2012, Paasonen, P., Olenius, T., Kupiainen, O., Kurtén, T., Petäjä, T., Birmili, W., Hamed, A., Hu, M., Huey, L.G., Plass-Duelmer, C., Smith, J.N., Wiedensohler, A., Loukonen, V., McGrath, M.J., Ortega, I.K., Laaksonen, A., Vehkamäki, H., Kerminen, V.-M., Kulmala, M.

Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (JA2B2) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid ([H2SO4]), dimethylamine ([DMA]) and trimethylamine ([TMA]), temperature and relative humidity (RH). We also tested how the model results change if we assume that the clusters with two sulphuric acid and two amine molecules would act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. The modelled formation rates JA2B2 were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients KA2B2 connecting the cluster formation rate and sulphuric acid concentrations as JA2B2=KA2B2[H2SO4]2 turned out to depend also on amine concentrations, temperature and relative humidity. We compared the modelled coefficients KA2B2 with the corresponding coefficients calculated from the atmospheric observations (Kobs) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of JA2B2 as a function of [H2SO4], temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating in particle formation. The observed inverse proportionality of the coefficient Kobs with RH and temperature agreed best with the modelled coefficient KA2B2 related to formation of a cluster with two H2SO4 and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H2SO4).

2012, Fountoukis, C., Riipinen, I., Denier van der Gon, H.A.C., Charalampidis, P.E., Pilinis, C., Wiedensohler, A., O'Dowd, C., Putaud, J.P., Moerman, M., Pandis, S.N.

A three-dimensional regional chemical transport model (CTM) with detailed aerosol microphysics, PMCAMx-UF, was applied to the European domain to simulate the contribution of direct emissions and secondary formation to total particle number concentrations during May 2008. PMCAMx-UF uses the Dynamic Model for Aerosol Nucleation and the Two-Moment Aerosol Sectional (TOMAS) algorithm to track both aerosol number and mass concentration using a sectional approach. The model predicts nucleation events that occur over scales of hundreds up to thousands of kilometers especially over the Balkans and Southeast Europe. The model predictions were compared against measurements from 7 sites across Europe. The model reproduces more than 70% of the hourly concentrations of particles larger than 10 nm (N10) within a factor of 2. About half of these particles are predicted to originate from nucleation in the lower troposphere. Regional nucleation is predicted to increase the total particle number concentration by approximately a factor of 3. For particles larger than 100 nm the effect varies from an increase of 20% in the eastern Mediterranean to a decrease of 20% in southern Spain and Portugal resulting in a small average increase of around 1% over the whole domain. Nucleation has a significant effect in the predicted N50 levels (up to a factor of 2 increase) mainly in areas where there are condensable vapors to grow the particles to larger sizes. A semi-empirical ternary sulfuric acid-ammonia-water parameterization performs better than the activation or the kinetic parameterizations in reproducing the observations. Reducing emissions of ammonia and sulfur dioxide affects certain parts of the number size distribution.

2012, Wiedensohler, A., Birmili, W., Nowak, A., Sonntag, A., Weinhold, K., Merkel, M., Wehner, B., Tuch, T., Pfeifer, S., Fiebig, M., Fjäraa, A.M., Asmi, E., Sellegri, K., Depuy, R., Venzac, H., Villani, P., Laj, P., Aalto, P., Ogren, J.A., Swietlick, E., Williams, P., Roldin, P., Quincey, P., Hüglin, C., Fierz-Schmidhauser, R., Gysel, M., Weingartner, E., Riccobono, F., Santos, S., Grüning, C., Faloon, K., Beddows, D., Harrison, R., Monahan, C., Jennings, S.G., O'Dowd, C.D., Marinoni, A., Horn, H.-G., Keck, L., Jiang, J., Scheckman, J., McMurry, P.H., Deng, Z., Zhao, C.S., Moerman, M., Henzing, B., de Leeuw, G., Löschau, G., Bastian, S.

