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- ItemA statistical proxy for sulphuric acid concentration(München : European Geopyhsical Union, 2011) Mikkonen, S.; Romakkaniemi, S.; Smith, J.N.; Korhonen, H.; Petäjä, T.; Plass-Duelmer, C.; Boy, M.; McMurry, P.H.; Lehtinen, K.E.J.; Joutsensaari, J.; Hamed, A.; Mauldin III, R.L.; Birmili, W.; Spindler, G.; Arnold, F.; Kulmala, M.; Laaksonen, A.Gaseous sulphuric acid is a key precursor for new particle formation in the atmosphere. Previous experimental studies have confirmed a strong correlation between the number concentrations of freshly formed particles and the ambient concentrations of sulphuric acid. This study evaluates a body of experimental gas phase sulphuric acid concentrations, as measured by Chemical Ionization Mass Spectrometry (CIMS) during six intensive measurement campaigns and one long-term observational period. The campaign datasets were measured in Hyytiälä, Finland, in 2003 and 2007, in San Pietro Capofiume, Italy, in 2009, in Melpitz, Germany, in 2008, in Atlanta, Georgia, USA, in 2002, and in Niwot Ridge, Colorado, USA, in 2007. The long term data were obtained in Hohenpeissenberg, Germany, during 1998 to 2000. The measured time series were used to construct proximity measures ("proxies") for sulphuric acid concentration by using statistical analysis methods. The objective of this study is to find a proxy for sulfuric acid that is valid in as many different atmospheric environments as possible. Our most accurate and universal formulation of the sulphuric acid concentration proxy uses global solar radiation, SO2 concentration, condensation sink and relative humidity as predictor variables, yielding a correlation measure (R) of 0.87 between observed concentration and the proxy predictions. Interestingly, the role of the condensation sink in the proxy was only minor, since similarly accurate proxies could be constructed with global solar radiation and SO2 concentration alone. This could be attributed to SO2 being an indicator for anthropogenic pollution, including particulate and gaseous emissions which represent sinks for the OH radical that, in turn, is needed for the formation of sulphuric acid.
- ItemOn the formation of sulphuric acid – Amine clusters in varying atmospheric conditions and its influence on atmospheric new particle formation(München : European Geopyhsical Union, 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).
- ItemHygroscopic properties of the Paris urban aerosol in relation to its chemical composition(München : European Geopyhsical Union, 2014) Kamilli, K.A.; Poulain, L.; Held, A.; Nowak, A.; Birmili, W.; Wiedensohler, A.Aerosol hygroscopic growth factors and chemical properties were measured as part of the MEGAPOLI "Megacities Plume Case Study" at the urban site Laboratoire d'Hygiène de la Ville de Paris (LHVP) in the city center of Paris from June to August 2009, and from January to February 2010. Descriptive hygroscopic growth factors (DGF) were derived in the diameter range from 25 to 350 nm at relative humidities of 30, 55, 75, and 90% by applying the summation method on humidified and dry aerosol size distributions measured simultaneously with a humidified differential mobility particle sizer (HDMPS) and a twin differential mobility particle sizer (TDMPS). For 90% relative humidity, the DGF varied from 1.06 to 1.46 in summer, and from 1.06 to 1.66 in winter. Temporal variations in the observed mean DGF could be well explained with a simple growth model based on the aerosol chemical composition measured by aerosol mass spectrometry (AMS) and black carbon photometry (MAAP). In particular, good agreement was observed when sulfate was the predominant inorganic factor. A clear overestimation of the predicted growth factor was found when the nitrate mass concentration exceeded values of 10 μg m−3, e.g., during winter.
- ItemHygroscopic properties of atmospheric aerosol particles over the Eastern Mediterranean: Implications for regional direct radiative forcing under clean and polluted conditions(München : European Geopyhsical Union, 2011) Stock, M.; Cheng, Y.F.; Birmili, W.; Massling, A.; Wehner, B.; Müller, T.; Leinert, S.; Kalivitis, N.; Mihalopoulos, N.; Wiedensohler, A.This work examines the effect of direct radiative forcing of aerosols in the eastern Mediterranean troposphere as a function of air mass composition, particle size distribution and hygroscopicity, and relative humidity (RH). During intensive field measurements on the island of Crete, Greece, the hygroscopic properties of atmospheric particles were determined using a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) and a Hygroscopicity Differential Mobility Analyzer-Aerodynamic Particle Sizer (H-DMA-APS). Similar to former studies, the H-TDMA identified three hygroscopic sub-fractions of particles in the sub-μm range: a more hygroscopic group, a less hygroscopic group and a nearly hydrophobic particle group. The average hygroscopic particle growth factors at 90 % RH were a significant function of particle mobility diameter (Dp): 1.42 (± 0.05) at 30 nm compared to 1.63 (± 0.07) at 250 nm. The H-DMA-APS identified up to three hygroscopic sub-fractions at mobility diameters of 1.0 and 1.2 μm. The data recorded between 12 August and 20 October 2005 were classified into four distinct synoptic-scale air mass types distinguishing between different regions of origin (western Mediterranean vs. the Aegean Sea) as well as the degree of continental pollution (marine vs. continentally influenced). The hygroscopic properties of particles with diameter Dp≥150 nm showed the most pronounced dependency on air mass origin, with growth factors in marine air masses exceeding those in continentally influenced air masses. Particle size distributions and hygroscopic growth factors were used to calculate aerosol light scattering coefficients at ambient RH using a Mie model. A main result was the pronounced enhancement of particle scattering over the eastern Mediterranean due to hygroscopic growth, both in the marine and continentally influenced air masses. When RH reached its summer daytime values around 70–80 %, up to 50–70 % of the calculated visibility reduction was due to the hygroscopic growth of the particles by water compared to the effect of the dry particles alone. The estimated aerosol direct radiative forcings for both, marine and continentally influenced air masses were negative indicating a net cooling of the atmosphere due to the aerosol. The radiative forcing ΔFr was nevertheless governed by the total aerosol concentration most of the time: ΔFr was typically more negative for continentally influenced aerosols (ca. −4 W m−2) compared to rather clean marine aerosols (ca. −1.5 W m−2). When RH occasionally reached 90 % in marine air masses, ΔFr even reached values down to −7 W m−2. Our results emphasize, on the basis of explicit particle hygroscopicity measurements, the relevance of ambient RH for the radiative forcing of regional atmospheres.
