Impact of vertical transport processes on the tropospheric ozone layering above Europe. Part I: Study of air mass origin using multivariate analysis,clustering and trajectories

A new method is proposed to classify ozone-rich layers observed in tropospheric profiles in terms of their origin using multivariate analysis. We combine principal component and discriminant analyses to quantify the respective ability of 21 measured physical parameters to describe the layers. Agglomerative hierarchical clustering shows the existence of clusters of air masses with specific physical characteristics. Quadratic discriminant analysis allows the definition of multidimensional borders between these clusters. The geophysical characteristics of the clusters are discussed and related to the origins of the layers: recently transported from the stratosphere (ST) or from the boundary layer (BL) or transported over long distances in the free troposphere.This clustering is compared to the results of a Lagrangian particle dispersion model for a 2-year period. The proportions of layers originating either from the BL or from the ST are highly consistent using both methods as well as the respective contribution of each reservoir to the total ozone mass. About 10% of the ozone measured in the tropospheric layers was exported recently from the BL and one-fifth has a recent stratospheric origin. The remaining proportion could not be attributed to any recent transport pathway. Season-dependent criteria allow very satisfactory reproduction of the seasonal variability of the layering as seen by the Lagrangian model. Analysis of the geographical origin of BL air masses suggests that the statistical clustering underestimates long-range transport, especially in fall.     

Monitoring of ozone in a marine environment in Tenerife (Canary Islands)

In the Aguere Valley (in the oceanic boundary layer at Tenerife, 28°N, 16°W, 580 m a.s.l.) the ozone levels were monitored for ambient air quality assessment. Although precursors are emitted in this area, the strong correlation between ozone levels and wind velocity indicates that ozone is transported into the valley from the ocean. The inland ozone supply along the valley is induced by an orographic channelling effect of the northern oceanic air masses. The highest ozone concentrations are mostly recorded during the nocturnal stage under the influence of fresh oceanic air masses, and during high wind speed events. The seasonal cycle is characterised by elevated ozone mixing ratios in the spring (nighttime levels >45 ppbv) and low mixing ratios in the summer (nighttime levels in the range 20–35 ppbv). Back-trajectory analysis shows that the ozone monitored in the Aguere Valley is associated with long-range transport processes. High ozone events in the spring are associated with transport from upper tropospheric levels, both over the North Atlantic-high latitudes (>45°N) and Europe. This downward transport was observed in the western edge of upper tropospheric cyclones, which suggests that the upper tropospheric/low stratospheric ozone sources play a significant role. In summer, ozone is mainly transported from the North Atlantic-high latitudes (>45°N) and from mid- to low-tropospheric levels. In autumn and winter, the high ozone concentrations are transported from sources located a few km above the North Atlantic-high latitudes (>45°N) and over Europe. The Central-North Atlantic (<45°N) and North Africa are not significant sources of ozone. The high spring and lower summer ozone events in the Aguere Valley agree with other North Atlantic ozone observation in the oceanic boundary layer. However, this behaviour contrasts with the high ozone events frequently recorded at Izaña BAPMoN station (located in the free troposphere in Tenerife) during the summer, which have been attributed in the literature to downward transport from upper levels. An intensification of the inversion layer that separates the oceanic boundary layer of the free troposphere during the summer in Canary Islands is interpreted as the cause of this different behaviour between ozone in the Aguere Valley and Izaña BAPMoN station.     

The role of halogen species in the troposphere

While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes.In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere.     

Formation and Transport of the Madrid Ozone Plume

Abstract

The main results of an experimental study focusing on the formation and transport of photochemical pollution in the Madrid air basin are presented. This southern European, heavily populated urban area is located on an elevated plateau at a height of 700 m, near a mountain range with maximum heights of around 2,400 m. Daily and seasonal cycles of ozone were documented during a one-year survey at three semi-rural sites located 30 km away from the urban center. Maximum hourly values of up to 140 ppb were measured, and the ozone generated within the urban plume on polluted days (when values exceeded 90 ppb) has been estimated at around 40-50 ppb.A meteorological characterization of these smoggy days pointed out the influence of thermally induced local wind flows on the concentration daily cycles at the measuring sites, denoting a preferred advection of the urban plume. Moreover, during intensive summer field campaigns, the use of meteorological and ozone sondes, as well as an instrumented aircraft, revealed some features about the horizontal and vertical distribution of the polluted air masses, as well as their evolution within the planetary boundary layer. Ozone plumes have been detected up to 100 km away from the city, usually mixed in a layer that reaches a height of 1,000-1,500 m in the afternoon. On some occasions, ozone-enriched layers have been detected as high as 4,000 m during morning hours, suggesting possible tropospheric injection induced by topographydriven flows or convective mesoscale systems that are usually present in the center of the Iberian Peninsula in the summer.     

