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Using coincident observations of total ozone from the Total Ozone Mapping Spectrometer (TOMS) and stratospheric ozone profiles from the Solar Backscattered Ultraviolet (SBUV) instruments, detailed maps of tropospheric ozone have been derived on a daily basis over a time period spanning more than two decades. The resultant climatological seasonal depictions of the tropospheric ozone residual (TOR) show much more detail than an earlier analysis that had used coincident TOMS and Stratospheric Aerosol and Gas Experiment (SAGE) ozone profiles, although there are many similarities between the TOMS/SAGE TOR and the TOMS/SBUV TOR climatologies. In particular, both TOR seasonal depictions show large enhancements in the southern tropics and subtropics in austral spring and at northern temperate latitudes during the summer. The much greater detail in this new data set clearly defines the regional aspect of tropospheric ozone pollution in northeastern India, eastern United States, eastern China, and west and southern Africa. Being able to define monthly climatologies for each year of the data record provides enough temporal resolution to illustrate significant interannual variability in some of these regions.
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This study presents measurements of acetonitrile, benzene, toluene, methanol and acetone made using the proton-transfer-reaction mass spectrometry (PTR-MS) technique at the Finokalia ground station in Crete during the Mediterranean INtensive Oxidant Study (MINOS) in July-August 2001. Three periods during the campaign with broadly consistent back trajectories are examined in detail. In the first, air was advected from Eastern Europe without significant biomass burning influence (mean acetonitrile mixing ratio 154 pmol/mol). In the second period, the sampled air masses originated in Western Europe, and were advected approximately east-south-east, before turning south-west over the Black Sea and north-western Turkey. The third well-defined period included air masses advected from Eastern Europe passing east and south of/over the Sea of Azov, and showed significant influence by biomass burning (mean acetonitrile mixing ratio 436 pmol/mol), confirmed by satellite pictures. The mean toluene:benzene ratios observed in the three campaign periods described were 0.35, 0.37 and 0.22, respectively; the use of this quantity to determine air mass age is discussed. Methanol and acetone were generally well-correlated both with each other and with carbon monoxide throughout the campaign. Comparison of the acetone and methanol measurements with the MATCH-MPIC model showed that the model underestimated both species by a factor of 4, on average. The correlations between acetone, methanol and CO implied that the relatively high levels of methanol observed during MINOS were largely due to direct biogenic emissions, and also that biogenic sources of acetone were highly significant during MINOS (~35%). This in turn suggests that the model deficit in both species may be due, at least in part, to missing biogenic emissions.
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The relationship between local meteorological conditions and the surface ozone variability was studied by means of statistical modeling, using ozone and meteorological parameters measured at Lovozero (250 m a.s.l., 68.5°N, 35.0°E, Kola Peninsula) for the period of 1999-2000. The regression model of daily mean ozone concentrations on such meteorological parameters as temperature, relative humidity and wind speed explains up to 70% of day-to-day ozone variability in terms of meteorological condition changes, if the seasonal cycle is also considered. A regression model was created for separated time scales of the variables. Short-term, synoptical and seasonal components are separated by means of Kolmogorov-Zurbenko filtering. The synoptical scale variations were chosen as the most informative from the point of their mutual relation with meteorological parameters. Almost 40% of surface ozone variations in time periods of 11-60 days can be explained by the regression model on separated scales that is 30% more efficient than ozone residuals usage. Quantitative and qualitative estimations of the relations between surface ozone and meteorological predictors let us preliminarily conclude that at the Lovozero site surface ozone variability is governed mainly by dynamical processes of various time scale rather than photochemistry, especially during the cold season.
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Several air pollution transport models have been developed at the National Environmental Research Institute in Denmark over the last decade (DREAM, DEHM, ACDEP and DEOM). A new 3-D nested Eulerian transport-chemistry model: REGIonal high resolutioN Air pollution model (REGINA) is based on modules and parameterisations from these models as well as new methods.<br> <br> The model covers the majority of the Northern Hemisphere with currently one nest implemented. The horizontal resolution in the mother domain is 150 km × 150 km, and the nesting factor is three. A chemical scheme (originally 51 species) has been extended with a detailed description of the ammonia chemistry and implemented in the model. The mesoscale numerical weather prediction model MM5v2 is used as meteorological driver for the model. The concentrations of air pollutants, such as sulphur and nitrogen in various forms, have been calculated, applying zero nesting and one nest. The model setup is currently being validated by comparing calculated values of concentrations to measurements from approximately 100 stations included in the European Monitoring and Evalutation Programme (EMEP).<br> <br> The present paper describes the physical processes and parameterisations of the model together with the modifications of the chemical scheme. Validation of the model calculations by comparison to EMEP measurements for a summer and a winter month is shown and discussed. Furthermore, results from a sensitivity study of the model performance with respect to resolution in emission and meteorology input data is presented. Finally the future prospects of the model are discussed.<br> <br> The overall validation shows that the model performs well with respect to correlation for both monthly and daily mean values.
