During the period May 12-23, 1992, an intercomparisono of Various ground-based remote sensing UV-visible spectrometers for the measurement of stratospheric NO2 slant columns was held at Lauder (New Zealand). All groups' results from Lauder were reported by the intercomparison referee, David Hofmann,in a special paper [Hofmann et al., 1995].

Simultaneous measurements of 7Be and 210Pb and the analyses of activity ratio, i.e., 7Be/210Pb, offer another useful analytical tool for improving our understanding of ozone variability occurring at high altitude because they can provide diagnostic indicators of horizontal and vertical transport processes. Generally, the increase (decrease) of 7Be with decrease (increase) of 210Pb in association with high (low) values of 7Be/210Pb indicates the mechanisms associated with vertical (for being favorable to the horizontal) transport processes. For the purpose of demonstrating these mechanisms for ozone transport, we have presented the distinct transport processes of ozone and background conditions for two Global Atmosphere Watch (GAW) stations: Mount Cimone station (44.18°N, 10.7°E, 2165 m asl) and Mount Waliguan station (36.29°N, 100.90°E, 3816 m asl), located high in the mountains of Italy and China, respectively. We have performed the frequency distribution analyses and various comparisons of variations of 7Be with 210Pb and variations of 7Be, 210Pb, and 7Be/210Pb with surface ozone. The maximum ozone levels occur in the summer, and minimum levels occur in the winter at these two high mountain stations. Our analyses suggest that the processes of the stratospheric intrusions/upper tropospheric transport combined with the long-range transport from polluted areas over eastern central China are the mechanisms that cause the ozone summer peak at the Mount Waliguan station. The ozone summer peak at the Mount Cimone station is mainly the result of photochemical production in the lower atmosphere associated with the transport of polluted air masses on regional and continental scales. Frequency distributions of 7Be, 210Pb, 7Be/210Pb, and surface ozone can be well represented by the lognormal distributions. Strikingly, we have found that the similarities of bimodal distributions for 7Be/210Pb at these two stations are clearly exhibited except for the magnitude, although the lognormal distributions of 7Be and 210Pb, with the noteworthy difference in altitude of these two stations, are significantly different. The measurements of 7Be and 210Pb combined with the analyses using 7Be/210Pb activity ratio can enhance our understanding of the transport processes in the atmosphere.

During the period May 12–23, 1992, seven groups from seven countries met in Lauder, New Zealand, to intercompare their remote sensing instruments for the measurement of atmospheric column NO2 from the surface. The purpose of the intercomparison was to determine the degree of intercomparability and to qualify instruments for use in the Network for the Detection of Stratospheric Change (NDSC). Three of the instruments which took part in the intercomparison are slated for deployment at primary NDSC sites. All instruments were successful in obtaining slant column NO2 amounts at sunrise and sunset on most of the 12 days of the intercomparison. The group as a whole was able to make measurements of the 90° solar zenith angle slant path NO2 column amount that agreed to about ±10% most of the time; however, the sensitivity of the individual measurements varied considerably. Part of the sensitivity problem for these measurements is the result of instrumentation, and part is related to the data analysis algorithms used. All groups learned a great deal from the intercomparison and improved their results considerably as a result of this exercise.

In this paper we present a study on stratospheric intrusion (SI) events recorded at a high mountain station in the Italian northern Apennines. Six years (1998–2003) of surface ozone and beryllium-7 concentration measurements as well as relative humidity values recorded at the GAW Mt. Cimone research station (44°11'N, 10°42'E; 2165 m asl) were analyzed. Moreover, three-dimensional backward trajectories calculated by the FLEXTRA model and potential vorticity values along these trajectories were used. In order to identify SI and evaluate their contribution to the tropospheric ozone at Mt. Cimone, a statistical methodology was developed. This methodology consists of different selection criteria based on observed and modeled stratospheric tracers as well as on tropopause height values recorded by radio soundings. On average, SI effects affected Mt. Cimone for about 36 days/year. The obtained 6-year SI climatology showed a clear seasonal cycle with a winter maximum and a spring-summer minimum. The seasonal cycle was also characterized by an interannual variation. In particular, during winter (autumn), SI frequency could be related to the intensity of the positive (negative) NAO phase. In order to separate direct SI from indirect SI, a restrictive selection criterion was set. This criterion, named Direct Intrusion Criterion (DIC), requested that all the analyzed tracers were characterized by stratospheric values. Direct SI affected Mt. Cimone for about 6 days/year, with frequency peaks in winter and early summer. At Mt. Cimone, SI contribution to background ozone concentrations was largest in winter. On average, an ozone increase of 8% (3%) with respect to the monthly running mean was found during direct (indirect) SI. Finally, the typical variations of stratospheric tracers during SI events were analyzed. The analysis of in situ atmospheric pressure values suggested that direct SI were connected with intense fronts affecting the region, while indirect SI were possibly connected with subsiding structures related with anticyclonic areas.