On the seasonal variation of the surface ozone in Athens,Greece

An attempt has been made to examine the seasonal variation of the surface ozone mixing ratio in Athens, Greece during the periods 1901–1940 and 1987–1998. The first finding is that in July and August while the daytime surface ozone mixing ratio from the beginning until the end of the 20th century has increased by approximately 1.8 times, the nighttime surface ozone mixing ratio remained approximately at the same level. The second finding is that the increase in the mean daytime mixing ratio during the transition period from winter to summer is equal to the increase in the maximum daytime mixing ratios, whilst the enhancement of the nighttime surface ozone maxima is stronger than that of the nighttime mean surface ozone mixing ratio. Plausible explanation for this finding is given through mechanisms like long-range transport and photochemical processes occurring in the boundary layer, free troposphere and lower stratosphere.     

Transport of nitrogen oxides, carbon monoxide and ozone to the Alpine Global Atmosphere Watch stations Jungfraujoch (Switzerland), Zugspitze and Hohenpeissenberg (Germany), Sonnblick (Austria) and Mt. Krvavec (Slovenia)

The Alpine stations Zugspitze, Hohenpeissenberg, Sonnblick, Jungfraujoch and Mt. Krvavec contribute to the Global Atmosphere Watch Programme (GAW) of the World Meteorological Organization (WMO). The aim of GAW is the surveillance of the large-scale chemical composition of the atmosphere. Thus, the detection of air pollutant transport from regional sources is of particular interest. In this paper, the origin of NO_x (measured with a photo-converter), CO and O₃ at the four Alpine GAW stations is studied by trajectory residence time statistics. Although these methods originated during the early 1980s, no comprehensive study of different atmospheric trace gases measured simultaneously at several background observatories in the Alps was conducted up to present.The main NO_x source regions detected by the trajectory statistics are the northwest of Europe and the region covering East Germany, Czech Republic and southeast Poland, whereas the main CO source areas are the central, north eastern and eastern parts of Europe with some gradient from low to high latitudes. Subsiding air masses from west and southwest are relatively poor in NO_x and CO.The statistics for ozone show strong seasonal effects. Near ground air masses are poor in ozone in winter but rich in ozone in summer. The main source for high ozone concentration in winter is air masses that subside from higher elevations, often enhanced by foehn effects at Hohenpeissenberg. During summer, the Mediterranean constitutes an important additional source for high ozone concentrations.Especially during winter, large differences between Hohenpeissenberg and the higher elevated stations are found. Hohenpeissenberg is frequently within the inversion, whereas the higher elevated stations are above the inversion.Jungfraujoch is the only station where the statistics detect an influence of air rich in CO and NO_x from the Po Basin.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