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We investigated the size distribution, scattering and absorption properties of Amazonian aerosols and the optical thickness of the aerosol layer under the pristine background conditions typical of the wet season, as well as during the biomass-burning-influenced dry season. The measurements were made during two campaigns in 1999 as part of the European contribution to the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA-EUSTACH). In moving from the wet to the dry season, median particle numbers were observed to increase from values comparable to those of the remote marine boundary layer (~400 cm<sup>-3</sup>) to values more commonly associated with urban smog (~4000 cm<sup>-3</sup>), due to a massive injection of submicron smoke particles. Aerosol optical depths at 500 nm increased from 0.05 to 0.8 on average, reaching a value of 2 during the dry season. Scattering and absorption coefficients, measured at 550 nm, showed a concomitant increase from average values of 6.8 and 0.4 Mm<sup>-1</sup> to values of 91 and 10 Mm<sup>-1</sup>, respectively, corresponding to an estimated decrease in single-scattering albedo from ca. 0.97 to 0.91. The roughly tenfold increase in many of the measured parameters attests to the dramatic effect that extensive seasonal biomass burning (deforestation, pasture cleaning) is having on the composition and properties of aerosols over Amazonia. The potential exists for these changes to impact on regional and global climate through changes to the extinction of solar radiation as well as the alteration of cloud properties.
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The mechanism of ice nucleation to form Type 2 PSCs is important for controlling the ice particle size and hence the possible dehydration in the polar winter stratosphere. This paper probes heterogeneous ice nucleation on sulfuric acid tetrahydrate (SAT). Laboratory experiments were performed using a thin-film, high-vacuum apparatus in which the condensed phase is monitored via Fourier transform infrared spectroscopy and water pressure is monitored with the combination of an MKS baratron and an ionization gauge. Results show that SAT is an efficient ice nucleus with a critical ice saturation ratio of S*<sub>ice</sub> = 1.3 to 1.02 over the temperature range 169.8-194.5 K. This corresponds to a necessary supercooling of 0.1-1.3 K below the ice frost point. The laboratory data is used as input for a microphysical/photochemical model to probe the effect that this heterogeneous nucleation mechanism could have on Type 2 PSC formation and stratospheric dehydration. In the model simulations, even a very small number of SAT particles (e.g., 10<sup>-3</sup> cm<sup>-3</sup>) result in ice nucleation on SAT as the dominant mechanism for Type 2 PSC formation. As a result, Type 2 PSC formation is more widespread, leading to larger-scale dehydration. The characteristics of the clouds are controlled by the assumed number of SAT particles present, demonstrating that a proper treatment of SAT is critical for correctly modeling Type 2 PSC formation and stratospheric dehydration.
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Major solar eruptions (coronal mass ejections) are accompanied by massive ejections of protons. When these charged particles head for the Earth through the interplanetary magnetic field with high flux and energy, a solar proton event (SPE) is recorded. Strong SPEs, in which energetic protons penetrate the atmosphere in large numbers are rare, but do have chemical effects (Crutzen, 1975; Jackman et al., 1990, 2001). They also have nucleonic effects by which they can almost instantaneously increase the atmospheric production of radio-nuclides, including <sup>14</sup>C (radiocarbon), but this has never been demonstrated. We show, using satellite observations and modeling, that the 2nd most intensive set of SPEs on record, that of August-December 1989, must have caused detectable increases in atmospheric <sup>14</sup>CO. This is confirmed by a sequence of peaks in the Baring Head (NZ) time series of <sup>14</sup>CO observations (Brenninkmeijer, 1993), probably providing a unique indication of production of <sup>14</sup>C by solar protons, thus demonstrating the use of SPE <sup>14</sup>CO as an atmospheric tracer.
