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Single particle analysis of ice crystal residuals observed in orographic wave clouds over Scandinavia during INTACC experiment

Individual ice crystal residual particles collected over Scandinavia during the INTACC (INTeraction of Aerosol and Cold Clouds) experiment in October 1999 were analyzed by Scanning Electron Microscopy (SEM) equipped with Energy-Dispersive X-ray Analysis (EDX). Samples were collected onboard the British Met Office Hercules C-130 aircraft using a Counterflow Virtual Impactor (CVI). This study is based on six samples collected in orographic clouds. The main aim of this study is to characterize cloud residual elemental composition in conditions affected by different airmasses. In total 609 particles larger than 0.1 μm diameter were analyzed and their elemental composition and morphology were determined. Thereafter a hierarchical cluster analysis was performed on the signal detected with SEM-EDX in order to identify the major particle classes and their abundance. A cluster containing mineral dust, represented by aluminosilicates, Fe-rich and Si-rich particles, was the dominating class of particles, accounting for about 57.5% of the particles analyzed, followed by low-Z particles, 23.3% (presumably organic material) and sea salt (6.7%). Sulfur was detected often across all groups, indicating ageing and in-cloud processing of particles. A detailed inspection of samples individually unveiled a relationship between ice crystal residual composition and airmass origin. Cloud residual samples from clean airmasses (that is, trajectories confined to the Atlantic and Arctic Oceans and/or with source altitude in the free troposphere) were dominated primarily by low-Z and sea salt particles, while continentally-influenced airmasses (with trajectories that originated or traveled over continental areas and with source altitude in the continental boundary layer) contained mainly mineral dust residuals. Comparison of residual composition for similar cloud ambient temperatures around –27°C revealed that supercooled clouds are more likely to persist in conditions where low-Z particles represent significant part of the analyzed cloud residual particles. This indicates that organic material may be poor ice nuclei, in contrast to polluted cases when ice crystal formation was observed at the same environmental conditions and when the cloud residual composition was dominated by mineral dust. The presented results suggest that the chemical composition of cloud nuclei and airmass origin have a strong impact on the ice formation through heterogeneous nucleation in supercooled clouds.
Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change

In spite of impressive advances in recent years, our present understanding of organic aerosol (OA) composition, physical and chemical properties, sources and transformation characteristics is still rather limited, and their environmental effects remain highly uncertain. This paper discusses and prioritizes issues related to organic aerosols and their effects on atmospheric processes and climate, providing a basis for future activities in the field. Four main topical areas are addressed: i) sources of OA; ii) formation transformation and removal of OA; iii) physical, chemical and mixing state of OA; iv) atmospheric modelling of OA. Key questions and research priorities regarding these four areas are synthesized in this paper, and outstanding issues for future research are presented for each topical area. In addition, an effort is made to formulate a basic set of consistent and universally applicable terms and definitions for coherent description of atmospheric OA across different scales and disciplines.
Technical note: A method for measuring size-resolved CCN in the atmosphere

We present a method to investigate cloud condensation nuclei (CCN) concentrations and activation efficiencies as a function of two independent variables, aerosol particle size and water vapor supersaturation. To date, most ambient CCN measurements have been made as the integral (total) CCN concentration as a function of water vapor supersaturation only. However, since CCN properties of aerosol particles are strongly dependent on particle size, as well as on chemical composition, which commonly varies with particle size, more detailed measurements can provide additional important information about the CCN activation. With size-resolved measurements, the effect of particle size on CCN activity can be kept constant, which makes it possible to directly assess the influence of particle chemistry. The instrumental set-up consists of a differential mobility analyzer (DMA) to select particles of a known size, within a narrow size range. A condensation nuclei (CN) counter (condensation particle counter, CPC) is used to count the total number of particles in that size range, and a CCN counter is used to count the number of CCN as a function of supersaturation, in that same size range. The activation efficiency, expressed as CCN/CN ratios, can thus directly be calculated as a function of particle size and supersaturation. We present examples of the application of this technique, using salt and smoke aerosols produced in the laboratory as well as ambient aerosols.
Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