In this paper we present in situ and tropospheric column measurements of NO2 in the Po river basin (northern Italy). The aim of the work is to provide a quantitative comparison between ground-based and satellite measurements in order to assess the validity of spaceborne measurements for estimating NO2 emissions and evaluate possible climatic effects. The study is carried out using in situ chemiluminescent instrumentation installed in the Po valley, a UV/Vis spectrometer installed at Mount Cimone (44.2°N, 10.7°E, 2165 m asl), and tropospheric column measurements obtained from the Global Ozone Monitoring Experiment (GOME) spectrometer. Results show that the annual cycle in surface concentrations and also some specific pollution periods observed by the air quality network are well reproduced by the GOME measurements. However, tropospheric columns derived from the surface measurements assuming a well-mixed planetary boundary layer (PBL) are much larger than the GOME columns and also have a different seasonal cycle. This is interpreted as indication of a smaller and less variable mixing height for NO2 in the boundary layer. Under particular meteorological conditions the agreement between UV/Vis tropospheric column observations and GOME measurements in the Mount Cimone area is good (R2 = 0.9) with the mixing properties of the atmosphere being the most important parameter for a valid comparison of the measurements. However, even when the atmospheric mixing properties are optimal for comparison, the ratio between GOME and ground-based tropospheric column data may not be unity. It is demonstrated that the values obtained (less than 1) are related to the fraction of the satellite ground pixel occupied by the NO2 hot spot.

The photolysis of atmospheric nitrous acid (HONO) is a significant source of OH radicals in remote and Polar Regions. HONO is produced in/on snow surfaces in a photochemical reaction from nitrate ions. In an attempt to quantify the production of HONO at a snow covered mid-latitude location we made measurements of HONO fluxes for a 10-day period at the Mt. Cimone (MTC) research station in the Italian northern Apennines (2165 m asl) during March 2004. Production fluxes under normal background conditions were small, and reached maximum values of 20 nmol m-2 h-1 on only two occasions. However, during a transport event of Saharan dust to MTC we observed deposition fluxes of up to -120 nmol m-2 h-1 of HONO on to the snow surface. The deposited Sahara dust had rendered the surface snow alkaline, so that large amounts of acids could be absorbed from the atmosphere.

In this paper we present a study on stratospheric intrusion (SI) events recorded at a high mountain station in the Italian northern Apennines. Six years (1998–2003) of surface ozone and beryllium-7 concentration measurements as well as relative humidity values recorded at the GAW Mt. Cimone research station (44°11'N, 10°42'E; 2165 m asl) were analyzed. Moreover, three-dimensional backward trajectories calculated by the FLEXTRA model and potential vorticity values along these trajectories were used. In order to identify SI and evaluate their contribution to the tropospheric ozone at Mt. Cimone, a statistical methodology was developed. This methodology consists of different selection criteria based on observed and modeled stratospheric tracers as well as on tropopause height values recorded by radio soundings. On average, SI effects affected Mt. Cimone for about 36 days/year. The obtained 6-year SI climatology showed a clear seasonal cycle with a winter maximum and a spring-summer minimum. The seasonal cycle was also characterized by an interannual variation. In particular, during winter (autumn), SI frequency could be related to the intensity of the positive (negative) NAO phase. In order to separate direct SI from indirect SI, a restrictive selection criterion was set. This criterion, named Direct Intrusion Criterion (DIC), requested that all the analyzed tracers were characterized by stratospheric values. Direct SI affected Mt. Cimone for about 6 days/year, with frequency peaks in winter and early summer. At Mt. Cimone, SI contribution to background ozone concentrations was largest in winter. On average, an ozone increase of 8% (3%) with respect to the monthly running mean was found during direct (indirect) SI. Finally, the typical variations of stratospheric tracers during SI events were analyzed. The analysis of in situ atmospheric pressure values suggested that direct SI were connected with intense fronts affecting the region, while indirect SI were possibly connected with subsiding structures related with anticyclonic areas.