A review of surface ozone in the polar regions

Surface ozone records from ten polar research stations were investigated for the dependencies of ozone on radiative processes, snow-photochemisty, and synoptic and stratospheric transport. A total of 146 annual data records for the Arctic sites Barrow, Alaska; Summit, Greenland; Alert, Canada; Zeppelinfjellet, Norway; and the Antarctic stations Halley, McMurdo, Neumayer, Sanae, Syowa, and South Pole were analyzed. Mean ozone at the Northern Hemisphere (NH) stations (excluding Summit) is ∼5 ppbv higher than in Antarctica. Statistical analysis yielded best estimates for the projected year 2005 median annual ozone mixing ratios, which for the Arctic stations were 33.5 ppbv at Alert, 28.6 ppbv at Barrow, 46.3 ppbv ppb at Summit and 33.7 ppbv at Zeppelinfjellet. For the Antarctic stations the corresponding ozone mixing ratios were 21.6 ppbv at Halley, 27.0 ppbv at McMurdo, 24.9 ppbv at Neumayer, 27.2 ppbv at Sanae, 29.4 ppbv at South Pole, and 25.8 ppbv at Syowa. At both Summit (3212 m asl) and South Pole (2830 m asl), annual mean ozone is higher than at the lower elevation and coastal stations. A trend analysis revealed that all sites in recent years have experienced low to moderate increases in surface ozone ranging from 0.02 to 0.26 ppbv yr⁻¹, albeit none of these changes were found to be statistically significant trends. A seasonal trend analysis showed above-average increases in ozone during the spring and early summer periods for both Arctic (Alert, Zeppelinfjellet) and Antarctic (McMurdo, Neumayer, South Pole) sites. In contrast, at Barrow, springtime ozone has been declining. All coastal stations experience springtime episodes with rapid depletion of ozone in the boundary layer, attributable to photochemically catalyzed ozone depletion from halogen chemistry. This effect is most obvious at Barrow, followed by Alert. Springtime depletion episodes are less pronounced at Antarctic stations. At South Pole, during the Antarctic spring and summer, photochemical ozone production yields frequent episodes with enhanced surface ozone. Other Antarctic stations show similar, though less frequent spring and summertime periods with enhanced ozone. The Antarctic data provide evidence that austral spring and summertime ozone production in Antarctica is widespread, respectively, affects all stations at least through transport events. This ozone production contributes to a several ppbv enhancement in the annual mean ozone over the Antarctic plateau; however, it is not the determining process in the Antarctic seasonal ozone cycle. Although Summit and South Pole have many similarities in their environmental conditions, this ozone production does not appear to be of equal importance at Summit. Amplitudes of diurnal, summertime ozone cycles at these polar sites are weaker than at lower latitude locations. Amplitudes of seasonal ozone changes are larger in the Southern Hemisphere (by ∼5 ppbv), most likely due to less summertime photochemical ozone loss and more transport of ozone-rich air to the Arctic during the NH spring and summer months.     

Vertical mixing above Summit,Greenland: Insights into seasonal and high frequency variability from the radionuclide tracers 7Be and 210Pb

The activity of the natural radionuclide tracers ⁷Be and ²¹⁰Pb has been determined in bulk aerosol samples collected over 2-day intervals for nearly five full years at Summit, Greenland. Year-round sampling was conducted in three campaigns; summer 1997 to summer 1998, summer 2000 to summer 2002, and summer 2003 to present. As in previous summer campaigns at Summit, and a year-round investigation at Dye 3, variations in the activities of the tracers on short time scales were strongly correlated despite the upper troposphere/lower stratosphere source of ⁷Be and the continental surface source of ²²²Rn (precursor of ²¹⁰Pb). This behavior is attributed to boundary layer dynamics exerting the dominant control on activities in air just above the ice sheet. Aerosols and associated species are depleted from the boundary layer above the snow when a strong inversion limits exchange with the free troposphere. Episodic weakening of the inversion allows ventilation of the boundary layer. This cycle drives simultaneous decreases and increases in the radionuclide tracers. The correlation between ⁷Be and ²¹⁰Pb on seasonal and annual bases was found to be stronger than at Dye 3, and the average activity of ⁷Be was lower at Summit despite the higher elevation (3.0 versus 2.5 km). These observations indicate that the boundary layer at Summit is more effectively isolated than at Dye 3. The activity of ⁷Be at Summit peaked in June or July all 5 years, closely following the seasonality of stratospheric injection of ⁷Be into the Arctic troposphere (based on seasonality of the ¹⁰Be/⁷Be ratio previously measured at Alert, NWT). This suggests that when the boundary layer at Summit is replenished by ventilation, it receives air reflecting the composition of the mid and upper troposphere.     

Ozone and meteorological boundary-layer conditions at Summit,Greenland, during 3–21 June 2000

The temporal and spatial distributions of boundary-layer ozone were studied during June 2000 at Summit, Greenland, using surface-level measurements and vertical profiling from a tethered balloon platform. Three weeks of continuous ozone surface data, 133 meteorological vertical profile data and 82 ozone vertical profile data sets were collected from the surface to a maximum altitude of 1400 m above ground.The lower atmosphere at Summit was characterized by the prevalence of strong stable conditions with strong surface temperature inversions. These inversions reversed to neutral to slightly unstable conditions between ∼9.00 and 18.00 h local time with the formation of shallow mixing heights of ∼70–250 m above the surface.The surface ozone mixing ratio ranged from 39 to 68 ppbv and occasionally had rapid changes of up to 20 ppb in 12 h. The diurnal mean ozone mixing ratio showed diurnal trends indicating meteorological and photochemical controls of surface ozone. Vertical profiles were within the range of 37–76 ppb and showed strong stratification in the lower troposphere. A high correlation of high ozone/low water vapor air masses indicated the transport of high tropospheric/low stratospheric air into the lower boundary layer. A ∼0.1–3 ppb decline of the ozone mixing ratio towards the surface was frequently observed within the neutrally stable mixed layer during midday hours. These data suggest that the boundary-layer ozone mixing ratio and ozone depletion and deposition to the snowpack are influenced by photochemical processes and/or transport phenomena that follow diurnal dependencies. With 37 ppb of ozone being the lowest mixing ratio measured in all data no evidence was seen for the occurrence of ozone depletion episodes similar to those that have been reported within the boundary layer at coastal Arctic sites during springtime.     