Peroxy radical (HO2+ΣRO2) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HOx. A good correlation exists between j(HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO2] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO2/(HO2+ΣRO2) ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h-1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3))/dln(NO)=1.0). The results imply that the N(O3) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NOx loadings in the European continental boundary layer.
Impacts of using reformulated and oxygenated fuel blends on the regional air quality of the upper Rhine valley

The effects of using three alternative gasoline fuel blends on regional air quality of the upper Rhine valley have been investigated. The first of the tested fuels is oxygenated by addition of ethyl-tertio-butyl ether (ETBE), the second is based on a reformulation of its composition and the third on is both oxygenated and reformulated. The upper Rhine valley is a very sensitive region for pollution episodes and several meteorological and air quality studies have already been performed. High temporal and spatial emission inventories are available allowing relevant and realistic modifications of the emission inventories. The calculation period, i.e., 11 May 1998, corresponds to a regional photochemical ozone pollution episode during which ozone concentrations exceeded several times the information threshold of the ozone directive of the European Union (180 μg m-3 as 1 hourly average). New emission inventories are set up using specific emission factors related to the alternative fuels by varying the fraction of gasoline passenger cars (from 50% to 100%) using the three fuel blends. Then air quality modeling simulations are performed using these emission inventories over the upper Rhine valley. The impact of alternative fuels on regional air quality is evaluated by comparing these simulations with the one using a reference emission inventory, e.g., where no modifications of the fuel composition are included. The results are analyzed by focusing on peak levels and daily averaged concentrations. The use of the alternative fuels leads to general reductions of ozone and volatile organic compounds (VOC) and increases of NOx levels. We found different behaviors related to the type of the area of concern i.e. rural or urban. The impacts on ozone are enhanced in urban areas where 15% reduction of the ozone peak and daily averaged concentrations can be reached. This behavior is similar for the NOx for which, in addition, an increase of the levels can be noted in urban plumes over rural areas. The most important decreases of the total VOC levels are mainly located over rural areas (more than 5% reduction of the levels except in urban plumes). By comparing these results with those from a local study related to the air quality of Strasbourg, we estimate that the regional contribution to the urban air quality of Strasbourg allows an enhancement of the results by using alternative fuel blends at the regional scale.
Sensitivity analysis by the adjoint chemistry transport model DRAISfor an episode in the Berlin Ozone (BERLIOZ) experiment

The Berlin Ozone Experiment (BERLIOZ) was carried out in summer 1998. One of its purposes was the evaluation of Chemistry Transport Models (CTM). CTM KAMM/DRAIS was one of the models considered. The data of 20 July were selected for evaluation. On that day, a pronounced ozone plume developed downwind of the city. Evaluation showed that the KAMM/DRAIS model is able to reproduce the meteorological and ozone data observed, except at farther distances (60–80 km) downwind of the city. In that region, the DRAIS model underestimates the measured ozone concentrations by 10–15 ppb, approximately. Therefore, this study was conducted to detect possible reasons for this deviation. A comprehensive sensitivity analysis was carried out to determine the most relevant model parameters. The adjoint DRAIS model was developed for this purpose, because for this study the application of this model is the most effective method of calculating the sensitivities. The least squares of the measured and simulated ozone concentrations between 08:00 UTC and 16:00 UTC at two stations 30 km and 70 km downwind of the city centre were chosen as distance function. The model parameters considered in this study are the complete set of initial and boundary species concentrations, emissions, and reaction rates, respectively. A sensitivity ranking showing the relevance of the individual parameters in the set is determined for each parameter set. In order to find out which modification in the parameter sets most reduces the cost function, simplified 4-D data assimilation was carried out. The result of this data assimilation shows that modifications of the reaction rates provide the best agreement between the measured and the simulated ozone concentrations at both stations. However, the modified reaction rates seem to be unrealistic for the whole simulation period. Therefore, the good agreement should not be overestimated. The agreement is still acceptable when the parameters in the other sets are modified together. The investigation demonstrates that an analysis of this type can help to explain inconsistencies between observations and simulations. But in the case considered here the inconsistencies cannot be explained by an error in only one parameter set.
Evaluation of high-resolution forecasts with the non-hydrostaticnumerical weather prediction model Lokalmodell for urban air pollutionepisodes in Helsinki, Oslo and Valencia

