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A new model system for mapping and forecasting nitrogen deposition to the Baltic Sea has been developed. The system is based on the Lagrangian variable scale transport-chemistry model ACDEP (Atmospheric Chemistry and Deposition model), and aims at delivering deposition estimates to be used as input to marine ecosystem models. The system is tested by comparison of model results to measurements from monitoring stations around the Baltic Sea. The comparison shows that observed annual mean ambient air concentrations and wet depositions are well reproduced by the model. Diurnal mean concentrations of NH<sub>x</sub> (sum of NH<sub>3</sub> and NH<sub>4</sub><sup>+</sup>) and NO<sub>2</sub> are fairly well reproduced, whereas concentrations of total nitrate (sum of HNO<sub>3</sub> and NO<sub>3</sub><sup>-</sup>) are somewhat overestimated. Wet depositions of nitrate and ammonia are fairly well described for annual mean values, whereas the discrepancy is high for the monthly mean values and the wet depositions are rather poorly described concerning the diurnal mean values. The model calculations show that the annual atmospheric nitrogen deposition has a pronounced south--north gradient with depositions in the range about 1.0 T N km<sup>-2</sup> in the south and 0.2 T N km<sup>-2</sup> in the north. The results show that in 1999 the maximum diurnal mean deposition to the Danish waters appeared during the summer in the algae growth season. For the northern parts of the Baltic the highest depositions were distributed over most of the year. Total deposition to the Baltic Sea was for the year 1999 estimated to 318 kT N for an area of 464 406 km<sup>2</sup> equivalent to an average deposition of 684 kg N/km<sup>2</sup>.
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The identification of widespread sources of passive tracers out of atmospheric concentration measurements has become an important challenge of modern meteorology. The paper proposes some mathematical tracks to address the reconstruction of the complex space-time geometry of the sources of linear tracers. The methods are based upon the use of retroplumes. The inverse problem is addressed in a deterministic non statistical frame. The information obtained by local measurements is spread by introducing the concept of illumination. The constraint that the source is non negative is also addressed. The experimental source ETEX1 is rebuilt in order to evaluate an impulse response of the algorithms.
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In the summer 2000 EXPORT aircraft campaign (European eXport of Precursors and Ozone by long-Range Transport), two comprehensively instrumented research aircraft measuring a variety of chemical species flew wing tip to wing tip for a period of one and a quarter hours. During this interval a comparison was undertaken of the measurements of nitrogen oxide (NO), odd nitrogen species (NO<sub>y</sub>), carbon monoxide (CO) and ozone (O<sub>3</sub>). The comparison was performed at two different flight levels, which provided a 10-fold variation in the concentrations of both NO (10 to 1000 parts per trillion by volume (pptv)) and NO<sub>y</sub> (200 to over 2500 pptv). Large peaks of NO and NO<sub>y</sub> observed from the Falcon 20, which were at first thought to be from the exhaust of the C-130, were also detected on the 4 channel NO<sub>xy</sub> instrument aboard the C-130. These peaks were a good indication that both aircraft were in the same air mass and that the Falcon 20 was not in the exhaust plume of the C-130. Correlations and statistical analysis are presented between the instruments used on the two separate aircraft platforms. These were found to be in good agreement giving a high degree of correlation for the ambient air studied. Any deviations from the correlations are accounted for in the estimated inaccuracies of the instruments. These results help to establish that the instruments aboard the separate aircraft are reliably able to measure the corresponding chemical species in the range of conditions sampled and that data collected by both aircraft can be co-ordinated for purposes of interpretation.
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We consider the equilibrium behavior of a polydisperse aqueous droplet population as a function of relative humidity (RH) when a soluble trace gas, such as nitric acid, is present in the system. The droplet population experiences a splitting when the RH is increased sufficiently. This splitting is not related to the traditional Köhler activation of cloud droplets, as it may occur at relative humidities below 100%. Remarkably, the splitting always takes place in such a way that the largest size class of the (discretized) droplet population starts taking up the soluble trace gas efficiently, growing steeply as a function of RH, and forcing the smaller droplets to shrink. We consider this behavior in terms of open and closed system Köhler curves (open system referring to one in which the trace gas concentration remains constant and closed system to one in which the gas concentration decreases as a result of uptake of the trace gas). We show how the open and closed system Köhler curves are related, and that the splitting of the population can be explained in terms of closed system curves crossing the Köhler maxima of the open system curves. We then go on to consider time-dependent situations, and show that due to gas-phase mass transfer limitations, the splitting of the size distributions moves toward smaller sizes as the rate of RH increase becomes more rapid. Finally, we consider stratospheric supercooled ternary solution droplet populations, and show that the splitting described using the new theory may lead to formation of bimodal size distributions in the stratosphere.
