Six years of regular ozone soundings over Switzerland

Summary The mean vertical ozone distribution as a function of season is computed from almost 6 years of regular soundings (three times per week) over Switzerland. By comparing the concurrent mean values of the total amount with the 35-year average at Arosa, and by using the correlation between ozone concentration at different levels with the total amount, adjusted values for the seasonal variation of the vertical ozone distribution are obtained which are thought to give a better representation of the long-term climatological mean. The data show a prominent biennial variation of the ozone content around the level of the maximum concentration which does not, however, show up in the total amount because it is missing in the lower stratosphere.     

Ozone concentration studies and ozone flux measurements near the ground at Poona

Using a modified Brewer bubbler ozone sensor, continuous measurements of the ozone concentration near the ground were made at Poona (18°N, 73°E) for one year 1969–1970. The surface ozone concentration shows a pronounced seasonal variation, with a minimum during the monsoon months and a maximum during the pre-monsoon summer months. There is also a marked diurnal variation in surface ozone concentration which clearly follows the diurnal variation of temperature and is again a maximum during the summer months and a minimum during the monsoon. A secondary maximum in ozone concentration occurs in the forenoon during the winter months, associated with the temperature inversions that occur near the ground in this season.Both ozone and radioactive tracers, such as Cs-137 both in air and in precipitation show variations indicating that they have identical source regions and sinks. The latitudinal anomaly of surface ozone and Cs-137 observed in the low latitudes over India is explained as arising from the reduction in the rate of transfer of these tracers from the stratosphere to the troposphere, as a result of the reversed circulation at the upper levels in this season.From continuous measurements of surface ozone made with three electrochemical sensors exposed at three levels, 0, 15 and 35 m above the ground, the ozone flux has been directly calculated for the first time in the tropics. The ozone flux was calculated using both the rate of decay method used by Kroening and Ney and Regener's profile method. The profile method gives values of the order of 1.71 to 7.04×10¹¹ mol/cm²/sec and that obtained by the rate of decay method is found to be 4.2 to 5.6×10¹¹ mol/cm²/sec and are in good agreement with the flux values reported by other investigators.     

Impact of coupled perturbations of atmospheric trace gases on Earth's climate and ozone

We have studied the effects on the ozone concentration and surface temperature, of perturbations in the atmospheric content of nitrous oxide, methane, carbon dioxide and chlorofluorocarbons (CFC). The sensitivity study has been carried out with a radiative-convective-photochemical model. The doubling of carbon dioxide concentration has the effect of warming the troposphere and cooling the stratosphere. As a result of this cooling, the change of ozone columnar density produced by 10 ppb of chlorine amount to 9.3% as compared to –10.9% obtained without temperature feedback. Perturbation in nitrous oxide correspond to an increase in NO _x of the stratosphere with consequent ozone reduction while doubling the methane concentration correspond to a slight increase in columnar density. The effect of the increased methane concentration in the stratosphere contributes to reduce the effect of CFC due to the enhanced formation of HCl. The perturbation of these two minor constituents appreciably increase the greenhouse effect to 2.30 from 1.67°, obtained when carbon dioxide alone is considered.     

Studies of variations in the vertical ozone profiles over India

The latitudinal and temporal variations in the vertical profiles of ozone over the Indian subcontinent are discussed. In the equatorial atmosphere represented by Trivandrum (8°N) and Poona (18°N), while tropospheric ozone shows marked seasonal variations, the basic pattern of the vertical distribution of ozone in the stratosphere remains practically unchanged throughout the year, with a maximum at about 28 to 26 km and a minimum just below the tropopause. The maximum total ozone occurs over Trivandrum in the summer monsoon season and the latitudinal anomaly observed over the Indian monsoon area at this time is explained as arising from the horizontal transport of ozone-rich stratospheric air from over the thermal equator to the southern regions.In the higher latitudes represented by New Delhi (28°N), the maximum occurs at 23 km. Delhi, which lies in the temperate regime in winter, shows marked day-to-day variations in association with western disturbances and the strong westerly jet stream that lies over north and central India at this time.Although the basic pattern of the vertical distribution of ozone in the equatorial atmosphere is generally the same in all seasons, significant though small changes occur in the lower stratosphere and in the troposphere. There are small perturbations in the ozone and temperature structures, distinct ozone maxima being always associated with temperature inversions. There are also large perturbances not related to temperature, ozone-depleted regions normally reflecting a stratification of either destructive processes or materials such as dust layers or clouds at these levels. Particularly interesting are the upper tropospheric levels just below the tropopause where the ozone concentration is consistently the smallest, in all seasons and at all places where soundings have been made in India.     

