Distributions of ozone and related trace gases at an urban site in western India

Continuous in-situ measurements of surface ozone (O₃), carbon monoxide (CO) and oxides of nitrogen (NOx) were conducted at Udaipur city in India during April 2010 to March 2011. We have analyzed the data to investigate both diurnal and seasonal variations in the mixing ratios of trace gases. The diurnal distribution of O₃ showed highest values in the afternoon hours and lower values from evening till early morning. The mixing ratios of CO and NOx showed a sharp peak in the morning hours but lowest in the afternoon hours. The daily mean data of O₃, CO and NOx varied in the ranges of 5–51 ppbv, 145–795 ppbv and 3–25 ppbv, respectively. The mixing ratios of O₃ were highest of 28 ppbv and lowest 19 ppbv during the pre-monsoon and monsoon seasons, respectively. While the mixing ratios of both CO and NOx showed highest and lowest values during the winter and monsoon seasons, respectively. The diurnal pattern of O₃ is mainly controlled by the variations in photochemistry and planetary boundary layer (PBL) depth. On the other hand, the seasonality of O₃, CO and NOx were governed by the long-range transport associated mainly with the summer and winter monsoon circulations over the Indian subcontinent. The back trajectory data indicate that the seasonal variations in trace gases were caused mainly by the shift in long-range transport pattern. In monsoon season, flow of marine air and negligible presence of biomass burning in India resulted in lowest O₃, CO and NOx values. The mixing ratios of CO and NOx show tight correlations during winter and pre-monsoon seasons, while poor correlation in the monsoon season. The emission ratio of ?CO/?NOx showed large seasonal variability but values were lower than those measured over the Indo Gangetic Plains (IGP). The mixing ratios of CO and NOx decreased with the increase in wind speed, while O₃ tended to increase with the wind speed. Effects of other meteorological parameters in the distributions of trace gases were also noticed.     

Seasonality of tropospheric ozone and water vapor over Delhi,India: a study based on MOZAIC measurement data

Tropospheric distributions of ozone (O₃) and water vapor (H₂O) have been presented based on the Measurements of OZone and water vapor by Airbus In-Service AirCraft (MOZAIC) data over the metro and capital city of Delhi, India during 1996–2001. The vertical mixing ratios of both O₃ and H₂O show strong seasonal variations. The mixing ratios of O₃ were often below 40 ppbv near the surface and higher values were observed in the free troposphere during the seasons of winter and spring. In the free troposphere, the high mixing ratio of O₃ during the seasons of winter and spring are mainly due to the long-range transport of O₃ and its precursors associated with the westerly-northwesterly circulation. In the lower and middle troposphere, the low mixing ratios of ∼20–30 ppbv observed during the months of July–September are mainly due to prevailing summer monsoon circulation over Indian subcontinent. The summer monsoon circulation, southwest (SW) wind flow, transports the O₃-poor marine air from the Arabian Sea and Indian Ocean. The monthly averages of rainfall and mixing ratio of H₂O show opposite seasonal cycles to that of O₃ mixing ratio in the lower and middle troposphere. The change in the transport pattern also causes substantial seasonal variation in the mixing ratio of H₂O of 3–27 g/kg in the lower troposphere over Delhi. Except for some small-scale anomalies, the similar annual patterns in the mixing ratios of O₃ and H₂O are repeated during the different years of 1996–2001. The case studies based on the profiles of O₃, relative humidity (RH) and temperature show distinct features of vertical distribution over Delhi. The impacts of long range transport of air mass from Africa, the Middle East, Indian Ocean and intrusions of stratospheric O₃ have also been demonstrated using the back trajectory model and remote sensing data for biomass burning and forest fire activities.     

