2006, Boy, M., Hellmuth, O., Korhonen, H., Nilsson, E.D., ReVelle, D., Turnipseed, A., Arnold, F., Kulmala, M.

The manuscript presents a detailed description of the meteorological and chemical code of Malte – a model to predict new aerosol formation in the lower troposphere. The aerosol dynamics are achieved by the new developed UHMA (University of Helsinki Multicomponent Aerosol Model) code with kinetic limited nucleation as responsible mechanism to form new clusters. First results indicate that the model is able to predict the on- and offset of new particle formation as well as the total aerosol number concentrations that were in good agreement with the observations. Further, comparison of predicted and measured H2SO4 concentrations showed a satisfactory agreement. The simulation results indicated that at a certain transitional particle diameter (2–7 nm), organic molecules can begin to contribute significantly to the growth rate compared to sulphuric acid. At even larger particle sizes, organic molecules can dominate the growth rate on days with significant monoterpene concentrations. The intraday vertical evolution of newly formed clusters and particles in two different size ranges resulted in two maxima at the ground. These particles grow around noon to the detectable size range and agree well with measured vertical profiles.

2010, Wehner, B., Siebert, H., Ansmann, A., Ditas, F., Seifert, P., Stratmann, F., Wiedensohler, A., Apituley, A., Shaw, R.A., Manninen, H.E., Kulmala, M.

Aerosol particle measurements in the atmospheric boundary layer performed by a helicopter-borne measurement payload and by a lidar system from a case study during the IMPACT field campaign in Cabauw (NL) are presented. Layers of increased number concentrations of ultrafine particles were observed in the residual layer, indicating relatively recent new-particle formation. These layers were characterized by a sub-critical Richardson number and concomitant increased turbulence. Turbulent mixing is likely to lead to local supersaturation of possible precursor gases which are essential for new particle formation. Observed peaks in the number concentrations of ultrafine particles at ground level are connected to the new particle formation in the residual layer by boundary layer development and vertical mixing.

2001, Kulmala, M., Hämeri, K., Aalto, P.P., Mäkelä, J.M., Pirjola, L., Nilsson, E. Douglas, Buzorius, G., Rannik, Ü., Dal Maso, M., Seidl, W., Hoffman, T., Janson, R., Hansson, H.-C., Viisanen, Y., Laaksonen, A., O’dowd, C.D.

Aerosol formation and subsequent particle growth in ambient air have been frequently observed at a boreal forest site (SMEAR II station) in Southern Finland. The EU funded project BIOFOR (Biogenic aerosol formation in the boreal forest) has focused on: (a) determination of formation mechanisms of aerosol particles in the boreal forest site; (b) verification of emissions of secondary organic aerosols from the boreal forest site; and (c) quantification of the amount of condensable vapours produced in photochemical reactions of biogenic volatile organic compounds (BVOC) leading to aerosol formation. The approach of the project was to combine the continuous measurements with a number of intensive field studies. These field studies were organised in three periods, two of which were during the most intense particle production season and one during a non-event season. Although the exact formation route for 3 nm particles remains unclear, the results can be summarised as follows: Nucleation was always connected to Arctic or Polar air advecting over the site, giving conditions for a stable nocturnal boundary layer followed by a rapid formation and growth of a turbulent convective mixed layer closely followed by formation of new particles. The nucleation seems to occur in the mixed layer or entrainment zone. However two more prerequisites seem to be necessary. A certain threshold of high enough sulphuric acid and ammonia concentrations is probably needed as the number of newly formed particles was correlated with the product of the sulphuric acid production and the ammonia concentrations. No such correlation was found with the oxidation products of terpenes. The condensation sink, i.e., effective particle area, is probably of importance as no nucleation was observed at high values of the condensation sink. From measurement of the hygroscopic properties of the nucleation particles it was found that inorganic compounds and hygroscopic organic compounds contributed both to the particle growth during daytime while at night time organic compounds dominated. Emissions rates for several gaseous compounds was determined. Using four independent ways to estimate the amount of the condensable vapour needed for observed growth of aerosol particles we get an estimate of 2–10×107 vapour molecules cm−3. The estimations for source rate give 7.5–11×104 cm−3 s−1. These results lead to the following conclusions: The most probable formation mechanism is ternary nucleation (water-sulphuric acid-ammonia). After nucleation, growth into observable sizes (~3 nm) is required before new particles appear. The major part of this growth is probably due to condensation of organic vapours. However, there is lack of direct proof of this phenomenon because the composition of 1–5 nm size particles is extremely difficult to determine using the present state-of-art instrumentation.

2010, Hamed, A., Birmili, W., Joutsensaari, J., Mikkonen, S., Asmi, A., Wehner, B., Spindler, G., Jaatinen, A., Wiedensohler, A., Korhonen, H., Lehtinen, K.E.J., Laaksonen, A.