Ozone distribution over Mediterranean,central and southeast Europe during the International Quiet Sun Year (1964–1965)

Summary Ozone observations made during 1964 and 1965 at nine Mediterranean, central and southeast European stations (latitudes 38–52°N, longitudes 9–23°E) reveal patterns of seasonal and shorter time-variations in total ozone as well as in vertical ozone distribution. During the winter-spring season, a significant increase (20%) of ozone occurs essentially simultaneously with the spring stratospheric warming, and is noticed at all stations.—Autocorrelation coefficients show that the total ozone on any day is strongly related to the total ozone of the preceding four days in summer or one or two days in winter-spring or autumn. Changes of total ozone in southeast Europe correlate closely with those in Mediterranean Europe, and less closely with those from north central Europe.—Power spectrum analysis detects the dependence of ozone changes on processes with periods longer than 6–8 days, and indicates a significant oscillation with a period of 14–15 days, perhaps a result of the direct influence of lower stratospheric circumhemispheric circulation. — Reliable vertical ozone soundings were not available from all stations. The mean vertical profiles at Arosa, Switzerland (47°N) and Belsk, Poland (51°) are very similar. More than 60% of the variability of the total ozone is contributed by changes in ozone concentration between 10 and 24 km; less than 10% is due to variations above 33 km. Changes in ozone partial pressure at different altitudes, and relationships of those changes to total ozone, indicates that a mean vertical ozone distribution may be described adequately by considering the ozone changes in four layers: a) the troposphere, b) the lower stratosphere up to 24 km, c) a transition layer from 24 km to a variable upper border at 33–37 km, and d) the layer above 33–37 km.Part of this paper was presented at the Ozone Seminar in Potsdam, Germany, 27 September 1966.     

Synoptic-scale fluctuations of total ozone in the atmosphere

A model, based on ozone-concentration tendency equation, is developed to study synoptic ozone-column variations. The application is referred to a middle-latitude site and to an atmospheric layer extending from the surface up to about 35-km altitude. Photochemical effects at the considered location for synoptic time scales are considered negligible. The data input consists of umkehr ozone profile, total ozone (obtained by Brewer No. 067, located at Rome) and horizontal wind at various levels. Analysis of several cases indicates that meridional advection is the main factor responsible for the observed synoptic-scale ozone fluctuations.     

Meridional distribution of tropospheric ozone from measurements aboard commercial airliners

Aboard commercial airliners twenty registrations of the ozone concentration of the upper troposphere were carried out within a period of 14 months between Europe and South Africa. Nearly each of these meridional ozone profiles shows an approximately constant ozone content between 25°S and 25°N with a pronounced seasonal variation. Most of these profiles show two marked peaks of the ozone concentration at about 30°N and between 40° and 45°N. Though the number of these registrations is not sufficient for statistical computations, the first results confirm the meridional ozone distribution, which was expected from studies with ozone-radiosonde soundings. Moreover a strong asymmetry of the northern and southern hemisphere is confirmed by these ozone measurements.     

Surface ozone in the aretic atmosphere

Near-surface atmospheric ozone measurements were carried out at Barrow, Alaska (71°, 19N, 156°W), from January 1965 to September 1967. Ozone was continuously monitored by microcoulombmetric analysis at a level 2 m above the ground. Daily ozone concentrations near the ground varied from 7 to less than 1 pphm by volume. Highest concentrations occurred in the spring and showed sharp increases lasting from several hours to a few days. These sudden rises in ozone concentration correlated with storm front passages. The concentration of surface ozone from late spring through the sumer and fall showed less variability from day to day than in the spring. The lowest ozone concentrations occurred from late May to early June.     