The operational numerical weather prediction model Lokalmodell LM with 7 km horizontal resolution was evaluated for forecasting meteorological conditions during observed urban air pollution episodes. The resolution was increased to experimental 2.8 km and 1.1 km resolution by one-way interactive nesting without introducing urbanisation of physiographic parameters or parameterisations. The episodes examined are two severe winter inversion-induced episodes in Helsinki in December 1995 and Oslo in January 2003, three suspended dust episodes in spring and autumn in Helsinki and Oslo, and a late-summer photochemical episode in the Valencia area. The evaluation was basically performed against observations and radiosoundings and focused on the LM skill at forecasting the key meteorological parameters characteristic for the specific episodes. These included temperature inversions, atmospheric stability and low wind speeds for the Scandinavian episodes and the development of mesoscale recirculations in the Valencia area. LM forecasts often improved due to higher model resolution especially in mountainous areas like Oslo and Valencia where features depending on topography like temperature, wind fields and mesoscale valley circulations were better described. At coastal stations especially in Helsinki, forecast gains were due to the improved physiographic parameters (land fraction, soil type, or roughness length). The Helsinki and Oslo winter inversions with extreme nocturnal inversion strengths of 18°C were not sufficiently predicted with all LM resolutions. In Helsinki, overprediction of surface temperatures and low-level wind speeds basically led to underpredicted inversion strength. In the Oslo episode, the situation was more complex involving erroneous temperature advection and mountain-induced effects for the higher resolutions. Possible explanations include the influence of the LM treatment of snow cover, sea ice and stability-dependence of transfer and diffusion coefficients. The LM simulations distinctly improved for winter daytime and nocturnal spring and autumn inversions and showed good skill at forecasting further episode-relevant meteorological parameters. The evaluation of the photochemical Valencia episode concentrated on the dominating mesoscale circulation patterns and showed that the LM succeeds well in describing all the qualitative features observed in the region. LM performance in forecasting the examined episodes thus depends on the key episode characteristics and also the season of the year with a need to improve model performance in very stable inversion conditions not only for urban simulations.
Impact of transatlantic transport episodes on summertime ozone in Europe

This paper reports on the transport of ozone (O3) and related species over the North Atlantic ocean and its impact on Europe. Measurements of nitrogen dioxide (NO2) and carbon monoxide (CO) columns from the GOME and MOPITT satellite instruments, respectively, are used in conjunction with the GEOS-CHEM global model of transport and tropospheric chemistry to identify the major events of long range transport that reach Europe over the course of summer 2000. Sensitivity model simulations are used to analyse observed O3 distributions with respect to the impact of long range transport events. For that purpose, we used in-situ O3 observations taken at the mountain site of Jungfraujoch as well as O3 vertical profiles taken in the vicinity of central European cities. Over the course of summer 2000, we identified 9 major episodes of transatlantic pollution transport; 7 events are associated with transient cyclones while 2 events occur through zonal transport (e.g. by advection in the strong low-level westerly winds established in summer between the Azores anticyclone and transient cyclones). We find that on average three episodes occur per month with the strongest ones being in June. The number and frequency of long range transport events that reach Europe are driven by the position and strength of the Azores anticyclone. Model sensitivity simulations indicate that the summer mean North American O3 contribution ranges from 3 to 5 ppb (7–11%) in the planetary boundary layer and 10 to 13 ppb (18–23%) in the middle and upper troposphere. During particular episodes, North American sources can result in O3 enhancements up to 25–28 ppb in the layer between 800–600 hPa and 10–12 ppb in the boundary layer. The impact of the zonal transport events on O3 distribution over Europe is more clearly seen below 700 hPa as they tend to transport pollution at lower levels while the events associated with transient cyclones are more likely to have an impact on the middle and upper troposphere (i.e. above 600 hPa). The air mass origins found in the GEOS-CHEM model are clearly confirmed by back trajectory analyses. During most of the 9 events, a strong contribution in North American O3 is in general associated with only little European O3 and vice-versa (in particular at the Jungfraujoch). A substantial North American contribution (e.g., 30% or higher) to O3 over Europe does not always result in pronounced O3 enhancements in the observations during our period of study.
The STARTWAVE atmospheric water database