Surface ozone at the Swiss Alpine site Arosa: the hemispheric background and the influence of large-scale anthropogenic emissions

An innovative and effective method using isentropic trajectory analysis based on the residence time of air masses over the polluted region of Europe was successfully applied to categorize surface ozone amounts at Arosa, Switzerland during 1996–1997. The “European representative” background ozone seasonal cycle at Arosa is associated with long-range transport of North Atlantic air masses, and displays the spring maximum–summer minimum with an annual average of 35 ppb. The photochemical ozone production due to the intense large-scale anthropogenic emission over Europe is estimated as high as 20 ppb in summer, whereas it is insignificant in winter. European sources contribute an annual net ozone production of 9–12 ppb at Arosa. Comparison with the selected regional representative site in Western Europe shows similar results indicating that the categorized ozone data at Arosa by this technique could be regarded as a representative for northern hemispheric mid-latitudes.     

What is the lesson from the unprecedented event over antarctica in 2002

Varotsos (2002a,b), suggested that both the smaller-sized ozone hole over Antarctica and its splitting in two holes in September 2002 occurred due to an unprecedented major sudden stratospheric warming caused by very strong planetary waves propagated in the southern hemisphere. Subsequently, a NASA press release of December 6, 2002, also reported the prevalence of very strong planetary waves in Antarctica. The aim of this Letter is to further discuss the morphology of the Antarctic ozone hole, to detect the causes that allowed the Antarctic stratosphere to exhibit this exceptional warming and to examine what it denotes about its mechanisms. Concerning the morphology, among the principal findings is that the ozone hole split occurred not only in the stratosphere but extended in the lower altitudes (upper troposphere). As to the causes of the major sudden stratospheric warming of 2002, a comparison with the previous warmings in Antarctica since 1964 is made. The smaller-sized Antarctic ozone hole of 2002 is approximately equal to that of 1988 when a strong sudden stratospheric warming occurred. If only the destruction of ozone by chlorofluorocarbons resulted in the delayed sudden stratospheric warmings in Antarctica, then the early sudden stratospheric warmings of 1988 and 2002 would not have occurred, since chlorofluorocarbon loading of the stratosphere has remained relatively stable in recent years. Furthermore, it appears that the El Nino characteristics in 1988 and 2002 are not similar.     

Fine-scale layering on the edge of a stratospheric intrusion

Observations of vertical profiles of ozone, humidity, static stability and VHF radar vertical power at Aberystwyth (52°N, 4°W) on 21 June 1996 revealed a pronounced layered structure at the western edge of a stratospheric intrusion, in a location where one would expect to see a tropopause fold. Despite the 3 km depth of the observed ozone anomaly, it was not represented as a fold in the ECMWF potential vorticity analyses; nor was it evident as a layer of enhanced wind shear. Ozone lidar measurements suggest that the fine-scale layering gave way to a single layer as the day progressed. Weak sporadic turbulence observed by the radar at the edge of the fold showed some mixing between stratospheric and tropospheric air.     

Changes in seasonal and diurnal cycles of ozone and temperature in the eastern U.S.

The pollutant tropospheric ozone causes human health problems, and environmental degradation and acts as a potent greenhouse gas. Using long-term hourly observations at five US air quality monitoring surface stations we studied the seasonal and diel cycles of ozone concentrations and surface air temperature to examine the temporal evolution over the past two decades. Such an approach allows visualizing the impact of natural and anthropogenic processes on ozone; nocturnal inversion development, photochemistry, and stratospheric intrusion. Analysis of the result provides an option for determining the duration for a regulatory ozone season. The application of the method provides independent confirmation of observed changes and trends in the ozone and temperature data records as reported elsewhere. The results provide further evidence supporting the assertion that ozone reductions can be attributed to emission reductions as opposed to weather variation. Despite a (～0.5 °C decade^?1) daytime warming trend, ozone decreased by up to 6 ppb decade^?1 during times of maximum temperature in the most polluted locations. Ozone also decreased across the emission reduction threshold of 2002 by 6–10 ppb indicating that emission reductions have been effective where and when it is most needed. Longer time series, and coupling with other data sources, may allow for the direct investigation of climate change influence on regional ozone air pollution formation and destruction over annual and daily time scales.     

