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In this paper, we study the transport of air masses to San Pietro Capofiume (SPC) in Po Valley, Italy, by means of back trajectories analysis. Our main aim is to investigate whether air masses originate over different regions on nucleation event days and on nonevent days, during three years when nucleation events have been continuously recorded at SPC. The results indicate that nucleation events occur frequently in air masses arriving from Central Europe, whereas event frequency is much lower in the air transported from southern directions and from the Atlantic Ocean. We also analyzed the behaviour of meteorological parameters during 96 h transport to SPC, and found that, on average, event trajectories undergo stronger subsidence during the last 12 h before the arrival at SPC than nonevent trajectories. This causes a reversal in the temperature and relative humidity (RH) differences between event and nonevent trajectories: between 96 and 12 h back time, temperature is lower and RH is higher for event than nonevent trajectories and between 12 and 0 h vice versa. Boundary layer mixing is stronger along the event trajectories compared to nonevent trajectories. The absolute humidity (AH) is similar for the event and nonevent trajectories between about 96 h and about 60 h back time, but after that, the event trajectories AH becomes lower due to stronger rain. We also studied transport of SO<sub>2</sub> to SPC, and conclude that although sources in Po Valley most probably dominate the measured concentrations, certain Central and Eastern European sources also make a substantial contribution.
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The objective of this study is to demonstrate how polar ozone depletion can be mapped and quantified by assimilating ozone data from satellites into the wind driven transport model DIAMOND, (Dynamical Isentropic Assimilation Model for OdiN Data). By assimilating a large set of satellite data into a transport model, ozone fields can be built up that are less noisy than the individual satellite ozone profiles. The transported fields can subsequently be compared to later sets of incoming satellite data so that the rates and geographical distribution of ozone depletion can be determined. By tracing the amounts of solar irradiation received by different air parcels in a transport model it is furthermore possible to study the photolytic reactions that destroy ozone. <br><br> In this study, destruction of ozone that took place in the Antarctic winter of 2003 and in the Arctic winter of 2002/2003 have been examined by assimilating ozone data from the ENVISAT/MIPAS and Odin/SMR satellite-instruments. Large scale depletion of ozone was observed in the Antarctic polar vortex of 2003 when sunlight returned after the polar night. By mid October ENVISAT/MIPAS data indicate vortex ozone depletion in the ranges 80–100% and 70–90% on the 425 and 475 K potential temperature levels respectively while the Odin/SMR data indicates depletion in the ranges 70–90% and 50–70%. The discrepancy between the two instruments has been attributed to systematic errors in the Odin/SMR data. <br><br> Assimilated fields of ENVISAT/MIPAS data indicate ozone depletion in the range 10–20% on the 475 K potential temperature level, (~19 km altitude), in the central regions of the 2002/2003 Arctic polar vortex. Assimilated fields of Odin/SMR data on the other hand indicate ozone depletion in the range 20–30%.
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Soluble compounds present in atmospheric aerosol facilitate their transformation into cloud droplets by depressing the equilibrium vapor pressure required for activation. Their impact depends on the amount of dissolved substance in the aerosol aqueous phase, which in turn is controlled by its solubility. This study explores the impact of particle curvature on solubility, expressed in terms of a Kelvin enhancement. The augmented solubility, termed "Curvature Enhanced Solubility" (CES), is then introduced into Köhler theory for assessment of its impact on CCN activity for several organic compounds with a wide range of aqueous solubility. The interfacial energy between solute and aqueous phase required for quantification of CES is determined from existing correlations based on bulk solubility, and concurrent measurements of contact angle and surface tension. A number of important findings arise from this study: <i>i)</i> CES can substantially increase solubility and impact CCN activity but only if the aerosol is initially wet, <i>ii)</i> CES can stabilize highly supersaturated solutions, and provide a mechanism for retention of an aerosol aqueous phase even at very low relative humidity (RH), and, <i>iii)</i> trace amounts of surfactant impurities can magnify the impact of CES.
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Absolute principal component analysis can be applied, with suitable modifications, to atmospheric aerosol size distribution measurements. This method quickly and conveniently reduces the dimensionality of a data set. The resulting representation of the data is much simpler, but preserves virtually all the information present in the original measurements. Here we demonstrate how to combine the simplified size distribution data with trace gas measurements and meteorological data to determine the origins of the measured particulate matter using absolute principal component analysis. We have applied the analysis to four different sets of field measurements that were conducted at three sites in southern Ontario. Several common factors were observed at all the sites; these were identified as photochemically produced secondary aerosol particles, regional pollutants (including accumulation mode aerosol particles), and trace gas variations associated with boundary layer dynamics. Each site also exhibited a factor associated specifically with that site: local industrial emissions in Hamilton (urban site), processed nucleation mode particles at Simcoe (polluted rural site), and transported fine particles at Egbert (downwind from Toronto).