Mobility particle size spectrometers often referred to as DMPS (Differential Mobility Particle Sizers) or SMPS (Scanning Mobility Particle Sizers) have found a wide range of applications in atmospheric aerosol research. However, comparability of measurements conducted world-wide is hampered by lack of generally accepted technical standards and guidelines with respect to the instrumental set-up, measurement mode, data evaluation as well as quality control. Technical standards were developed for a minimum requirement of mobility size spectrometry to perform long-term atmospheric aerosol measurements. Technical recommendations include continuous monitoring of flow rates, temperature, pressure, and relative humidity for the sheath and sample air in the differential mobility analyzer. We compared commercial and custom-made inversion routines to calculate the particle number size distributions from the measured electrical mobility distribution. All inversion routines are comparable within few per cent uncertainty for a given set of raw data. Furthermore, this work summarizes the results from several instrument intercomparison workshops conducted within the European infrastructure project EUSAAR (European Supersites for Atmospheric Aerosol Research) and ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) to determine present uncertainties especially of custom-built mobility particle size spectrometers. Under controlled laboratory conditions, the particle number size distributions from 20 to 200 nm determined by mobility particle size spectrometers of different design are within an uncertainty range of around ±10% after correcting internal particle losses, while below and above this size range the discrepancies increased. For particles larger than 200 nm, the uncertainty range increased to 30%, which could not be explained. The network reference mobility spectrometers with identical design agreed within ±4% in the peak particle number concentration when all settings were done carefully. The consistency of these reference instruments to the total particle number concentration was demonstrated to be less than 5%. Additionally, a new data structure for particle number size distributions was introduced to store and disseminate the data at EMEP (European Monitoring and Evaluation Program). This structure contains three levels: raw data, processed data, and final particle size distributions. Importantly, we recommend reporting raw measurements including all relevant instrument parameters as well as a complete documentation on all data transformation and correction steps. These technical and data structure standards aim to enhance the quality of long-term size distribution measurements, their comparability between different networks and sites, and their transparency and traceability back to raw data.

2012, Ansmann, A., Seifert, P., Tesche, M., Wandinger, U.

The polarization lidar photometer networking (POLIPHON) method introduced to separate coarse-mode and fine-mode particle properties of Eyjafjallajökull volcanic aerosols in 2010 is extended to cover Saharan dust events as well. Furthermore, new volcanic dust observations performed after the Grimsvötn volcanic eruptions in 2011 are presented. The retrieval of particle mass concentrations requires mass-specific extinction coefficients. Therefore, a review of recently published mass-specific extinction coefficients for Saharan dust and volcanic dust is given. Case studies of four different scenarios corroborate the applicability of the profiling technique: (a) Saharan dust outbreak to central Europe, (b) Saharan dust plume mixed with biomass-burning smoke over Cape Verde, and volcanic aerosol layers originating from (c) the Eyjafjallajökull eruptions in 2010 and (d) the Grimsvötn eruptions in 2011. Strong differences in the vertical aerosol layering, aerosol mixing, and optical properties are observed for the different volcanic events.

2012, Chen, J., Zhao, C.S., Ma, N., Liu, P.F., Göbel, T., Hallbauer, E., Deng, Z.Z., Ran, L., Xu, W.Y., Liang, Z., Liu, H.J., Yan, P., Zhou, X.J., Wiedensohler, A.

Visibility degradation is a pervasive and urgent environmental problem in China. The occurrence of low visibility events is frequent in the North China Plain, where the aerosol loading is quite high and aerosols are strongly hygroscopic. A parameterization of light extinction (Kex) for low visibilities on hazy days is proposed in this paper, based on visibility, relative humidity (RH), aerosol hygroscopic growth factors and particle number size distributions measured during the Haze in China (HaChi) Project. Observational results show that a high aerosol volume concentration is responsible for low visibility at RH <90%; while for RH >90%, decrease of visibility is mainly influenced by the increase of RH. The parameterization of Kex is developed on the basis of aerosol volume concentrations and RH, taking into accounts the sensitivity of visibility to the two factors and the availability of corresponding data. The extinction coefficients calculated with the parameterization schemes agree well with the directly measured values.

2012, Engler, C., Birmili, W., Spindler, G., Wiedensohler, A.