Downward transport and modification of tropospheric ozone through moist convection

This study estimated the largely unstudied downward transport and modification of tropospheric ozone associated with tropical moist convection using a coupled meteorology-chemistry model. High-resolution cloud resolving model simulations were conducted for deep moist convection events over West Africa during August 2006 to estimate vertical transport of ozone due to convection. Model simulations realistically reproduced the characteristics of deep convection as revealed by the estimated spatial distribution of temperature, moisture, cloud reflectivity, and vertical profiles of temperature and moisture. Also, results indicated that vertical transport reduced ozone by 50% (50 parts per billion by volume, ppbv) in the upper atmosphere (12–15 km) and enhanced ozone by 39% (10 ppbv) in the lower atmosphere (<2 km). Field observations confirmed model results and indicated that surface ozone levels abruptly increased by 10–30 ppbv in the area impacted by convection due to transport by downdrafts from the upper troposphere. Once in the lower troposphere, the lifetime of ozone decreased due to enhanced dry deposition and chemical sinks. Ozone removal via dry deposition increased by 100% compared to non-convective conditions. The redistribution of tropospheric ozone substantially changed hydroxyl radical formation in the continental tropical boundary layer. Therefore, an important conclusion of this study is that the redistribution of tropospheric ozone, due to deep convection in non-polluted tropical regions, can simultaneously reduce the atmospheric loading of ozone and substantially impact the oxidation capacity of the lower atmosphere via the enhanced formation of hydroxyl radicals.     

Emission characteristic of ozone related trace gases at a semi-urban site in the Indo-Gangetic plain using inter-correlations

Measurements of surface O₃, CO, NO_x and light NMHCs were made during December 2004 at Hissar, a semi-urban site in the state of Haryana in north-west region of the Indo-Gangetic Plain (IGP). The night-time O₃ values were higher when levels of CO, NO and NO₂ were lower but almost zero values were observed during the episodes of elevated mixing ratios of CO (above 2000 ppbv) and NO_x (above 50 ppbv). Slopes derived from linear fits of O₃ versus CO and O₃ versus NO_x scatter plots were also negative. However, elevated levels of O₃ were observed when CO and NO_x were in the range of 200–300 ppbv and 20–30 ppbv, respectively. Slope of CO-NO_x of about 33 ppbv/ppbv is much larger than that observed in the US and Europe indicating significant impact of incomplete combustion processes emitting higher CO and lesser NO_x. Correlations and ratios of these trace gases including NMHCs show dominance of recently emitted pollutants mostly from biomass burning at this site.     

Measurements of surface ozone at semi-arid site Anantapur (14.62°N, 77.65°E, 331 m asl) in India

In the present study, an attempt has been made to examine the governing photochemical processes of surface ozone (O₃) formation in rural site. For this purpose, measurements of surface ozone and selected meteorological parameters have been made at Anantapur (14.62°N, 77.65°E, 331 m asl), a semi-arid zone in India from January 2002 to December 2003. The annual average diurnal variation of O₃ shows maximum concentration 46 ppbv at noon and minimum 25 ppbv in the morning with 1σ standard deviation. The average seasonal variation of ozone mixing ratios are observed to be maximum (about 60 ppbv) during summer and minimum (about 22 ppbv) in the monsoon period. The monthly daytime and nighttime average surface ozone concentration shows a maximum (55 ± 7 ppbv; 37 ± 7.3 ppbv) in March and minimum (28 ± 3.4 ppbv; 22 ± 2.3 ppbv) in August during the study period. The monthly average high (low) O₃ 48.9 ± 7.7 ppbv (26.2 ± 3.5 ppbv) observed at noon in March (August) is due to the possible increase in precursor gas concentration by anthropogenic activity and the influence of meteorological parameters. The rate of increase of surface ozone is high (1.52 ppbv/h) in March and lower (0.40 ppbv/h) in July. The average rate of increase of O₃ from midnight to midday is 1 ppbv/h. Surface temperature is highest (43–44°C) during March and April months leading to higher photochemical production. On the other hand, relative humidity, which is higher during the rainy season, shows negative correlation with temperature and ozone mixing ratio. It can be seen that among the two parameters are measured, correlation of surface ozone with wind speed is better (R ²=0.84) in compare with relative humidity (R ²=0.66).     