The variability of free tropospheric ozone over Beltsville,Maryland (39N, 77W) in the summers 2004–2007

Ozone profiles are often used to investigate day-to-day and year-to-year variability in origins of free tropospheric ozone. With this in mind, more than 50 ozonesonde launches were conducted in Beltsville, MD, during the summers of 2004 through 2007. Budgets of free tropospheric ozone were calculated for each ozone profile in the four summers using a laminar identification (LID) method and unusual episodes were analyzed with respect to meteorological variables. The laminar method showed that stratosphere-to-troposphere transport (ST) accounted for greater than 50% of the free tropospheric ozone column on 17% of days sampled, a more pronounced influence than regional convective and lightning (RCL) sources. The ST origins were confirmed with trajectories, and tracers (water vapor and potential vorticity). The amount of free tropospheric ozone from ST and RCL sources varied from year-to-year (up to 13%) and can be explained by differences in mean meteorological patterns. On average, almost 30% of the free tropospheric column was attributed to ST influence, about twice as much as RCL, although the LID method may not capture weeks-old lightning influences as in a chemical model. The prevalence of ST ozone in summertime Beltsville soundings was similar to six sounding sites in the IONS-04 campaign [Thompson, A.M., et al., 2007b. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 1. Summertime upper tropospheric/lower stratosphere ozone over northeastern North America. J. Geophys. Res. 112, D12S12; Thompson, A.M., et al., 2007c. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 2. Tropospheric ozone budgets and variability over northeastern North America. J. Geophys. Res. 112, D12S13.] and to statistics from a 30 year climatology of European soundings [Collette, A., Ancellet, G., 2005. Impact of vertical transport processes on the tropospheric ozone layering above Europe. Part II: Climatological analysis of the past 30 years. Atmos. Environ. 39, 5423–5435]. The Beltsville record also demonstrated the value of soundings for air quality forecasting in an urban area. The 22 nighttime soundings collected over Beltsville in 2004–2007 can be divided into distinct polluted and unpolluted subsets, the former 20 ppbv higher in residual layer ozone (1 km) than the latter. These distinctions propagated to daytime differences of 10 ppbv at the surface in the Washington, DC, area, with the high-ozone residual layers leading to non-attainment of the National Ambient Air Quality Standard for ozone. More frequent ozone observations aloft appear essential for better understanding ozone variability and for enabling air quality modelers to achieve more accurate ozone forecasts.     

What is causing high ozone at Summit,Greenland?

Causes for the unusually high and seasonally anomalous ozone concentrations at Summit, Greenland were investigated. Surface data from continuous monitoring, ozone sonde data, tethered balloon vertical profiling data, correlation of ozone with the radionuclide tracers ⁷Be and ²¹⁰Pb, and synoptic transport analysis were used to identify processes that contribute to sources and sinks of ozone at Summit. Northern Hemisphere (NH) lower free troposphere ozone mixing ratios in the polar regions are ∼20 ppbv higher than in Antarctica. Ozone at Summit, which is at 3212 m above sea level, reflects its altitude location in the lower free troposphere. Transport events that bring high ozone and dry air, likely from lower stratospheric/higher tropospheric origin, were observed ∼40% of time during June 2000. Comparison of ozone enhancements with radionuclide tracer records shows a year-round correlation of ozone with the stratospheric tracer ⁷Be. Summit lacks the episodic, sunrise ozone depletion events, which were found to reduce the annual, median ozone at NH coastal sites by up to ∼3 ppbv. Synoptic trajectory analyses indicated that, under selected conditions, Summit encounters polluted continental air with increased ozone from central and western Europe. Low ozone surface deposition fluxes over long distances upwind of Summit reduce ozone deposition losses in comparison to other NH sites, particularly during the summer months. Surface-layer photochemical ozone production does not appear to have a noticeable influence on Summit's ozone levels.     