Five years of PM10 and PM2.5 ambient air measurements at a roadside, an urban, and a regional background site in Leipzig (Germany) were analyzed for violations of the legal PM10 limit value (EC, 1999). The annual mean PM10 concentrations at the three sites were well below the legal threshold of 40 μg m−3 (32.6, 22.0 and 21.7 μg m−3, respectively). At roadside, the daily maximum value of 50 μg m−3 was exceeded on 232 days (13% of all days) in 2005–2009, which led to a violation of the EC directive in three out of five years. We analysed the meteorological factors and local source contributions that eventually led to the exceedances of the daily limit value. As noted in other urban environments before, most exceedance days were observed in the cold season. Exceedance days were most probable under synoptic situations characterised by stagnant winds, low temperatures and strong temperature inversions in winter time. However, these extreme situations accounted for only less than half of the exeedance days. We also noticed a significant number of exceedance days that occurred in the cold season under south-westerly winds, and in the warm season in the presence of easterly winds. Our analysis suggests that local as well as regional sources of PM are equally responsible for exceedances days at the roadside site. The conclusion is that a combined effort of local, national and international reduction measures appears most likely to avoid systematic exceedances of the daily limit value in the future.

2012, Healy, R.M., Sciare, J., Poulain, L., Kamili, K., Merkel, M., Müller, T., Wiedensohler, A., Eckhardt, S., Stohl, A., Sarda-Estève, R., McGillicuddy, E., O'Connor, I.P., Sodeau, J.R., Wenger, J.C.

An Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) was deployed to investigate the size-resolved chemical composition of single particles at an urban background site in Paris, France, as part of the MEGAPOLI winter campaign in January/February 2010. ATOFMS particle counts were scaled to match coincident Twin Differential Mobility Particle Sizer (TDMPS) data in order to generate hourly size-resolved mass concentrations for the single particle classes observed. The total scaled ATOFMS particle mass concentration in the size range 150–1067 nm was found to agree very well with the sum of concurrent High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and Multi-Angle Absorption Photometer (MAAP) mass concentration measurements of organic carbon (OC), inorganic ions and black carbon (BC) (R2 = 0.91). Clustering analysis of the ATOFMS single particle mass spectra allowed the separation of elemental carbon (EC) particles into four classes: (i) EC attributed to biomass burning (ECbiomass), (ii) EC attributed to traffic (ECtraffic), (iii) EC internally mixed with OC and ammonium sulfate (ECOCSOx), and (iv) EC internally mixed with OC and ammonium nitrate (ECOCNOx). Average hourly mass concentrations for EC-containing particles detected by the ATOFMS were found to agree reasonably well with semi-continuous quantitative thermal/optical EC and optical BC measurements (r2 = 0.61 and 0.65–0.68 respectively, n = 552). The EC particle mass assigned to fossil fuel and biomass burning sources also agreed reasonably well with BC mass fractions assigned to the same sources using seven-wavelength aethalometer data (r2 = 0.60 and 0.48, respectively, n = 568). Agreement between the ATOFMS and other instrumentation improved noticeably when a period influenced by significantly aged, internally mixed EC particles was removed from the intercomparison. 88% and 12% of EC particle mass was apportioned to fossil fuel and biomass burning respectively using the ATOFMS data compared with 85% and 15% respectively for BC estimated from the aethalometer model. On average, the mass size distribution for EC particles is bimodal; the smaller mode is attributed to locally emitted, mostly externally mixed EC particles, while the larger mode is dominated by aged, internally mixed ECOCNOx particles associated with continental transport events. Periods of continental influence were identified using the Lagrangian Particle Dispersion Model (LPDM) "FLEXPART". A consistent minimum between the two EC mass size modes was observed at approximately 400 nm for the measurement period. EC particles below this size are attributed to local emissions using chemical mixing state information and contribute 79% of the scaled ATOFMS EC particle mass, while particles above this size are attributed to continental transport events and contribute 21% of the EC particle mass. These results clearly demonstrate the potential benefit of monitoring size-resolved mass concentrations for the separation of local and continental EC emissions. Knowledge of the relative input of these emissions is essential for assessing the effectiveness of local abatement strategies.