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Mountain wave PSC dynamics and microphysics from ground-based lidar measurements and meteorological modeling

The day-long observation of a polar stratospheric cloud (PSC) by two co-located ground-based lidars at the Swedish research facility Esrange (67.9° N, 21.1° E) on 16 January 1997 is analyzed in terms of PSC dynamics and microphysics. Mesoscale modeling is utilized to simulate the meteorological setting of the lidar measurements. Microphysical properties of the PSC particles are retrieved by comparing the measured particle depolarization ratio and the PSC-averaged lidar ratio with theoretical optical data derived for different particle shapes. In the morning, nitric acid trihydrate (NAT) particles and then increasingly coexisting liquid ternary aerosol (LTA) were detected as outflow from a mountain wave-induced ice PSC upwind Esrange. The NAT PSC is in good agreement with simulations for irregular-shaped particles with length-to-diameter ratios between 0.75 and 1.25, maximum dimensions from 0.7 to 0.9 µm, and a number density from 8 to 12 cm-3 and the coexisting LTA droplets had diameters from 0.7 to 0.9 µm, a refractive index of 1.39 and a number density from 7 to 11 cm-3. The total amount of condensed HNO3 was in the range of 8–12 ppbv. The data provide further observational evidence that NAT forms via deposition nucleation on ice particles as a number of recently published papers suggest. By early afternoon the mountain-wave ice PSC expanded above the lidar site. Its optical data indicate a decrease in minimum particle size from 3 to 1.9 µm with time. Later on, following the weakening of the mountain wave, wave-induced LTA was observed only. Our study demonstrates that ground-based lidar measurements of PSCs can be comprehensively interpreted if combined with mesoscale meteorological data.
Polycyclic aromatic hydrocarbons (PAHs) in the atmospheres of two French alpine valleys: sources and temporal patterns

Alpine valleys represent some of the most important crossroads for international heavy-duty traffic in Europe, but the full impact of this traffic on air quality is not known due to a lack of data concerning these complex systems. As part of the program "Pollution des Vallées Alpines" (POVA), we performed two sampling surveys of polycyclic aromatic hydrocarbons (PAHs) in two sensitive valleys: the Chamonix and Maurienne Valleys, between France and Italy. Sampling campaigns were performed during the summer of 2000 and the winter of 2001, with both periods taking place during the closure of the "Tunnel du Mont-Blanc". The first objective of this paper is to describe the relations between PAH concentrations, external parameters (sampling site localization, meteorological parameters, sources), and aerosol characteristics, including its carbonaceous fraction (OC and EC). The second objective is to study the capacity of PAH profiles to accurately distinguish the different emission sources. Temporal evolution of the relative concentration of an individual PAH (CHR) and the PAH groups BghiP+COR and BbF+BkF is studied in order to differentiate wood combustion, gasoline, and diesel emissions, respectively. The results show that the total particulate PAH concentrations were higher in the Chamonix valley during both seasons, despite the cessation of international traffic. Seasonal cycles, with higher concentrations in winter, are also stronger in this valley. During winter, particulate PAH concentration can reach very high levels (up to 155 ng.m-3) in this valley during cold anticyclonic periods. The examination of sources shows the impact during summer of heavy-duty traffic in the Maurienne valley and of gasoline vehicles in the Chamonix valley. During winter, Chamonix is characterized by the strong influence of wood combustion in residential fireplaces, even if the temporal evolution of specific PAH ratios are difficult to interpret. Information on sources given by PAH profiles can only be considered in qualitative terms.
Aerosol-ozone correlations during dust transport episodes

Its location in the Mediterranean region and its physical characteristics render Mt. Cimone (44°11′ N, 10°42′ E), the highest peak of the Italian northern Apennines (2165 m asl), particularly suitable to study the transport of air masses from the north African desert area to Europe. During these northward transports 12 dust events were registered in measurements of the aerosol concentration at the station during the period June–December 2000, allowing the study of the impact of mineral dust transports on free tropospheric ozone concentrations, which were also measured at Mt. Cimone. Three-dimensional backward trajectories were used to determine the air mass origin, while TOMS Aerosol Index data for the Mt. Cimone area were used to confirm the presence of absorbing aerosol over the measurement site. A trajectory statistical analysis allowed identifying the main source areas of ozone and aerosols. The analysis of these back trajectories showed that central Europe and north and central Italy are the major pollution source areas for ozone and fine aerosol, whereas the north African desert regions were the most important source areas for coarse aerosol and low ozone concentrations. During dust events, the Mt. Cimone mean volume concentration for coarse particles was 6.18 µm3/cm3 compared to 0.63 µm3/cm3 in dust-free conditions, while the ozone concentrations were 4% to 21% lower than the monthly mean background values. Our observations show that surface ozone concentrations were lower than the background values in air masses coming from north Africa, and when these air masses were also rich in coarse particles, the lowest ozone values were registered. Moreover, preliminary results on the possible impact of the dust events on PM10 and ozone values measured in Italian urban and rural areas showed that during the greater number of the considered dust events, significant PM10 increases and ozone decreases have occurred in the Po valley.
Analysis of a jet stream induced gravity wave associated with an observed ice cloud over Greenland