Estimation of the Natural Background of Ozone Present at Surface Rural Locations

The natural background in the ozone concentration at rural locations in the United States and western Europe has been estimated by use of several approaches. The approaches utilized include the following: (1) historical trends in ozone concentration measurements, (2) recent ozone measurements at remote sites, (3) use of tracers of air originating in the stratosphere or upper troposphere and (4) results from applications of tropospheric photochemical models. While each of these approaches has its own limitations it appears that the natural background of ozone during the warmer months of the year is in the range of 10 to 20 ppb. Most of the ozone originating in the lower stratosphere or upper troposphere is lost by chemical or physical removal processes as well as undergoing dilution by air in the lower troposphere before reaching ground level rural locations. Lower tropospheric photochemical processes, those below 5 km, are likely to account for most of the ozone measured at rural locations during the warmer months of the year.

A key aspect to improved quantitation of the contributions from lower tropospheric photochemical processes to ozone concentrations continues to be more extensive atmospheric measurements of the distribution of reactive species of nitrogen. The emission densities of anthropogenic sources of NO_x are known to be highly variable over populated areas of continents as well as between continental areas and the oceans. The emission densities of biogenic sources of NO_x are small, likely to be highly variable, but poorly quantitated. These wide variations indicate the need for use of three dimensional tropospheric photochemical models over large continental regions.

Available results do indicate higher efficiencies for ozone formation at lower NO_x concentrations, especially below 1 ppb.     

Impact of ozone mini-holes on the heterogeneous destruction of stratospheric ozone

A comprehensive study of ozone mini-holes over the mid-latitudes of both hemispheres is presented, based on model simulations with the coupled climate-chemistry model ECHAM4.L39(DLR)/CHEM representing atmospheric conditions in 1960, 1980, 1990 and 2015. Ozone mini-holes are synoptic-scale regions of strongly reduced total ozone, directly associated with tropospheric weather systems. Mini-holes are supposed to have chemical and dynamical impacts on ozone levels. Since ozone levels over northern mid-latitudes show a negative trend of approximately -4%/decade and since it exists a negative correlation between total column ozone and erythemally active solar UV-radiation reaching the surface it is important to understand and assess the processes leading to the observed ozone decline. The simulated mini-hole events are validated with a mini-hole climatology based on daily ozone measurements with the TOMS (total ozone mapping spectrometer) instrument on the satellite Nimbus-7 between 1979 and 1993. Furthermore, possible trends in the event frequency and intensity over the simulation period are assessed. In the northern hemisphere the number of mini-hole events in early winter decreases between 1960 and 1990 and increases towards 2015. In the southern hemisphere a positive trend in mini-hole event frequency is detected between 1960 and 2015 in spring associated with the increasing Antarctic Ozone Hole. Finally, the impact of mini-holes on the stratospheric heterogeneous ozone chemistry is investigated. For this purpose, a computer-based detection routine for mini-holes was developed for the use in ECHAM4.L39(DLR)/CHEM. This method prevents polar stratospheric cloud formation and therefore heterogeneous ozone depletion inside mini-holes. Heterogeneous processes inside mini-holes amount to one third of heterogeneous ozone destruction in general over northern mid- and high-latitudes during winter (January-April) in the simulation.     

Long-term changes in the tropospheric column ozone from the ozone soundings over Europe

The tropospheric column of ozone is analyzed from the measurements of the vertical profile of ozone by balloon-born ozonesondes. The data base includes ∼16,000 ozone profiles collected above six European stations—three of them have begun the ozonesoundings since 1970. We present a trend analysis (with data up to 2005) focusing on detection of the long-term tropospheric ozone variability over the European network. The ozone time series have been examined separately for each station and season (DJF, MAM, JJA, SON) using a flexible trend model. A trend component of the model is taken as a smooth curve without a priori defined shape. A large increase in the European tropospheric ozone since the beginning of the 1970s (net change of ∼10% in summers and ∼30% in winters) and a kind of stabilization in the early 1990s have been corroborated by the study. This pattern comes from the most extensive data set of ozonesoundings over Hohenpeissenberg and Payern. The decadal differences in the trend pattern between these and other European stations are disclosed. The results of a stepwise regression model using various characteristics of the ozone and temperature profiles as explanatory variables for the tropospheric column ozone (TCO₃) variations show that the ozone changes may be reconstructed using the ozone mixing ratio at 500 hPa, the thermal tropopause (TT) height, and the difference between ozonepause and TT heights. It appears that the last two factors induce 20–30% of the net TCO₃ change over Hohenpeissenberg in the 1970–2004 period.