MTBE in Drinking Water Production – Occurrence and Efficiency of Treatment Technologies

In Germany, the gasoline additive methyl tert‐butyl ether (MTBE) is almost constantly detected in measurable concentrations in surface waters and is not significantly removed during riverbank filtration. The removal of MTBE from water has been the focus of many studies that mostly were performed at high concentration levels and centred in understanding the mechanisms of elimination. In order to assess the performance of conventional and advanced water treatment technologies for MTBE removal in the low concentration range further studies were undertaken. Laboratory experiments included aeration, granulated activated carbon (GAC) adsorption, ozonation and advanced oxidation processes (AOP). The results show that the removal of MTBE by conventional technologies is not easily achieved. MTBE is only removed by aeration at high expense. Ozonation at neutral pH values did not prove to be effective in eliminating MTBE at all. The use of ozone/H₂O₂ (AOP) may lead to a partly elimination of MTBE. However, the ozone/H₂O₂ concentrations required for a complete removal of MTBE from natural waters is much higher than the ozone levels applied nowadays in waterworks. MTBE is only poorly adsorbed on activated carbon, thus GAC filtration is not efficient in eliminating MTBE. A comparison with real‐life data from German waterworks reveals that if MTBE is detected in the raw water it is most often found in the corresponding drinking water as well due to the poor removal efficiency of conventional treatment steps.     

Statistical interpolation of ozone measurements from satellite data (TOMS, SBUV and SAGE II) using the kriging method

This study demonstrates that ordinary kriging in spherical coordinates using experimental semi-variograms provides highly usable results, especially near the pole in winter and/or where there could be data missing over large areas. In addition, kriging allows display of the spatial variability of daily ozone measurements at different pressure levels. Three satellite data sets were used: Total Ozone Mapping Spectrometer (TOMS) data, Solar Backscattered UltraViolet (SBUV), and the Stratospheric Aerosol and Gas Experiment (SAGE II) ozone profiles. Since SBUV is a nadir-viewing instrument, measurements are only taken along the sun-synchronous polar orbits of the satellite. SAGE II is a limb-viewing solar occultation instrument, and measurements have high vertical resolution but poor daily coverage. TOMS has wider coverage with equidistant distribution of data (resolution 1° × 1.25°) but provides no vertical information. Comparisons of the resulting SBUV-interpolated (column-integrated) ozone field with TOMS data are strongly in agreement, with a global correlation of close to 98%. Comparisons of SBUV-interpolated ozone profiles with daily SAGE II profiles are relatively good, and comparable to those found in the literature. The interpolated ozone layers at different pressure levels are shown.     

Annual and semiannual oscillations of stratospheric ozone

The global structures of annual oscillation (AO) and semiannual oscillation (SAO) of stratospheric ozone are examined by applying spherical harmonic analysis to the ozone data obtained from the Nimbus-7 solar backscattered UV-radiation (SBUV) measurements for the period November 1978 to October 1980. Significant features of the results are: (1) while the stratospheric ozone AO is prevalent only in the polar regions, the ozone SAO prevails both in the equatorial and polar stratospheres; (2) the vertical distribution of the equatorial ozone SAO has a broad maximum of the order of 0.5 (mixing ratio in g/g) and the maximum appears earlier at high altitude (shifting from May [and November] at 0.3 mb [60 km] to November [and May] at 40 mb); (3) above the 40 km level, the maximum of the polar ozone SAO shifts upward towards later phase with altitude with a rate of approximately 10 km/month in both hemispheres; (4) vertical distributions of the polar ozone AOs and SAOs show two peaks in amplitude with a minimum (nodal layer) in between and a rapid phase change with altitude takes place in the respective nodal layers; and (5) the heights of the ozone AO- and SAO-peaks decrease with latitude. The main part of AOs and SAOs of stratospheric ozone including hemispheric asymmetries is ascribable to: (i) temperature dependent ozone photochemistry in the upper stratosphere and mesosphere, (ii) variations of radiation field in the lower stratosphere affected by the annual cycle of solar illumination and temperature in the upper stratosphere and (iii) meridional ozone transport by dynamical processes in the lower stratosphere.     