A 10-year study of background surface ozone concentrations on the island of Gozo in the Central Mediterranean

A 10-year study of surface ozone mixing ratios in the Central Mediterranean was conducted based on continuous ozone measurements from 1997 to 2006 by a background regional Global Atmospheric Watch (GAW) station on the island of Gozo. The mean annual maximum mixing ratio is of the order of 66 ppbv in April–May with a broad secondary maximum of 64 ppbv in July–September. No long-term increase or decrease in the background level of surface ozone could be observed over the last 10 years. This is contrary to observations made in the Eastern Mediterranean, where a slow decrease in the background ozone mixing ratio was observed over the past 7 years. Despite the very high average annual ozone mixing ratio exceeding 50 ppbv—in fact, the highest average background ozone mixing ratio ever measured in Europe—, the diurnal O _{3 max}/O _{3 min} index of <1.40 indicates that the island of Gozo is a good site for measuring background surface ozone. However, frequent photosmog events from June to September during the past 10 years with ozone mixing ratios exceeding 90 ppbv indicate that the Central Mediterranean is prone to long-range transport of air pollutants from Europe by northerly winds. This was particularly evident during the so-called “August heatwave” of the year 2003 when the overall ozone mixing ratio was 4.6 ppbv higher than the average of all other 9 months of August since 1997. Air mass back-trajectory analysis of the August 2003 photosmog episodes on Gozo confirmed that ozone pollution originated from the European continent. Regression analysis was used to analyse the 10-year data set in order to model the behaviour of the ozone mixing ratio in terms of the meteorological parameters of wind speed, relative humidity, global radiation, temperature, month of year, wind sector, atmospheric pressure, and time of day (predictors). Most of these predictors were found to significantly affect the ozone mixing ratios. From March to November, the monthly average of the AOT40 threshold value for the protection of crops and vegetation against ozone was constantly exceeded on Gozo during the past 10 years.     

A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

Distributions of O3, CO and NMHCs over the rural sites in central India

The surface level measurements of O₃, CO, CH₄ and light NMHCs were made at eight different rural sites in the central part of India during February, 2004. The online analyzer was used for in-situ measurement of O₃ while air samples were collected for the analyses of CO, CH₄ and NMHCs using the gas chromatography techniques. The average mixing ratios of O₃, which were in the range of 60–90 ppbv, are significantly higher compared to the typical values reported for urban sites of India. The increase rates of O₃ in the forenoon hours were estimated to be in the range of about 8.8–10 ppbv h⁻¹. The slopes of ∆O₃/∆CO, which is an indicator of the efficiency of photochemical production, were in the range of 0.24–0.33 ppbv ppbv⁻¹. However, levels of primary pollutants e.g., NMHCs, CO, etc. at these sites were much lower than urban sites, but higher compared to previously observed values surrounding marine region of India. The estimated ratios of NMHCs and CO indicate fossil fuel combustion process as the dominant source of primary pollutants in this corridor.     

Variations in surface ozone and NOx at Kannur: a tropical, coastal site in India

Continuous measurements of surface ozone (O₃), NOx (NO + NO₂) and meteorological parameters have been made in Kannur (11.9?°N, 75.4?°E, 5?m asl), India from November 2009 to October 2010. It was observed that O₃ and NOx showed distinct diurnal and seasonal variabilities at this site. The annual average diurnal profile of O₃ showed a peak of (30.3?±?10.4) ppbv in the late afternoon and a minimum of (3.2?±?0.7) ppbv in the early morning. The maximum value of O₃ mixing ratio was observed in winter (44?±?3.1) ppbv and minimum during monsoon (18.46?±?3.5) ppbv. The rate of production of O₃ was found to be higher in December (10.1?ppbv/h) and lower in July (1.8?ppbv/h) during the time interval 0800?C1000?h. A correlation coefficient of 0.52 for the relationship between O₃ and [NO₂]/[NO] reveals the role of NO₂ photolysis that generates O₃ at this site. The correlation between O₃ and meteorological parameters indicate the influence of seasonal changes on O₃ production. Investigations were further extended to explore the week day weekend variations in O₃ mixing ratio at an urban site reveals the enhancement of O₃. The variations of O₃ mixing ratio with seasonal air mass flows were elucidated with the aid of backward air trajectories. This study also indicates how vapor phase organic species present in the ambient air at this location may influence the complex chemistry involving (VOCs) that enhances the production of O₃ at this location.     