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Principal component analysis provides a fast and robust method to reduce the data dimensionality of an aerosol size distribution data set. Here we describe a methodology for applying principal component analysis to aerosol size distribution measurements. We illustrate the method by applying it to data obtained during five field studies. Most variations in the sub-micrometer aerosol size distribution over periods of weeks can be described using 5 components. Using 6 to 8 components preserves virtually all the information in the original data. A key aspect of our approach is the introduction of a new method to weight the data; this preserves the orthogonality of the components while taking the measurement uncertainties into account. We also describe a new method for identifying the approximate number of aerosol components needed to represent the measurement quantitatively. Applying Varimax rotation to the resultant components decomposes a distribution into independent monomodal distributions. Normalizing the components provides physical meaning to the component scores. The method is relatively simple, computationally fast, and numerically robust. The resulting data simplification provides an efficient method of representing complex data sets and should greatly assist in the analysis of size distribution data.
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An air pollution plume from Southern and Eastern Asia, including regions in India and China, was predicted by the FLEXPART particle dispersion model to arrive in the upper troposphere over Europe on 24–25 March 2006. According to the model, the plume was exported from Southeast Asia six days earlier, transported into the upper troposphere by a warm conveyor belt, and travelled to Europe in a fast zonal flow. This is confirmed by the retrievals of carbon monoxide (CO) from AIRS satellite measurements, which are in excellent agreement with the model results over the entire transport history. The research aircraft DLR Falcon was sent into this plume west of Spain on 24 March and over Southern Europe on 25 March. On both days, the pollution plume was found close to the predicted locations and, thus, the measurements taken allowed the first detailed characterization of the aerosol content and chemical composition of an anthropogenic pollution plume after a nearly hemispheric transport event. The mixing ratios of CO, reactive nitrogen (NO<sub>y</sub>) and ozone (O<sub>3</sub>) measured in the Asian plume were all clearly elevated over a background that was itself likely elevated by Asian emissions: CO by 17–34 ppbv on average (maximum 60 ppbv) and O<sub>3</sub> by 2–9 ppbv (maximum 22 ppbv). Positive correlations existed between these species, and a ΔO<sub>3</sub>/ΔCO slope of 0.25 shows that ozone was formed in this plume, albeit with moderate efficiency. Nucleation mode and Aitken particles were suppressed in the Asian plume, whereas accumulation mode aerosols were strongly elevated and correlated with CO. The suppression of the nucleation mode was likely due to the large pre-existing aerosol surface of the transported larger particles. Super-micron particles, likely desert dust, were found in part of the Asian pollution plume and also in surrounding cleaner air. The aerosol light absorption coefficient was enhanced in the plume (average values for individual plume encounters 0.25–0.70 Mm<sup>−1</sup>), as was the fraction of non-volatile Aitken particles. This indicates that black carbon (BC) was an important aerosol component. During the flight on 25 March, which took place on the rear of a trough located over Europe, a mixture of Asian pollution and stratospheric air was found. Asian pollution was mixing into the lower stratosphere, and stratospheric air was mixing into the pollution plume in the troposphere. Turbulence was encountered by the aircraft in the mixing regions, where the thermal stability was low and Richardson numbers were below 0.2. The result of the mixing can clearly be seen in the trace gas data, which are following mixing lines in correlation plots. This mixing with stratospheric air is likely very typical of Asian air pollution, which is often lifted to the upper troposphere and, thus, transported in the vicinity of stratospheric air.
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This paper evaluates the performance of various linear ozone photochemistry parametrizations using the stratosphere-troposphere data assimilation system of the Met Office. A set of experiments were run for the period 23 September 2003 to 5 November 2003 using the Cariolle (v1.0 and v2.1), LINOZ and Chem2D-OPP (v0.1 and v2.1) parametrizations. All operational meteorological observations were assimilated, together with ozone retrievals from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). Experiments were validated against independent data from the Halogen Occultation Experiment (HALOE) and ozonesondes. Additionally, a simple offline method for comparing the parametrizations is introduced. <br><br> It is shown that in the upper stratosphere and mesosphere, outside the polar night, ozone analyses are controlled by the photochemistry parametrizations and not by the assimilated observations. The most important factor in getting good results at these levels is to pay attention to the ozone and temperature climatologies in the parametrizations. There should be no discrepancies between the climatologies and the assimilated observations or the model, but there is also a competing demand that the climatologies be objectively accurate in themselves. Conversely, in the lower stratosphere outside regions of heterogeneous ozone depletion, the ozone analyses are dominated by observational increments and the photochemistry parametrizations have little influence. <br><br> We investigate a number of known problems in LINOZ and Cariolle v1.0 in more detail than previously, and we find discrepancies in Cariolle v2.1 and Chem2D-OPP v2.1, which are demonstrated to have been removed in the latest available versions (v2.8 and v2.6 respectively). In general, however, all the parametrizations work well through much of the stratosphere, helped by the presence of good quality assimilated MIPAS observations.