Using an objective model to estimate overall ozone levels at different urban locations

Ground-level tropospheric ozone is one of the air pollutants of most concern. Ozone levels become particularly high in regions close to high ozone precursor emissions and during summer, when high insolation and high temperatures are common. Ozone levels continue to exceed both target values and the long-term objectives established in EU legislation to protect human health and prevent damage to ecosystems, agricultural crops and materials. Researchers or decision-makers frequently need information about atmospheric pollution patterns in urbanized areas. The preparation of this type of information is a complex task, due to the influence of several factors and their variability over time. In this work, some results of urban ozone distribution patterns in the city of Badajoz, which is the largest (140,000 inhabitants) and most industrialized city in Extremadura region (southwest Spain) are shown. Twelve sampling campaigns, one per month, were carried out to measure ambient air ozone concentrations, during periods that were selected according to favourable conditions to ozone production, using an automatic portable analyzer. Later, to evaluate the overall ozone level at each sampling location during the time interval considered, the measured ozone data were analysed using a new methodology based on the formulation of the Rasch model. As a result, a classification of all locations according to the ozone level, which was the value of the Rasch measure, was obtained. Moreover, information about unexpected behaviours of ozone patterns was generated. Finally, overall ozone level at locations where no measurements were available was estimated which can be used to generate hazard assessment maps.     

北京城区大气混合层内臭氧垂直结构特征的初步分析——基于臭氧探空

本文利用2013年6月至2015年10月北京南苑观象台两年多午后臭氧探空资料,初步分析了北京城区大气混合层内臭氧浓度的垂直分布规律以及典型天气条件下大气边界层臭氧的变化特征.主要结果有：（1）季节平均而言,地表至对流层中部（8 km）的臭氧浓度在夏季最高,冬季最低,相差50~130 μg·m^-3,最大差异在边界层.总体而言,对流层臭氧浓度随高度有比较缓慢的增加,但是边界层内臭氧浓度的垂直结构随季节有比较大的差异：夏季混合层中部存在一个臭氧浓度极大值,这与夏季比较强的光化学生成臭氧有关;而在冬季地面臭氧浓度很低,平均值小于40 μg·m^-3,说明冬季地面是臭氧很强的汇.（2）臭氧浓度季节内变率的季节差异也十分明显,夏季最大、冬季最小.季节内变率在从边界层向自由对流层过渡区域最小（夏季为24 μg·m^-3,冬季仅为10 μg·m^-3）,在边界层内变率较大,夏季可达64 μg·m^-3（冬季为30 μg·m^-3）,这也说明边界层化学过程明显影响臭氧浓度的变化.（3）我们从所有白天样本中严格筛选了部分混合层样本,并把臭氧浓度在由混合层向自由大气过渡时的垂直分布分成了三类,即臭氧浓度随高度增大（Ⅰ型）、减小（Ⅱ型）以及基本稳定不变（Ⅲ型）;臭氧垂直结构类型有明显的季节特征,夏季主要是Ⅱ型,而冬季则以Ⅰ型为主.（4）此外,我们还针对一些典型天气过程（强风、静稳雾天和PM_2.5污染）边界层内臭氧的变化特征进行了分析,结果表明：强风切变产生的机械对流引起的充分混合,有利于高层臭氧向低层输送,使得混合层内臭氧浓度的垂直梯度明显减小,同时混合层高度较高,达3 km以上;在高湿度静稳天气控制下,大气混合层较稳定,对北京上空污染物的垂直扩散十分不利：颗粒物浓度升高,削弱到达近地层的太阳辐射,从而降低臭氧的生成效率,混合层内臭氧浓度与混合层厚度都处于较低水平.     

Estimation of the ozone decrease possibility in the lower part of the <Emphasis Type="Italic">D</Emphasis> region under the action of a powerful radiowave

The possibility of the influence of a powerful radiowave on the ozone concentration in the lower part of the ionospheric D region is discussed on the basis of experiments at the Sura heating facility in March 2009, the results of which were published relatively recently by a group of authors. The results, which were obtained with the use of exact equations of the mesospheric ozone photochemistry, substantially disagree with some conclusions derived by the authors but do not completely deny their hypothesis on the possible influence on the ozone of internal gravity waves formed at heights of the ionospheric E region.     