Ammonia measurements at Niwot Ridge,Colorado and point arena,California using the tungsten oxide denuder tube technique

The applicability of the tungsten oxide denuder tube technique for the measurement of ammonia in the rural troposphere was investigated. The technique is based on selective chemisorption of NH₃ from a gas stream, thermal desorption, conversion to NO, and analysis by NO–O₃ chemiluminescence. Nitric acid, which is also collected and desorbed as NO, was distinguished from NH₃ by differences in desorption temperature. Substituted amines were also collected, but desorbed at a slightly lower temperature than NH₃ in dry air. At high relative humidities, alkylamines may be hydrolyzed to NH₃ on the denuder surface and hence detected as NH₃. Overheating of the denuder tube during the temperature-programmed desorption was found to cause significant irreversible degradation of system performance.The technique was used to measure NH₃ mixing ratios at two rural locations in the United States. At a mountain site in Colorado during the winter of 1984, the average NH₃ mixing ratio was 0.20 ppbv (=0.08 ppbv). At an isolated coastal site in northern California during the spring of 1985, the average NH₃ mixing ratio was 0.36 ppbv (=0.17 ppbv). Correlations of the latter measurements with wind direction and NO _x level suggest that the NH₃ mixing ratio in Pacific marine air at 40°N is <-0.25 ppbv.     

Hydrogen peroxide measurements in the marine atmosphere

Hydrogen peroxide, one of the key compounds in multiphase atmospheric chemistry, was measured on an Atlantic cruise (ANT VII/1) of the German research vessel Polarstern from 15 September to 9 October 1988, in rain and ambient air by a chemiluminescence technique. For gas phase H₂O₂ cryogenic sampling was employed. The presented results show an increase of gas-phase mixing ratios of about 45 pptv per degree latitude between 50° N and 0°, and a maximum of 3.5 ppbv around the equator. Generally higher mixing ratios were observed in the Southern Hemisphere, with a clear diurnal variation. The H₂O₂ mixing ratio is correlated to the UV radiation intensity and to the temperature difference between air and ocean surface water.     

Low Ozone Episodes at Amphitrite Point Marine Boundary Layer Observatory,British Columbia,Canada

At Amphitrite Point, ozone (O₃) mixing ratios are observed to drop steadily to 5–15?ppb over a period of 12 hours or less with a frequency approaching one event per week (with highest frequencies occurring in summer and fall). Analysis of 47 such O₃ depletion events reveals that low O₃ episodes are a predominantly nocturnal phenomenon associated with anticyclonic conditions characterized by light onshore or alongshore winds and an absence of fog and mist. Back-trajectories show air carried to the Amphitrite Point Observatory (APO) during depletion events remains in the marine boundary layer and is not brought to the surface from aloft. There is no strong correlation with other “criteria” pollutants (CO, NO_x, SO₂, PM_2.5) that might be indicative of a mechanism for O₃ destruction linked to human, terrestrial, or marine pollutant sources. However, CO₂ mixing ratios are observed to increase, coincident with O₃ depletion. Together, these results point to a natural marine boundary layer phenomenon in which O₃ destruction dominates O₃ production and/or replenishment by vertical mixing. While there are several candidate mechanisms, the conditions for O₃ depletion (and CO₂ buildup) to occur are set by meteorology and, in particular, development of a stable marine boundary layer in which vertical mixing is suppressed. Support for this interpretation is provided by simultaneous increases in CO₂ in the stable marine boundary that are indicative of an important role played by marine biogenic processes (respiration). Future research should be directed at elucidating the chemical mechanisms responsible for O₃ destruction in the coastal zone, which means that there would be a need for a much broader range of measurements at APO (including halogenated species) as well as offshore measurements of both chemical and marine boundary layer meteorological variables.     

Modeling tropospheric ozone formation over East China in springtime

In this study, we investigate the springtime O₃ formation over East China (April 2008) using the Weather Research and Forecasting Model with Chemistry (WRF/Chem). A simple process analysis scheme is added to WRF/Chem, which could calculate the contributions of photochemical and physical processes to O₃ formation. WRF/Chem calculates the hourly 3-D O₃ mixing ratios, photochemical O₃ production rates (CPR) and physical processes contribution rates (PCR) on a two nested domain system, with inner domain focusing on East China. Model evaluation shows that the modeled results agree relatively well with the observations. On the ground level, the high O₃ mixing ratios (>45 ppbv) are located over Fujian and Jiangxi provinces. The O₃ levels over the Yangtze River Delta (YRD) and northern Jiangsu are low (<30 ppbv). The distribution patterns of CPR and PCR over East China reveal that the high O₃ mixing ratios over Jiangxi and Fujian are caused by both local photochemical generation and regional transport, while the O₃ concentrations over the YRD region are transported and diffused from surrounding areas. In addition, the contributions of biogenic and anthropogenic emissions as well as the regional transport from domain’s upstream regions are discussed. On average, the biogenic and anthropogenic emissions account for 2.6 and 4.5 ppbv of daytime mean O₃ mixing ratios in East China, respectively.     