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Fingerlike structures reaching from lower into extra-tropical latitudes significantly contribute to the tropical-extratropical exchange of air masses. This is also an exchange of upper tropospheric and stratospheric air. Those so called streamers can, on a horizontal plane, be detected in N<sub>2</sub>O or O<sub>3</sub> since they are characterised by high N<sub>2</sub>O or low O<sub>3</sub> values compared to undisturbed mid-latitude values. A climatology of streamer events has been established, employing the chemical-transport model KASIMA, which is driven by ECMWF re-analyses (ERA) and operational analyses. For the first time, the seasonal and geographical distribution of streamer frequencies has been determined on the basis of 9 years of meteorological analyses.<br> <br> For the current investigation, a meridional gradient criterion has been newly formulated and applied to the N<sub>2</sub>O distributions calculated with KASIMA. A climatology has been derived by counting all streamer events between 21 and 25 km for the years 1990 to 1998. The results have been compared with a streamer climatology which has been established in the same way employing data of a multi-year simulation with the coupled chemistry-climate model ECHAM4.L39(DLR)/CHEM (E39/C). Both climatologies are qualitatively in agreement, in particular in the northern hemisphere, where much higher streamer frequencies are found in winter than in summer. In the southern hemisphere, the KASIMA analyses indicate strongest streamer activity in September. E39/C streamer frequencies clearly displays an offset from June to October, pointing to model deficiencies with respect to tropospheric dynamics. KASIMA and E39/C results agree well from November to May. Some of the findings give strong indications that the streamer events found in the altitude region between 21 and 25 km are mainly forced from the troposphere and are not directly related to the dynamics of the stratosphere, in particular not to the dynamics of the polar vortex.<br> <br> Sensitivity simulations with E39/C, which represent recent and possible future atmospheric conditions, have been employed to answer the question how climate change would alter streamer frequencies. This shows that the seasonal cycle does not change but that significant changes occur in months of minimum and maximum streamer frequencies. This could have an impact on the mid-latitude distribution of chemical tracers and compounds.
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In-situ observations of aerosol particles contained in cirrus crystals are presented and compared to interstitial aerosol size distributions (non-activated particles in between the cirrus crystals). The observations were conducted in cirrus clouds in the Southern and Northern Hemisphere mid-latitudes during the INCA project. The first campaign in March and April 2000 was performed from Punta Arenas, Chile (54°S) in pristine air. The second campaign in September and October 2000 was performed from Prestwick, Scotland (53°N) in the vicinity of the North Atlantic flight corridor. Size distribution measurements of crystal residuals (particles remaining after evaporation of the crystals) show that small aerosol particles (D<sub>p</sub>< 0.1 <font face="Symbol">m</font>m) dominate the number density of residuals. The crystal residual size distributions were significantly different in the two campaigns. On average the residual size distributions were shifted towards larger sizes in the Southern Hemisphere. For a given integral residual number density, the calculated particle volume was on average three times larger in the Southern Hemisphere. This may be of significance to the vertical redistribution of aerosol mass by clouds in the tropopause region. In both campaigns the mean residual size increased slightly with increasing crystal number density. The form of the residual size distribution did not depend on temperature as one might have expected considering different modes of nucleation. The observations of ambient aerosol particles were consistent with the expected higher pollution level in the Northern Hemisphere. The fraction of residual particles only contributes to approximately a percent or less of the total number of particles, which is the sum of the residual and interstitial particles. Excellent agreement between the CVI and FSSP-300 probes was found supporting the assumption that each crystal is associated with only one residual particle.
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A technique is demonstrated for estimating atmospheric mixing time-scales from in-situ data, using a Lagrangian model initialised from an Eulerian chemical transport model (CTM). This method is applied to airborne tropospheric CO observations taken during seven flights of the Mediterranean Intensive Oxidant Study (MINOS) campaign, of August 2001. The time-scales derived, correspond to mixing applied at the spatial scale of the CTM grid. They are relevant to the family of hybrid Lagrangian-Eulerian models, which impose Eulerian grid mixing to an underlying Lagrangian model. The method uses the fact that in Lagrangian tracer transport modelling, the mixing spatial and temporal scales are decoupled: the spatial scale is determined by the resolution of the initial tracer field, and the time scale by the trajectory length. The chaotic nature of lower-atmospheric advection results in the continuous generation of smaller spatial scales, a process terminated in the real atmosphere by mixing. Thus, a mix-down lifetime can be estimated by varying trajectory length so that the model reproduces the observed amount of small-scale tracer structure. Selecting a trajectory length is equivalent to choosing a mixing timescale. For the cases studied, the results are very insensitive to CO photochemical change calculated along the trajectories. That is, it was found that if CO was treated as a passive tracer, this did not affect the mix-down timescales derived, since the slow CO photochemistry does not have much influence at small spatial scales. The results presented correspond to full photochemical calculations. The method is most appropriate for relatively homogeneous regions, i.e. it is not too important to account for changes in aircraft altitude or the positioning of stratospheric intrusions, so that small scale structure is easily distinguished. The chosen flights showed a range of mix-down time upper limits: a very short timescale of 1 day for 8 August, due possibly to recent convection or model error, 3 days for 3 August, probably due to recent convective and boundary layer mixing, and 6-9 days for 16, 17, 22a, 22c and 24 August. These numbers refer to a mixing spatial scale of 2.8°, defined here by the resolution of the Eulerian grid from which tracer fields were interpolated to initialise the Lagrangian model. For the flight of 3 August, the observed concentrations result from a complex set of transport histories, and the models are used to interpret the observed structure, while illustrating where more caution is required with this method of estimating mix-down lifetimes.