The role of water-vapour photodissociation on the formation of a deep minimum in mesopause ozone

A one-dimensional atmospheric photochemical model with an altitude grid of about 1.5 km was used to examine the structure of the global mean vertical ozone profile and its night-time-to-daytime variation in the upper atmosphere. Two distinct ozone layers are predicted, separated by a sharp drop in the ozone concentration near the mesopause. This naturally occurring mesopause ozone deep minimum is primarily produced by the rapid increase in the destruction of water vapour, and hence increase in HO_x, at altitudes between 80 and 85 km, a region where water-vapour photodissociation by ultraviolet radiation of the solar Lyman-alpha line is significant, and where the supply of water vapour is maintained by methane oxidation even for very dry conditions at the tropospheric-stratospheric exchange region. The model indicates that the depth of the mesopause ozone minimum is limited by the efficiency with which inactive molecular hydrogen is produced, either by the conversion of atomic hydrogen to molecular hydrogen via one of the reaction channels of H with HO₂, or by Lyman-alpha photodissociation of water vapour via the channel that leads to the production of molecular hydrogen. The ozone concentration rapidly recovers above 85 km due to the rapid increase in O produced by the photodissociation of O₂ by absorption of ultraviolet solar radiation in the Schumann-Runge bands and continuum. Above 90 km, there is a decrease in ozone due to photolysis as the production of ozone through the three-body recombination of O₂ and O becomes slower with decreasing pressure. The model also predicts two peaks in the night-time/daytime ozone ratio, one near 75 km and the other near 110 km, plus a strong peak in the night-time/daytime ratio of OH near 110 km. Recent observational evidence supports the predictions of the model.     

Summertime Characteristics of the Atmospheric Boundary Layer and Relationships to Ozone Levels over the Eastern United States

— This paper examines the spatial and temporal distributions of the mixing height, ventilation coefficient (defined as the product of mixing height and surface wind speed), and cloud cover over the eastern United States during the summer of 1995, using the high-resolution meteorological data generated by MM5 (Version 1), a mesoscale model widely used in air quality studies. The ability of MM5 to simulate the key temporal and spatial features embedded in the time series of observations of temperature, wind speed, and moisture is assessed using spectral decomposition methods. Also, mixing heights estimated from the MM5 outputs are compared with those derived from observations at a few locations where data with high temporal resolution are available in the Northeast. In addition, the uncertainties associated with the estimation of the evolution of the boundary layer during the morning time are examined. The results indicate that nighttime mixing heights averaged <200?m, rising to 1 km by 10 EST, and to about 2.5?km in the afternoon. Ventilation coefficients followed a similar diurnal pattern, increasing from 500?m²/s at night?to 15,000?m²/s in the afternoon; the increase due to the growing mixing height and increasing surface wind speeds. Spatial variability of these parameters was relatively small (coefficient of variation=0.25) at?night and in the afternoon when conditions were quasi-stationary, but increased (to 0.5) during morning?and evening hours when mixing heights and wind speeds were changing rapidly. Analyses of surface ozone observations from about 400 sites throughout the eastern United States indicate that days with numerous stations reporting surface ozone concentrations in excess of 80 ppb (i.e., “high ozone” days) generally had less daytime cloud cover, lower surface wind speeds, higher mixing heights, and lower ventilation coefficients than did comparable “low ozone” days. Such meteorological features are consistent with a synoptic anticyclone centered over the mid-south region (Kentucky, Tennessee). Low ozone days were characterized by more disturbed weather conditions (low pressure systems, fronts, greater cloud cover, and precipitation events). Ozone observations at two elevated platforms (～400?m agl) in Garner, NC, and Chicago, IL, indicated that ozone concentrations aloft were about 40% larger on “high ozone” days than on “low ozone” days. On average, high levels of ozone persist aloft for about 2 to 3 days. Strong vertical mixing in the daytime can bring this pool of upper-level ozone downward to augment surface ozone production. Since ozone can be transported downwind several hundred kilometers from its source region over this time scale, depending on upper-level winds, effective ozone control strategies must take into consideration spatial scales ranging from local to regional, and time scales of the order of several days.     