Seasonal and Diurnal Variation of Surface Ozone and a Preliminary Analysis of Exceedance of its Critical Levels at a Semi-arid Site in India

The mixing ratios of surface O₃ were measured at St. John's College, Agra, an urban and traffic influenced area for the period of 2000–2002. The monthly averaged O₃ mixing ratios ranged between 8 to 40 ppb with an annual average of 21 ppb. Strong diurnal and seasonal variations in O₃ mixing ratios were observed throughout the year except for monsoon season. The mixing ratios of O₃ follow the surface temperature cycle and solar radiation (r = 0.72 and r = 0.65 with temperature and solar radiation, respectively). Concentrations were higher with winds associated with NE and NW direction indicating the impact of pollution sources on surface O₃ concentration. Exceedance of ozone critical level was calculated using the AOT 40 index and found to be 840 ppb.h and 2430 ppb.h for summer and winter seasons, respectively. The present O₃ exposures are lower than the critical level of O₃ and suggest that the present level of O₃ does not have any impact on reduction in crop yields.     

Hydroxyl and Peroxy Radical Chemistry in a Rural Area of Central Pennsylvania: Observations and Model Comparisons

Atmospheric hydroxyl (OH), hydroperoxy (HO₂), total peroxy (HO₂ and organic peroxy radicals, RO₂) mixing ratios and OH reactivity (first order OH loss rate) were measured at a rural site in central Pennsylvania during May and June 2002. OH and HO₂ mixing ratios were measured with laser induced fluorescence (LIF); HO₂ + RO₂ mixing ratios were measured with chemical ionization mass spectrometry (CIMS). The daytime maximum mixing ratios were up to 0.6 parts per trillion by volume (pptv) for OH, 30 pptv for HO₂, and 45 pptv for HO₂ + RO₂. A parameterized RACM (Regional Atmospheric Chemistry Mechanism) box model was used to predict steady state OH, HO₂ and HO₂ + RO₂ concentrations by constraining the model to the measured OH reactivity and previously measured volatile organic compound (VOC) distributions. The averaged model calculations are generally in good agreement with the observations. For OH, the model matched the observations for day and night, with an average observed-to-modeled ratio of 0.80. In previous studies such as PROPHET98, nighttime NO was near 0 pptv and observed nighttime OH was significantly larger than modeled OH. In this study, nighttime observed and modeled OH agree to within measurement and model uncertainties because the main source of the nighttime OH was the reaction HO₂ + NO → OH + NO₂, with the NO being continually emitted from the surrounding fertilized corn field. The observed-to-modeled ratio for HO₂ is 1.0 on average, although daytime HO₂ is underpredicted by a factor of 1.2 and nighttime HO₂ is over-predicted by a factor of ∼2. The average measured and modeled HO₂ + RO₂ agree well during daytime, but the modeled value is about twice the measured value during nighttime. While measured HO₂ + RO₂ values agree with modeled values for NO mixing ratios less than a few parts per billion by volume (ppbv), it increases substantially above the expected value for NO greater than a few ppbv. This observation of the higher-than-expected HO₂ + RO₂ with the CIMS technique confirms the observed increase of HO₂ above expected values at higher NO mixing ratios in HO₂ measurements with the LIF technique. The maximum instantaneous O₃ production rate calculated from HO₂ and RO₂ reactions with NO was as high as 10–15 ppb h⁻¹ at midday; the total daily O₃ production varied from 13 to 113 ppbv d⁻¹ and was 48 ppbv d⁻¹ on average during this campaign.     