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Single wavelength polarization lidar observations collected at Mt. Cimone (44.2º N, 10.7º E, 1870 m a.s.l.) during the June 2000 MINATROC campaign are analyzed to derive tropospheric profiles of aerosol extinction, depolarization, surface area and volume. Lidar retrievals for the 2170-2245 m level are compared to the same variables as computed from in situ measurements of particles size distributions, performed at the mountain top Station (2165 m a.s.l.) by a differential mobility analyzer (DMA) and an optical particle counter (OPC). A sensitivity analysis of this closure experiment shows that mean relative differences between the backscatter coefficients obtained by the two techniques undergo a sharp decrease when hygroscopic growth to ambient humidity is considered for the DMA dataset, otherwise representative of dry aerosols. Minimization of differences between lidar and size distribution-derived backscatter coefficients allowed to find values of the "best" refractive index, specific to each measurement. These results show the refractive index to increase for air masses proceeding from Africa and Western Europe. Lidar depolarization was observed to minimize mainly in airmasses proceeding from Western Europe, thus indicating a spherical, i.e. liquid nature for such aerosols. Conversely, African, Mediterranean and East Europe aerosol showed a larger depolarizing fraction, mainly due to coexisting refractory and soluble fractions. The analysis shows average relative differences between lidar and in-situ observations of 5% for backscatter, 36% for extinction 41% for surface area and 37% for volume. These values are well within the expected combined uncertainties of the lidar and in situ retrievals. Average differences further decrease during the Saharan dust transport event, when a lidar signal inversion model considering non-spherical scatterers is employed. The quality of the closure obtained between particle counter and lidar-derived aerosol surface area and volume observations constitutes a validation of the technique adopted to retrieve such aerosol properties on the basis of single-wavelength lidar observations.
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Size distribution measurements performed at five different stations have been investigated during a one-year period between 01 June 2000 and 31 May 2001 with focus on diurnal, seasonal and geographical differences of size distribution properties. The stations involved cover a large geographical area ranging from the Finnish Lapland (67º N) down to southern Sweden (56º N) in the order Värriö, Pallas, Hyytiälä, Aspvreten and Vavihill. The shape of the size distribution is typically bimodal during winter with a larger fraction of accumulation mode particles compared to the other seasons. Highest Aitken mode concentration is found during summer and spring during the year of study. The maximum of nucleation events occur during the spring months at all stations. Nucleation events occur during other months as well, although not as frequently. Large differences were found between different categories of stations. Northerly located stations such as Pallas and Värriö presented well-separated Aitken and accumulation modes, while the two modes often overlap significantly at the two southernmost stations Vavihill and Aspvreten.<br> <br> A method to cluster trajectories was used to analyse the impact of long-range transport on the observed aerosol properties. Clusters of trajectories arriving from the continent were clearly associated with size distributions shifted towards the accumulation mode. This feature was more pronounced the further south the station was located. Marine- or Arctic-type clusters were associated with large variability in the nuclei size ranges.<br> <br> A quasi-lagrangian approach was used to investigate transport related changes in the aerosol properties. Typically, an increase in especially Aitken mode concentrations was observed when advection from the north occurs, i.e. allowing more continental influence on the aerosol when comparing the different measurement sites. When trajectory clusters arrive to the stations from SW, a gradual decrease in number concentration is experienced in all modes as latitude of measurement site increases.
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A Berner low pressure impactor was used to collect size-segregated aerosol samples at Finokalia, located on the north-eastern coast of Crete, Greece during July 2000 and January 2001. Several samples were also collected during the summer campaign aboard the research vessel "AEGAIEO" in the Aegean Sea. Gravimetric analysis and inversion techniques yielded daily PM1 and PM10 mass concentrations. The samples were also analysed by PIXE giving the elemental size distributions of Al, Si, K, Ca, Ti, Mn, Fe, Sr, S, Cl, Ni, V, Cu, Cr, Zn, and Pb. The crustal elements and sea-salt had a unimodal supermicron size distribution. Sulphur was found predominantly in submicron fractions. K, V, and Ni exhibited a bimodal distribution with a submicron mode produced by forest fires and oil combustion. The anthropogenic elements had broad and not well-defined distributions. The time series for PM1 and PM10 mass and elemental concentrations showed both daily and seasonal variation. Higher mass concentrations were observed during two incursions of Saharan dust, whilst higher concentrations of S, Cu, Zn, and Pb were encountered in samples collected in air masses arriving from northern Greece or the western coast of Turkey. Elevated concentrations of chlorine were found in samples with air masses either originating above the Atlantic Ocean and arriving at Finokalia via western Europe or recirculating over the western coast of the Black Sea.