A polar stratospheric ice cloud (PSC type II) was observed by airborne lidar above Greenland on 14 January 2000. It was the unique observation of an ice cloud over Greenland during the SOLVE/THESEO 2000 campaign. Mesoscale simulations with the hydrostatic HRM model are presented which, in contrast to global analyses, are capable to produce a vertically propagating gravity wave that induces the low temperatures at the level of the PSC afforded for the ice formation. The simulated minimum temperature is ~8 K below the driving analyses and ~4.5 K below the frost point, exactly coinciding with the location of the observed ice cloud. Despite the high elevations of the Greenland orography the simulated gravity wave is not a mountain wave. Analyses of the horizontal wind divergence, of the background wind profiles, of backward gravity wave ray-tracing trajectories, of HRM experiments with reduced Greenland topography and of several diagnostics near the tropopause level provide evidence that the wave is emitted from an intense, rapidly evolving, anticyclonically curved jet stream. The precise physical process responsible for the wave emission could not be identified definitely, but geostrophic adjustment and shear instability are likely candidates. In order to evaluate the potential frequency of such non-orographic polar stratospheric cloud events, the non-linear balance equation diagnostic is performed for the winter 1999/2000. It indicates that ice-PSCs are only occasionally generated by gravity waves emanating from spontaneous adjustment.
Long-range transport of ozone and related pollutants over the North Atlantic in spring and summer

This paper presents strong experimental evidence for a major perturbation in ozone concentrations over large parts of the North Atlantic Ocean from the surface to 8 km associated with continental pollutants. The evidence was gathered in the course of 7 flights by the UK Meteorological Office C-130 aircraft based on the Azores, and 4 ferry flights between the UK to the Azores in spring and summer 1997 as a component of the NERC-funded ACSOE project. The total latitude range covered was approximately 55°N–25°N, and the longitude range was approximately 0° to 40°W. Many profiles were made between the sea surface and altitudes up to 9 km to survey the composition of the marine atmosphere. The C-130 aircraft was comprehensively equipped to measure many chemical and physical parameters along with standard meteorological instrumentation. Thus it was able to measure ozone and speciated NOy, along with tracers including water vapour, carbon monoxide and condensation nuclei, in near real time. The overall "picture" of the troposphere over large parts of the North Atlantic is of layers of pollution from the continents of different ages interspersed with layers of air uplifted from the marine boundary layer. The lowest ozone concentrations were recorded in the marine boundary layer where there is evidence for extensive ozone destruction in summer. Flights were made to penetrate the outflow of hurricane Erica, to determine the southerly extent of polluted air in summer, to examine the impact of frontal systems on the composition of remote marine air, and to trace long-range pollution from the west coast of the USA interspersed with air with a stratospheric origin. In one of the spring flights it is possible that a plume of polluted air with high ozone and NOy, and with an origin in southeast Asia, was intercepted off the coast of Portugal. The concentrations of NOx, in this plume were sufficient for ozone formation to be continuing along its track from west to east. The instrument to measure NOy almost certainly was only measuring the sum of organic nitrates (mostly in the form of PAN) plus NOx. The high correlation between NOy and ozone under these conditions strongly suggests a non-stratospheric source for most of the ozone encountered over large parts of the atmosphere upwind of Europe. There was a marked seasonal variation in the NOy with about twice as much present in the spring flights than in the summer flights. The overall ozone levels in both spring and summer were somewhat similar although the highest ozone concentration encountered (~100 ppbv) was observed in summer in some polluted layers in mid Atlantic with an origin in the boundary layer over the southeastern USA. The bulk of the pollutants, ozone, CO, and NOy, were in the free troposphere at altitudes between 3 and 8 km. The only instances of pollution at lower levels were in the form of ship plumes, which were encountered several times. The data therefore strongly support the need for more in-situ aircraft experiments to quantify and understand the phenomenon of long-range transport of pollution from continent to continent. Observations at ground-based stations are inadequate for this purpose and satellite data is incomplete both in terms of its altitude detail and in the extent of chemical speciation, particularly for ascertaining whether chemical production and destruction processes for ozone are occurring.
Ultra-violet absorption cross sections of isotopically substituted nitrous oxide species: 14N14NO, 15N14NO, 14N15NO and 15N15NO

The isotopically substituted nitrous oxide species 14N14NO, 15N14NO, 14N15NO and 15N15NO were investigated by ultra-violet (UV) absorption spectroscopy. High precision cross sections were obtained for the wavelength range 181 to 218nm at temperatures of 233 and 283K. These data are used to calculate photolytic isotopic fractionation constants as a function of wavelength. The fractionation constants were used in a three-dimensional chemical transport model in order to simulate the actual fractionation of N2O in the stratosphere, and the results were found to be in good agreement with field studies.
Remote sensing of water cloud droplet size distributions using the backscatter glory: a case study