Tropospheric ozone and oxides of nitrogen over the north-western Pacific in summer

In summer, atmospheric ozone was measured from an aircraft platform simultaneously with nitric oxide (NO), oxides of nitrogen (NO _y ), and water vapor over the Pacific Ocean in east Asia from 34° N to 19° N along the longitude of 138±3°E. NO _y was measured with the aid of a ferrous sulfate converter. The altitude covered was from 0.5 to 5 km. A good correlation in the smoothed meridional distributions between ozone and NO _y was seen. In particular, north of 25° N, ozone and NO _y mixing ratios were considerably higher than those observed in tropical marine air south of 25° N. NO _y and O₃ reached a minimum of 50 pptv and 4 ppbv respectively in the boundary layer at a latitude of 20° N. The NO concentration between 2 and 5 km at the same latitude was 30 pptv. The profiles of ozone and water vapor mixing ratios were highly anti-correlated between 25° N and 20° N. In contrast, it was much poorer at the latitude of 33° N, suggesting a net photochemical production of ozone there.     

Ozone Concentrations in Rural Regions of the Yangtze Delta in China

Elevated concentrations of ozone have been observed at six non-urban, surface monitoring sites in the Yangtze Delta of China during a 16-month field experiment carried out in 1999 and 2000 as part of the joint Chinese-American China-MAP Project (the Yangtze Delta of china as an Evolving Metro-Agro-Plex). The average daytime (0900–1600 h) ozone levels for the monitoring period at sites ranged from 35 to 47 ppbv (parts per billion by volume) and the mean ozone levels from 26 to 35 ppbv. Observed data show seasonal variation obviously, with highest mixing ratios of ozone in May. Average daytime ozone levels in May at sites were between 60 and 79 ppbv. High ozone concentrations were most prevalent during the late spring. Frequency counts of hourly mean ozone concentration over 60 ppbv and 40 ppbv appeared peak values of 22–39% and 42–74% in May at sites. Even higher daytime ozone levels were observed during two regional episodes, in which average daytime (0900–1600 h) ozone concentrations during 10 May and 23 May 2000 were 68 to 81 ppbv, during Oct. 18 and Oct. 28, 1999 were 59 to 67 ppbv at sites. Peak value of ozone mixing ratio appearing in late spring, instead of in summer, was attributed to summer monsoon. Backward trajectories showed that ozone episodes associated with meteorological conditions. Also many high ozone levels associated with high CO levels and high CO to NO _x ratios, which suggests a contribution from sources of emission involving incomplete combustion.     

Diurnal cycles of formic and acetic acids in the northern part of the Guayana shield,Venezuela

Formic and acetic acids were measured in a scrub-grass savanna and in a nearby semideciduous forest. Gaseous HCOOH and CH₃COOH were collected using the mist-scrubber technique, and were determined using ion chromatography. A strong diurnal cycle was observed at both sites, with higher mixing ratios during daytime. Concentrations in the savanna were always higher than in the forest. Most of the time HCOOH/CH₃COOH ratios greater than one were recorded at the savanna site, and ratios less than one at the forest site. Boundary-layer mixing ratios in the savanna region, derived from measurements during midday, are 1.3±0.4 ppbv and 0.7±0.3 ppbv for HCOOH and CH₃COOH. Dry depositions velocities between 0.5 and 1 cm s^-1 were estimated for the savanna region. Atmospheric residence times of <3 days and >5 days were estimated for the rainy and dry season, respectively.     

On the Spatial Distribution and Seasonal Variation of Lower-Troposphere Ozone over Europe

Surface ozone data from 25 Europeanlow-altitude sites and mountain sites located between79°N and 28°N were studied. The analysiscovered the time period March 1989–February 1993.Average summer and winter O₃ concentrations inthe boundary layer over the continent gave rise togradients that were strongest in the north-west tosouth-east direction and west-east direction, respectively. WintertimeO₃ ranged from 19 to 27 ppbover the continent, compared to about 32 ppb at thewestern border, while for summer the continentalO₃ values ranged between 39 and 56 ppb and theoceanic mixing ratios were around 37 ppb. In the lowerfree troposphere average wintertime O₃ mixingratios were around 38 ppb, with only an 8 ppbdifference between 28°N and 79°N. For summerthe average O₃ levels decreased from about 55 ppbover Central Europe to 32 ppb at 79°N. Inaddition, O₃ and O_x(= O₃ + NO₂)in polluted and clean air were compared. Theamplitudes of the seasonal ozone variations increasedin the north-west to south-east direction, while thetime of the annual maximum was shifted from spring (atthe northerly sites) to late summer (at sites inAustria and Hungary), which reflected the contributionof photochemical ozone production in the lower partsof the troposphere.