- ItemMobility particle size spectrometers: Harmonization of technical standards and data structure to facilitate high quality long-term observations of atmospheric particle number size distributions(München : European Geopyhsical Union, 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.
- ItemRelating particle hygroscopicity and CCN activity to chemical composition during the HCCT-2010 field campaign(München : European Geopyhsical Union, 2013) Wu, Z.J.; Poulain, L.; Henning, S.; Dieckmann, K.; Birmili, W.; Merkel, M.; van Pinxteren, D.; Spindler, G.; Müller, K.; Stratmann, F.; Herrmann, H.; Wiedensohler, A.Particle hygroscopic growth at 90% RH (relative humidity), cloud condensation nuclei (CCN) activity, and size-resolved chemical composition were concurrently measured in the Thüringer Wald mid-level mountain range in central Germany in the fall of 2010. The median hygroscopicity parameter values, κ, of 50, 75, 100, 150, 200, and 250 nm particles derived from hygroscopicity measurements are respectively 0.14, 0.14, 0.17, 0.21, 0.24, and 0.28 during the sampling period. The closure between HTDMA (Hygroscopicity Tandem Differential Mobility Analyzers)-measured (κHTDMA) and chemical composition-derived (κchem) hygroscopicity parameters was performed based on the Zdanovskii–Stokes–Robinson (ZSR) mixing rule. Using size-averaged chemical composition, the κ values are substantially overpredicted (30 and 40% for 150 and 100 nm particles). Introducing size-resolved chemical composition substantially improved closure. We found that the evaporation of NH4NO3, which may happen in a HTDMA system, could lead to a discrepancy in predicted and measured particle hygroscopic growth. The hygroscopic parameter of the organic fraction, κorg, is positively correlated with the O : C ratio (κorg = 0.19 × (O : C) − 0.03). Such correlation is helpful to define the κorg value in the closure study. κ derived from CCN measurement was around 30% (varied with particle diameters) higher than that determined from particle hygroscopic growth measurements (here, hydrophilic mode is considered only). This difference might be explained by the surface tension effects, solution non-ideality, gas-particle partitioning of semivolatile compounds, and the partial solubility of constituents or non-dissolved particle matter. Therefore, extrapolating from HTDMA data to properties at the point of activation should be done with great care. Finally, closure study between CCNc (cloud condensation nucleus counter)-measured (κCCN) and chemical composition (κCCN, chem) was performed using CCNc-derived κ values for individual components. The results show that the κCCN can be well predicted using particle size-resolved chemical composition and the ZSR mixing rule.
- ItemMeteorological and trace gas factors affecting the number concentration of atmospheric Aitken (DP Combining double low line 50 nm) particles in the continental boundary layer: Parameterization using a multivariate mixed effects model(München : European Geopyhsical Union, 2011) Mikkonen, S.; Korhonen, H.; Romakkaniemi, S.; Smith, J.N.; Joutsensaari, J.; Lehtinen, K.E.J.; Hamed, A.; Breider, T.J.; Birmili, W.; Spindler, G.; Plass-Duelmer, C.; Facchini, M.C.; Laaksonen, A.Measurements of aerosol size distribution and different gas and meteorological parameters, made in three polluted sites in Central and Southern Europe: Po Valley, Italy, Melpitz and Hohenpeissenberg in Germany, were analysed for this study to examine which of the meteorological and trace gas variables affect the number concentration of Aitken (Dp= 50 nm) particles. The aim of our study was to predict the number concentration of 50 nm particles by a combination of in-situ meteorological and gas phase parameters. The statistical model needs to describe, amongst others, the factors affecting the growth of newly formed aerosol particles (below 10 nm) to 50 nm size, but also sources of direct particle emissions in that size range. As the analysis method we used multivariate nonlinear mixed effects model. Hourly averages of gas and meteorological parameters measured at the stations were used as predictor variables; the best predictive model was attained with a combination of relative humidity, new particle formation event probability, temperature, condensation sink and concentrations of SO2, NO2 and ozone. The seasonal variation was also taken into account in the mixed model structure. Model simulations with the Global Model of Aerosol Processes (GLOMAP) indicate that the parameterization can be used as a part of a larger atmospheric model to predict the concentration of climatically active particles. As an additional benefit, the introduced model framework is, in theory, applicable for any kind of measured aerosol parameter.