The STARTWAVE (STudies in Atmospheric Radiative Transfer and Water Vapour Effects) project aims to investigate the role which water vapour plays in the climate system, and in particular its interaction with radiation. Within this framework, an ongoing water vapour database project was set up which comprises integrated water vapour (IWV) measurements made over the last ten years by ground-based microwave radiometers, Global Positioning System (GPS) receivers and sun photometers located throughout Switzerland at altitudes between 330 and 3584 m. At Bern (46.95° N, 7.44° E) tropospheric and stratospheric water vapour profiles are obtained on a regular basis and integrated liquid water, which is important for cloud characterisation, is also measured. Additional stratospheric water vapour profiles are obtained by an airborne microwave radiometer which observes large parts of the northern hemisphere during yearly flight campaigns. The database allows us to validate the various water vapour measurement techniques. Comparisons between IWV measured by the Payerne radiosonde with that measured at Bern by two microwave radiometers, GPS and sun photometer showed instrument biases within ±0.5 mm. The bias in GPS relative to sun photometer over the 2001 to 2004 period was –0.8 mm at Payerne (46.81° N, 6.94° E, 490 m), which lies in the Swiss plains north of the Alps, and +0.6 mm at Davos (46.81° N, 9.84° E, 1598 m), which is located within the Alps in the eastern part of Switzerland. At Locarno (46.18° N, 8.78° E, 366 m), which is located on the south side of the Alps, the bias is +1.9 mm. The sun photometer at Locarno was found to have a bias of –2.2 mm (13% of the mean annual IWV) relative to the data from the closest radiosonde station at Milano. This result led to a yearly rotation of the sun photometer instruments between low and high altitude stations to improve the calibrations. In order to demonstrate the capabilites of the database for studying water vapour variations, we investigated a front which crossed Switzerland between 18 November 2004 and 19 November 2004. During the frontal passage, the GPS and microwave radiometers at Bern and Payerne showed an increase in IWV of between 7 and 9 mm. The GPS IWV measurements were corrected to a standard height of 500 m, using an empirically derived exponential relationship between IWV and altitude. A qualitative comparison was made between plots of the IWV distribution measured by the GPS and the 6.2 µm water vapour channel on the Meteosat Second Generation (MSG) satellite. Both showed that the moist air moved in from a northerly direction, although the MSG showed an increase in water vapour several hours before increases in IWV were detected by GPS or microwave radiometer. This is probably due to the fact that the satellite instrument is sensitive to an atmospheric layer at around 320 hPa, which makes a contribution of one percent or less to the IWV.
Effect of humidity on nitric acid uptake to mineral dust aerosol particles

This study presents the first laboratory observation of HNO3 uptake by airborne mineral dust particles. The model aerosols were generated by dry dispersion of Arizona Test Dust (ATD), SiO2, and by nebulizing a saturated solution of calcium carbonate. The uptake of 13N-labeled gaseous nitric acid was observed in a flow reactor on the 0.2–2 s reaction time scale at room temperature and atmospheric pressure. The amount of nitric acid appearing in the aerosol phase at the end of the flow tube was found to be a linear function of the aerosol surface area. SiO2 particles did not show any significant uptake, while the CaCO3 aerosol was found to be more reactive than ATD. Due to the smaller uncertainty associated with the reactive surface area in the case of suspended particles as compared to bulk powder samples, we believe that we provide an improved estimate of the rate of uptake of HNO3 to mineral dust. The fact that the rate of uptake was smaller at a concentration of 1012 than at 1011 was indicative of a complex uptake mechanism. The uptake coefficient averaged over the first 2 s of reaction time at a concentration of 1012 molecules cm-3 was found to increase with increasing relative humidity, from 0.022±0.007 at 12% RH to 0.113±0.017 at 73% RH , which was attributed to an increasing degree of solvation of the more basic minerals. The extended processing of the dust by higher concentrations of HNO3 at 85% RH led to a water soluble coating on the particles and enhanced their hygroscopicity.