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CO vertical profiles have been retrieved from solar absorption FTIR spectra recorded at the NDSC station of the Jungfraujoch (46.5º N, 8º E and 3580 m a.s.l.) for the period from January 1997 to May 2001. The characterisation of these profiles has been established by an information content analysis and an estimation of the error budgets. A partial validation of the profiles has been performed through comparisons with correlative measurements. The average volume mixing ratios (vmr) in the 3 km layer above the station have been compared with coincident surface measurements. The agreement between monthly means from both measurement techniques is very good, with a correlation coefficient of 0.87, and no significant bias observed. The FTIR total columns have also been compared to CO partial columns above 3580 m a.s.l. derived from the MOPITT (Measurement Of Pollution In The Troposphere) instrument for the period March 2000 to May 2001. Relative to the FTIR columns, the MOPITT partial columns exhibit a positive bias of 8±8% for daytime and of 4±7% for nighttime measurements.
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Convection reduces greenhouse effect by transporting a certain amount of non-radiative dynamic energy to the upper atmosphere, where this energy dissipates and radiates into space without interaction with greenhouse substances in the lower atmosphere. In this paper we show that the height of the convective layer z<sub>c</sub> is finite and independent of atmospheric optical thickness τ<sub>s</sub> at large values of the latter. We derive an analytical formula for z<sub>c</sub> at large values of τ<sub>s</sub> for condensable and non-condensable greenhouse substances. The formula obtained yields reasonable quantitative estimates of the observed height of convective layer on Venus and at low latitudes on Earth, where atmospheric thickness of water vapor is maximum.<br> <br> The dissipative power of dynamic convective processes is limited by the incoming flux of solar radiation. Height of convective layer being finite, values of optical depth at the top of the convective layer and at the mean height of convective energy dissipation increase proportionally to the atmospheric optical thickness, while the contribution of convective energy fluxes to formation of the outgoing flux of thermal radiation proportionally diminishes. As far as optical thickness of condensable greenhouse substances grows exponentially with increasing surface temperature, the obtained results lead to the conclusion that the outgoing thermal radiation into space in the presence of convection tends exponentially to zero with increasing surface temperature, instead of reaching a finite plateau as suggested by earlier radiative-convective studies.
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Nitrogen oxides (NO+NO<sub>2</sub>=NO<sub>x</sub> and reservoir species) are important trace gases in the troposphere with impact on human health, atmospheric chemistry and climate. Besides natural sources (lightning, soil emissions) and biomass burning, fossil fuel combustion is estimated to be responsible for about 50% of the total production of NO<sub>x</sub>. Since human activity in industrialized countries largely follows a seven-day cycle, fossil fuel combustion is expected to be reduced during weekends. This "weekend effect" is well known from local, ground based measurements, but has never been analysed on a global scale before.<br> <br> The Global Ozone Monitoring Experiment (GOME) on board the ESA-satellite ERS-2 allows measurements of NO<sub>2</sub> column densities. By estimating and subtracting the stratospheric column, and considering radiative transfer, vertical column densities (VCD) of tropospheric NO<sub>2</sub> can be determined (e.g. Leue et al., 2001). We demonstrate the statistical analysis of weekly cycles of tropospheric NO<sub>2 </sub>VCDs for different regions of the world. In the cycles of the industrialized regions and cities in the US, Europe and Japan a clear Sunday minimum of tropospheric NO<sub>2</sub> VCD can be seen. Sunday NO<sub>2</sub> VCDs are about 25-50% lower than working day levels. Metropolitan areas with other religious and cultural backgrounds (Jerusalem, Mecca) show different weekly patterns corresponding to different days of rest. In China, no weekly pattern can be found.<br> <br> The presence of a weekly cycle in the measured tropospheric NO<sub>2 </sub>VCD may help to identify the different anthropogenic source categories. Furthermore, we estimated the lifetime of tropospheric NO<sub>2</sub> by analysing the mean weekly cycle exemplarily over Germany, obtaining a value of about 6 h in summer and 18-24 h in winter.