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An intercomparison of three Fourier transform spectrometers (FTSs) with significantly different resolutions is presented. The highest-resolution instrument has a maximum optical path difference of 250 cm, and the two lower-resolution instruments have maximum optical path differences of 50 cm and 25 cm. The results indicate that the two lower-resolution instruments can retrieve total column amounts of O<sub>3</sub>, HCl, N<sub>2</sub>O and CH<sub>4</sub> using the SFIT2 retrieval code with percent differences from the high-resolution instrument generally better than 4%. Total column amounts of the stratospheric species (O<sub>3</sub> and HCl) have larger differences than those of the tropospheric species (N<sub>2</sub>O and CH<sub>4</sub>). Instrument line shape (ILS) information is found to be of critical importance when retrieving total columns of stratospheric gases from the lower-resolution instruments. Including the ILS information in the retrievals significantly reduces the difference in total column amounts between the three instruments. The remaining errors for stratospheric species total column amounts can be attributed to the lower sensitivity of the lower-resolution FTSs to the stratosphere.
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The direct detection of glyoxal (CHOCHO), the smallest α-dicarbonyl, in the open atmosphere by active differential optical absorption spectroscopy (DOAS) has recently been demonstrated (Volkamer et al., 2005a) and triggered the very recent successful detection of CHOCHO from space (Kurosu et al., 2005; Wittrock et al., 2006; Beirle et al., 2006). Here we report the first comprehensive analysis of CHOCHO by passive multi axis differential optical absorption spectroscopy (MAX-DOAS). CHOCHO and NO<sub>2</sub> slant column measurements were conducted at the Massachusetts Institute of Technology (MIT), Cambridge, USA, and on board the research vessel Ron Brown in the Gulf of Maine as part of the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) 2004 campaign. For a day with nearly clear sky conditions, radiative transfer modeling was employed to derive diurnal CHOCHO mixing ratios in the planetary boundary layer (PBL) for both sites. CHOCHO mixing ratios at MIT varied from 40 to 140 ppt, with peak values observed around noon. Mixing ratios over the Gulf of Maine were found to be up to 2.5 times larger than at MIT. The CHOCHO-to-NO<sub>2</sub> ratio at MIT was <0.03, and enhancements of this ratio by up to two orders of magnitude were found over the Gulf of Maine. This paper focuses on the methodological aspects involved with MAX-DOAS measurements of CHOCHO.
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In this paper we present a case study of a record low ozone event observed over the UK in January 2006. We focus on the dynamical processes that cause this event. This is done by examining the observations, meteorological analyses and back trajectories calculated by the NAME III atmospheric dispersion model. We show that this model, hitherto only used for tropospheric pollution studies, can be an important and effective tool for the examination of transport in the upper troposphere/lower stratosphere (UTLS) and mid-stratosphere regions. <br><br> A record low total ozone column of 177 DU was observed at Reading, UK, on 19 January 2006. Low ozone values were also recorded at other stations in Northwest Europe around this date. Ozonesonde measurements indicate the depletion is occurring in two distinct vertical regions, with around a third of the reduction in total ozone column values originating from the mid-stratosphere and the rest from the UTLS region. Evidence suggests that air inside the stratospheric polar vortex was poor in ozone prior to 19 January and the occurrence of a major stratospheric warming shifted this air over Northwest Europe. In addition we show that moderate ozone depletion, related to the lifting of the tropopause and divergence in the lower stratosphere associated with the presence of an anticyclone, is also a plausible mechanism for the record low ozone column that is observed. <br><br> In order to confirm that both mid-stratosphere and UTLS transport processes are responsible for the record low ozone values, we perform turbulent back trajectory calculations using the Met Office NAME III model. The results show that air parcels in the mid-stratosphere that arrive over the British Isles on 19 January originate in the polar vortex, and furthermore that air parcels near the tropopause arrive from low latitudes and are transported anticyclonically. Therefore this strongly suggests that the record low ozone values are due to a combination of a raised tropopause with increased divergence in the lower stratosphere and the presence of low ozone stratospheric air aloft.
