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The Distribution of Ozone and Ozone-Depleting Substances in the Atmosphere and Observed Changes

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The Distribution of Ozone and Ozone-Depleting Substances in the Atmosphere and Observed Changes THE DISTRIBUTION OF OZONE AND OZONE-DEPLETING SUBSTANCES IN THE ATMOSPHERE AND OBSERVED CHANGES 1.1 GLOBAL OZONE MEASUREMENT (see Chapter 3). Intrusions of stratospheric air are also a signif- AND MONITORING icant source of ozone in the troposphere (see Chapter 2). Globally, the distribution and climatology of tropospheric Ozone (O3), an allotrope of ordinary oxygen (O2), is the most important trace constituent in the stratosphere. Although it is ozone appear to be highly variable and have not yet been present in relative concentrations of no more than a few parts well established by comprehensive measurements. Although per million, it is such an efficient absorber of ultraviolet radia- this is a very important area of current research, this docu- tion that it is the largest source of heat in the atmosphere at ment will deal primarily with the state of current knowledge altitudes between about 10 and 50 km. UV absorption by of ozone in the stratosphere. ozone causes the temperature inversion that is responsible for Regular measurments of the ozone content of the atmos- the existence of the stratosphere. Ozone is also an important phere were initiated in the early 1920s by G.M.B. Dobson radiator, with strong emission bands in the 9.6 mm infrared using spectrographic instruments. He built his first version of region. In the UV-B region (290–315 nm) it absorbs with an what is now known as the Dobson ozone spectrophotometer efficiency that increases exponentially with decreasing wave- in 1927. It makes precise measurements of the relative intensi- length, and so strongly that at 290 nm the radiation at the ties of sunlight at pairs of wavelengths in the UV spectrum; 1 ground is reduced by more than a factor of 104 from that the total ozone column is deduced from these measurements above the ozone layer (see Chapter 4). This strong variation and the known absorption coefficients of ozone at the wave- of absorption efficiency with wavelength in the UV-B region lengths of measurement. Canada acquired a Dobson in 1948. is the basis of the Dobson and Brewer operational methods Until the 1950s there were only about 20 regularly operating of measuring ozone. stations in the world, most of which were located in the Ozone is the main source of the highly reactive OH northern hemisphere. Some of these had already interrupted radical, which causes the removal of many organic molecules their measurement programs in the late 1950s. At this time from the atmosphere. In the troposphere, it is also a pollutant, the reason for studying ozone was the hope that research which means that its natural concentration is augmented by into stratospheric motion, of which ozone was a useful tracer, anthropogenic sources. Because its extra oxygen bond can be would lead to improved models for forecasting the weather. easily broken, ozone is a strong oxidant that is both corrosive It is for this reason that we have such a comprehensive data to materials and toxic to plants and animals. A principal com- base of ozone measurements for the 1960s and 1970s, well ponent of urban smog, it is produced in and downwind of before ozone depletion became a scientific issue. Systematic urban centres by photochemical reactions involving volatile ozone observations using common observational methods and calibration procedures laid out by the International organic hydrocarbons (VOCs) and oxides of nitrogen (NOx) 1 Equivalent thickness of the ozone layer, expressed as a vertical column of pure ozone. The standard unit is the Dobson Unit, equal to 10–5m at 0˚C and sea level pressure (STP). The global average of total ozone is approximately 300 DU, equivalent to a thickness of 3 mm. 15 Figure 1.1 Geographical distribution of ground-based ozone measurement stations in 1975 and 1995. 16 OZONE SCIENCE: A CANADIAN PERSPECTIVE ON THE CHANGING OZONE LAYER Ozone Commission in collaboration with the World Meteoro- angles between 60° and 90°. As the sun sets (or rises) the mean logical Organization (WMO) were started in preparation for scattering height of radiation changes as a result of the attenu- the International Geophysical Year (1957–1958). These ation of the direct and scattered radiation by ozone absorption standard procedures formed the basis of the Global Ozone and Rayleigh scattering. Since both ozone absorption and Observing System, which presently has more than 160 contin- Rayleigh attenuation increase toward shorter wavelengths, uously operating stations. Three main types of instruments the mean scattering height moves upward more rapidly as a are used for routine total ozone observations: Dobson and function of the solar zenith angle for shorter wavelengths Brewer spectrophotometers that can measure total ozone with than it does for longer wavelengths. The short-wavelength up to 1% accuracy [e.g., Kerr et