Cloud single scattering properties are mainly determined by the effective radius of the droplet size distribution. There are only few exceptions where the shape of the size distribution affects the optical properties, in particular the rainbow and the glory directions of the scattering phase function. Using observations by the Compact Airborne Spectrographic Imager (CASI) in 180° backscatter geometry, we found that high angular resolution aircraft observations of the glory provide unique new information which is not available from traditional remote sensing techniques: Using only one single wavelength, 753nm, we were able to determine not only optical thickness and effective radius, but also the width of the size distribution at cloud top. Applying this novel technique to the ACE-2 CLOUDYCOLUMN experiment, we found that the size distributions were much narrower than usually assumed in radiation calculations which is in agreement with in-situ observations during this campaign. While the shape of the size distribution has only little relevance for the radiative properties of clouds, it is extremely important for understanding their formation and evolution.
Assessment of the applicability of NO-NO2-O3 photostationary state to long-term measurements at the Hohenpeissenberg GAW Station, Germany

Continuous measurements of concentrations of reactive gases, radiation, and meteorological parameters are carried out at the Meteorological Observatory Hohenpeissenberg (MOHp) as part of the Global Atmosphere Watch (GAW) Program. NO, NO2, O3 and JNO2 data from a four-year period (March 1999-December 2002) are evaluated for consistency with photochemical steady state (PSS, Φ=1) conditions. The extent of deviation from PSS reveals a strong dependence on wind direction at the station. Median values of Φ in the south sector are in the range of 2.5-5.7 and show a high variability. In contrast, values for the other directions show a relatively low variability around a median level of 2. When taking into account peroxy radical concentrations (Φext=1) PSS was reached in 13-32% of all cases for the years 1999-2002. The differences in wind sectors can be explained by local effects. It is shown that the height of the sample inlet line, its distance to the forest and the surrounding topography has a strong impact on both the absolute and relative deviations from PSS. Global irradiance and thus, photolysis of NO2 is reduced within the dense forest. Since the reaction of NO with O3 is still proceeding under these conditions, increased NO2/NO ratios are produced locally in air which is transported through the forest and advected to the MOHp site. Estimates of the peroxy radical concentration (RO2) inferred from PSS are compared with peroxy radical measurements made at the site in June 2000 during a three-week campaign. The PSS derived RO2 levels were higher than corresponding measured levels by at least a factor of 2-3. This analysis was made for a wind sector with minimal local effects on PSS. Thus the corresponding Φ median of 2 can be regarded as an upper limit for a deviation from PSS due to chemical reactions, i.e. by peroxy radicals and possible other oxidants converting additional NO to NO2.
Partially oxidised organic components in urban aerosol using GCXGC-TOF/MS

Partially oxidised organic compounds associated with PM2.5 aerosol collected in London, England, have been analysed using direct thermal desorption coupled to comprehensive gas chromatography-time of flight mass spectrometry (GCXGC-TOF/MS). Over 10000 individual organic components were isolated from around 10µg of aerosol material in a single procedure and with no sample pre-treatment. Chemical functionalities observed using this analytical technique ranged from alkanes to poly-oxygenated species. The chemical band structures commonly used in GCXGC for group type identifications overlap for this sample type, and have required mass spectrometry as an additional level of instrument dimensionality. An investigation of oxygenated volatile organic compounds (o-VOC) contained within urban aerosol has been performed and in a typical sample around 130 o-VOCs were identified based on retention behaviour and spectral match. In excess of 100 other oxygenated species were also observed but lack of mass spectral library or pure components prevents positive identification. Many of the carbonyl species observed could be mechanistically linked to gas phase aromatic hydrocarbon oxidation and there is good agreement in terms of speciation between the urban samples analysed here and those degradation products observed in smog chamber experiments of aromatic oxidation. The presence of partially oxidised species such as linear chain aldehydes and ketones and cyclic products such as furanones suggests that species generated early in the oxidative process may undergo gas to particle partitioning despite their relatively high volatility.
Uptake study of ClONO2 and BrONO2 by Halide containing droplets

The uptake kinetics of gaseous ClONO2 and BrONO2 on aqueous surfaces were measured, as a function of temperature and liquid composition (pure water and NaCl or NaBr containing solutions) using the droplet train technique coupled to a mass spectrometer. The uptake kinetics are driven by the reactivity of these gases and, for both compounds, the uptake rates on pure water or on NaCl solutions (0.1M) are comparable. The uptake coefficient γ of ClONO2 does not depend on the temperature while that of BrONO2 increases slightly when the temperature is raised from 272 to 280K. For ClONO2 and BrONO2, the uptake rates increase on NaBr-doped droplets, enabling the estimation of the mass accommodation coefficient α. The corresponding values for α are 0.108±0.033 for ClONO2 and 0.063±0.021 for BrONO2 where the statistical errors correspond to ±2σ. The reactions of ClONO2 and BrONO2 on NaCl solutions lead respectively to the formation of Cl2 and BrCl. The uptake of ClONO2 on NaBr solutions generates BrCl as primary product, which in turn can react with NaBr to produce Br2. As expected, the only product of BrONO2 reaction on NaBr solution is Br2.