Estimating the atmospheric ozone transmission for solar radiation models

Accurate calculation of the solar radiation at the earth’s surface requires evaluation of the atmospheric ozone transmission. To use the existing methods one needs to know the atmospheric ozone amount. The serious lack of ozone data makes almost impossible the application of these methods in most of the world. In this paper a new method of estimating the overall ozone attenuation in the Northern Hemisphere is presented. Multiyear monthly latitudinal average ozone data are used. A daily ozone transmission function is proposed, and values of it are calculated for each latitudinal circle from 0° to 70°N at 10 longitude-degree intervals. By regression techniques parameterized expressions of the daily ozone transmission in the Northern Hemisphere are obtained as a function of the latitude. The model is applied to Athens, and the results are in excellent agreement with those obtained by extremely detailed calculations of the ozone transmission. The reliability of the model, under special regional ozone conditions, is investigated. Calculations for 67 locations in the Northern Hemisphere prove that the deviations do not exceed 1 percent. The influence of the year-by-year ozone variability is also examined, and the maximum deviation is found to be near 1.6 percent. The proposed model can be easily incoporated into solar radiation models in order to provide the ozone depletion at any place in the Northern Hemisphere where atmospheric ozone data are not available.     

The average tropospheric ozone content and its variation with season and latitude as a result of the global ozone circulation

Evaluations of radiosonde soundings over North America and Europe, measurements aboard commercial airlines, and permanent ozone registrations at nineteen ground-based stations between Tromsö, Norway, and Hermanus, South Africa, yield three belts of higher ozone intrusion from the stratosphera and maximum values of the annual means at about 30°N, at between 40°–45°N and at about 60°N. A marked decrease of the annual mean values of the tropospheric ozone is detected towards the equator and the pole, respectively.In the northen hemisphere the maximum of the annual cycle of the tropospheric ozone concentration occurs in spring at high latitudes and in summer at mid-latitudes.For the tropical region from 30°S to 30°N a strong asymmetry of the northern and southern hemisphere occurs. This fact is discussed in detail. The higher troposphere of the tropics seems to be a wellmixed reservoir and mainly supplied with ozone from the tropopause gap region in the northern hemisphere. The ozone distribution in the lower troposphere of the whole tropics seems to be controlled by the up and down movements of the Hadley cell. The features of large-scale and seasonal variation of tropospheric ozone are discussed in connection with the ozone circulation in the stratosphere, the dynamic processes near the tropopause and the destruction rate at the earth's surface.     

Short-term ground ozone fluctuations at Poona

Short-term fluctuations superimposed on the diurnal variations of surface ozone recorded at Poona during 1969–1970 are discussed.While there is a net production of ozone during electrical discharges in a thunder cloud, the surface ozone recorder often registered a decrease in surface ozone concentration. This decrease coincided with updraughts generated during the formation of a thunderstorm. Similar sharp increases in ozone were observed with downdraughts. In cases of lightning without the development of a thunderstorm over the station, an increase in ozone density was observed just after the first lightning discharge.Apart from the fluctuations associated with thunderstorms in summer, sharp fluctuations in density were also noticed during winter, in the mornings. Abrupt falls in ozone occur with the formation of a stable layer near the ground at night and a sudden surge after the breaking up of the layers in the morning. The changes in ozone are, however, much more pronounced than those in temperature and wind and this striking correlation between surface ozone, surface air temperature and wind provides a unique tool for the study of low-level temperature inversions, their establishment and destruction.     

Aerosols: A limitation on the determination of ozone from BUV observations

Summary Recent satellite experiments have measured the radiance of the earth at ultraviolet wavelengths and the data thus obtained has been used to determine atmospheric ozone concentrations. It is pointed out in this paper that in the presence of significant concentrations of aerosols at high altitudes, it is not possible from observations of backscattered ultraviolet radiation to separate the effects of aerosols from those attributable to ozone.The earth's daytime horizon was scanned on several occasions between 1963 and 1967 from an altitude of 80 km. For at least one of the flights analyzed we interpret the data to indicate the existence of an aerosol layer at 50 km. This observation, in combination with related observations of other experimenters, implies a limitation on the ability of the backscattered ultraviolet technique to determine ozone concentrations, particularly at altitudes in the region between 35 and 50 km. This limitation may be overcome by altering the viewing geometry and making observations of the earth's horizon. Data thus obtained may be used to deduce the concentrations of both ozone and aerosols.