During the EU-project Influence of Stratosphere-Troposphere exchange in a Changing Climate on Atmospheric Transport and Oxidation Capacity (STACCATO), a combined approach of a measurement network and numerical simulations was used to estimate the strength and frequency of stratosphere-to-troposphere transport (STT) events and their influence on tropospheric chemistry. Measurements of surface ozone, beryllium-7, and beryllium-10 concentrations and meteorological parameters at four European high mountain stations, as well as atmospheric profiles obtained by ozone soundings and a high-resolution lidar, were carried out. In order to simulate STT events, seven different models have been applied by the STACCATO partners. These are two trajectory models (LAGRANTO and FLEXTRA), a Lagrangian transport model (FLEXPART), a Lagrangian chemistry-transport model (STOCHEM), a Eulerian transport model (TM3), and two general circulation models (ECHAM4 and MA-ECHAM4). In order to investigate the strengths and weaknesses of each of these models and to identify the reasons for their discrepancies, a detailed comparison with measured data is presented in this paper. These models provided fluxes and concentrations of a stratospheric tracer, as well as the vertical profiles of ozone and radionuclides for a stratospheric intrusion case study that occurred over Europe in the year 1996. The comparison of the model results with the measurement data and the satellite observations revealed that all the models captured the general behavior of the event. However, great differences were found in the intensity and spatial development of the simulated intrusion event.

Ground-based in situ measurements of 1,1-difluoroethane (HFC-152a, CH3CHF2) which is regulated under the Kyoto Protocol are reported under the auspices of the AGAGE (Advanced Global Atmospheric Gases Experiment) and SOGE (System of Observation of halogenated Greenhouse gases in Europe) programs. Observations of HFC-152a at five locations (four European and one Australian) over a 10 year period were recorded. The annual average growth rate of HFC-152a in the midlatitude Northern Hemisphere has risen from 0.11 ppt/yr to 0.6 ppt/yr from 1994 to 2004. The Southern Hemisphere annual average growth rate has risen from 0.09 ppt/yr to 0.4 ppt/yr from 1998 to 2004. The 2004 average mixing ratio for HFC-152a was 5.0 ppt and 1.8 ppt in the Northern and Southern hemispheres, respectively. The annual cycle observed for this species in both hemispheres is approximately consistent with measured annual cycles at the same locations in other gases which are destroyed by OH. Yearly global emissions of HFC-152a from 1994 to 2004 are derived using the global mean HFC-152a observations and a 12-box 2-D model. The global emission of HFC-152a has risen from 7 Kt/yr to 28 Kt/yr from 1995 to 2004. On the basis of observations of above-baseline elevations in the HFC-152a record and a consumption model, regional emission estimates for Europe and Australia are calculated, indicating accelerating emissions from Europe since 2000. The overall European emission in 2004 ranges from 1.5 to 4.0 Kt/year, 5–15% of global emissions for 1,1-difluoroethane, while the Australian contribution is negligible at 5–10 tonnes/year, <0.05% of global emissions.

This paper provides a review of stratosphere-troposphere exchange (STE), with a focus on processes in the extratropics. It also addresses the relevance of STE for tropospheric chemistry, particularly its influence on the oxidative capacity of the troposphere. After summarizing the current state of knowledge, the objectives of the project Influence of Stratosphere-Troposphere Exchange in a Changing Climate on Atmospheric Transport and Oxidation Capacity (STACCATO), recently funded by the European Union, are outlined. Several papers in this Journal of Geophysical Research–Atmospheres special section present the results of this project, of which this paper gives an overview. STACCATO developed a new concept of STE in the extratropics, explored the capacities of different types of methods and models to diagnose STE, and identified their various strengths and shortcomings. Extensive measurements were made in central Europe, including the first monitoring over an extended period of time of beryllium-10 (10Be), to provide a suitable database for case studies of stratospheric intrusions and for model validation. Photochemical models were used to examine the impact of STE on tropospheric ozone and the oxidizing capacity of the troposphere. Studies of the present interannual variability of STE and projections into the future were made using reanalysis data and climate models.