphere can be disastrous. Recall from Box that the chemishy of ozone in the stratosphere involves a delicate balance of reactions that maintain a stable concentration of ozone. Chlorofiuorocarbons (CFCs) shift that balance by acting as catalysts for the destruction of O3 molecules. 

We see that chiorine atoms provide an aitemative mechanism for the reaction of ozone with oxygen atoms. The iower-energy pathway breaks down ozone in the stratosphere at a significantiy faster rate than in the absence of the cataiyst. This disturbs the deiicate baiance among ozone, oxygen atoms, and oxygen molecules in a way that poses a serious threat to the iife-protecting ozone iayer. 

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