al.1988] and the less accurate light, which is scattered higher in the atmosphere, travels M-83 and M-124 filter ozonometers [e.g., Bojkov et. al. 1994]. along a path which passes, on average, through less ozone. Figure 1.1 shows the geographical distribution of stations. The variation of the intensity of light as a function of wave- The World Ozone and UV Radiation Data Centre, the interna- length and zenith angle can therefore be used to determine tional repository for all ground-based measurements of ozone, the vertical profile of ozone, provided that the ozone is housed at Environment Canada in Toronto. distribution remains constant throughout the period. A relatively small number of stations make regular The vertical resolution of the Umkehr method is about measurements of the vertical profile of ozone concentration two scale heights (5–10 km) in the stratosphere [Mateer and using balloon-borne ozonesondes. Two principal types of Dutsch 1964; Mateer and Deluisi 1992; McElroy and Kerr ozonesonde exist: the Brewer-Mast [Brewer and Milford 1960] 1995]. The Umkehr method is relatively insensitive to the and the ECC [Komhyr 1969]. Both types measure the ozone distribution of ozone in the lower atmosphere (0 to 15 km). concentration in situ, via its reaction with an aqueous solution Figure 1.2 [McElroy and Kerr 1995] shows the performance of potassium iodide. The technique is very sensitive and can of the Brewer Umkehr as compared with the mean profile give very fine vertical resolution. It is also capable of excellent inferred from measurements made by lidar, ozonesondes, and accuracy, but sensitivity to contamination as well as errors a microwave radiometer. It can be seen that the Umkehr arising from improper handling or occasional mechanical retrieval performs very well in the 20–40 km altitude range defects in the sonde itself render it less reliable than optical and provides useful information to 45 or 50 km. methods. For this reason sonde data are compared, whenever possible, with Brewer or Dobson total ozone measurements. Only a few stations have been making regular measure- ments since before the 1980s. Since ozone loss now appears to have started sometime between 1970 and 1980, their records are of particular significance. The time series of ozone sound- ings from these stations represent some of the longest records of ozone measurement that exist, as well as the only time series of measurements in the free troposphere and the most precise vertically resolved measurements in the lower stratos- phere. The stations with important long-term records are: Hohenpeissenberg and Lindenberg (Germany), Payerne (Switzerland), Uccle (Belgium), Boulder, Wallops Island (contiguous United States), Barrow (Alaska), Hilo (Hawaii), Resolute, Churchill, Goose Bay, and Edmonton (Canada), Tateno and Sapporo (Japan), and the South Pole and Syowa in Antarctica. A much larger number of stations have started making soundings more recently, and a number of other stations have important but intermittent records. Regular ozone soundings have been made since 1966 in Canada and are currently made weekly at six stations. Additional flights are made during times of special interest, like the Arctic spring. Figure 1.2 Comparison of an Umkehr-derived profile with the mean of other profile measurements (two lidars, one sonde, and one Umkehr observations are made by using an ultraviolet microwave) [McElroy and Kerr, 1995]. spectrophotometer to measure the intensity of light from the zenith sky at various wavelengths over a range of solar zenith CHAPTER 1: THE DISTRIBUTION OF OZONE AND OZONE-DEPLETING SUBSTANCES IN THE ATMOSPHERE AND OBSERVED CHANGES 17 Umkehr observations have been made since the effect was first studied by Götz [Götz et al. 1934] in the 1920s, and Umkehr observations are included as a regular part of the automated observing schedules of the Brewer spectropho- tometer. Analysis of these data for trends in the vertical distribution of ozone at higher altitudes is complex, and although such studies have been published for Dobson observations [Mateer and Dutsch 1964; Deluisi et al. 1989; WMO 1994] up to now, much less has been done with data from the newer Brewer instruments [Hahn et al. 1995; McElroy et al. 1997]. Dobson ozone spectrophotometers were installed at five sites in Canada between 1957 and 1964. These were replaced in the mid-1980s by the automated Brewer ozone spectropho- Figure 1.3 Canadian ground-based ozone measurement stations in 1997. tometer, developed by scientists at Environment Canada. The Brewer compares the intensities of five UV-B wavelengths The Network for the Detection of Stratospheric Change in order to better correct for the influence of absorbers other (NDSC) is a set of high-quality, ground-based, remote- than ozone. It is now in use at some 90 sites worldwide. sounding research stations for observing and understanding Brewer instruments have been installed recently at seven the physical and chemical state of the stratosphere. Ozone additional sites in Canada (Table 1; Figure 1.3).
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