In anthropogenically influenced atmospheres, sulphur dioxide (SO2) is the main precursor of gaseous sulphuric acid (H2SO4), which in turn is a main precursor for atmospheric particle nucleation. As a result of socio-economic changes, East Germany has seen a dramatic decrease in anthropogenic SO2 emissions between 1989 and present, as documented by routine air quality measurements in many locations. We have attempted to evaluate the influence of changing SO2 concentrations on the frequency and intensity of new particle formation (NPF) using two different data sets (1996–1997; 2003–2006) of experimental particle number size distributions (diameter range 3–750 nm) from the atmospheric research station Melpitz near Leipzig, Germany. Between the two periods SO2 concentrations decreased by 65% on average, while the frequency of NPF events dropped by 45%. Meanwhile, the average formation rate of 3 nm particles decreased by 68% on average. The trends were statistically significant and therefore suggest a connection between the availability of anthropogenic SO2 and freshly formed new particles. In contrast to the decrease in new particle formation, we found an increase in the mean growth rate of freshly nucleated particles (+22%), suggesting that particle nucleation and subsequent growth into larger sizes are delineated with respect to their precursor species. Using three basic parameters, the condensation sink for H2SO4, the SO2 concentration, and the global radiation intensity, we were able to define the characteristic range of atmospheric conditions under which particle formation events take place at the Melpitz site. While the decrease in the concentrations and formation rates of the new particles was rather evident, no similar decrease was found with respect to the generation of cloud condensation nuclei (CCN; particle diameter >100 nm) as a result of atmospheric nucleation events. On the contrary, the production of CCN following nucleation events appears to have increased by tens of percents. Our aerosol dynamics model simulations suggest that such an increase can be caused by the increased particle growth rate.

2010, Duplissy, J., Enghoff, M.B., Aplin, K.L., Arnold, F., Aufmhoff, H., Avngaard, M., Baltensperger, U., Bondo, T., Bingham, R., Carslaw, K., Curtius, J., David, A., Fastrup, B., Gagné, S., Hahn, F., Harrison, R.G., Kellett, B., Kirkby, J., Kulmala, M., Laakso, L., Laaksonen, A., Lillestol, E., Lockwood, M., Mäkelä, J., Makhmutov, V., Marsh, N.D., Nieminen, T., Onnela, A., Pedersen, E., Pedersen, J.O.P., Polny, J., Reichl, U., Seinfeld, J.H., Sipilä, M., Stozhkov, Y., Stratmann, F., Svensmark, H., Svensmark, J., Veenhof, R., Verheggen, B., Viisanen, Y., Wagner, P.E., Wehrle, G., Weingartner, E., Wex, H., Wilhelmsson, M., Winkler, P.M.

During a 4-week run in October–November 2006, a pilot experiment was performed at the CERN Proton Synchrotron in preparation for the Cosmics Leaving OUtdoor Droplets (CLOUD) experiment, whose aim is to study the possible influence of cosmic rays on clouds. The purpose of the pilot experiment was firstly to carry out exploratory measurements of the effect of ionising particle radiation on aerosol formation from trace H2SO4 vapour and secondly to provide technical input for the CLOUD design. A total of 44 nucleation bursts were produced and recorded, with formation rates of particles above the 3 nm detection threshold of between 0.1 and 100 cm−3s−1, and growth rates between 2 and 37 nm h−1. The corresponding H2O concentrations were typically around 106 cm−3 or less. The experimentally-measured formation rates and \htwosofour concentrations are comparable to those found in the atmosphere, supporting the idea that sulphuric acid is involved in the nucleation of atmospheric aerosols. However, sulphuric acid alone is not able to explain the observed rapid growth rates, which suggests the presence of additional trace vapours in the aerosol chamber, whose identity is unknown. By analysing the charged fraction, a few of the aerosol bursts appear to have a contribution from ion-induced nucleation and ion-ion recombination to form neutral clusters. Some indications were also found for the accelerator beam timing and intensity to influence the aerosol particle formation rate at the highest experimental SO2 concentrations of 6 ppb, although none was found at lower concentrations. Overall, the exploratory measurements provide suggestive evidence for ion-induced nucleation or ion-ion recombination as sources of aerosol particles. However in order to quantify the conditions under which ion processes become significant, improvements are needed in controlling the experimental variables and in the reproducibility of the experiments. Finally, concerning technical aspects, the most important lessons for the CLOUD design include the stringent requirement of internal cleanliness of the aerosol chamber, as well as maintenance of extremely stable temperatures (variations below 0.1 °C

2001, Spanke, Jörg, Rannik, Üllar, Forkel, Renate, Nigge, Walter, Hoffman, Thorsten

The contribution of monoterpenes to aerosol formation processes within and above forests is not well understood. This is also true for the particle formation events observed during the BIOFOR campaigns in Hyytiälä, Finland. Therefore, the diurnal variation of the concentrations of several biogenic volatile organic compounds (BVOCs) and selected oxidation products in the gas and particle phase were measured on selected days during the campaigns in Hyytiälä, Finland. α-pinene and Δ3-carene were found to represent the most important monoterpenes above the boreal forest. A clear vertical gradient of their concentrations was observed together with a change of the relative monoterpene composition with height. Based on concentration profile measurements of monoterpenes, their fluxes above the forest canopy were calculated using the gradient approach. Most of the time, the BVOC fluxes show a clear diurnal variation with a maximum around noon. The highest fluxes were observed for α-pinene with values up to 20 ng m−2 s−1 in summer time and almost 100 ng m−2 s−1 during the spring campaign. Furthermore, the main oxidation products from α-pinene, pinonaldehyde, and from β-pinene, nopinone, were detected in the atmosphere above the forest. In addition to these more volatile oxidation products, pinic and pinonic acid were identified in the particle phase in a concentration range between 1 and 4 ng m−3. Beside these direct measurement of known oxidation products, the chemical sink term in the flux calculations was used to estimate the amount of product formation of the major terpenes (α-pinene, β-pinene, Δ3-carene). A production rate of very low volatile oxidation products (e.g., multifunctional carboxylic) from ·OH- and O3-reaction of monoterpenes of about 1.3·104 molecules cm−3 s−1 was estimated for daylight conditions during summer time. Additionally, model calculations with the one-dimensional multilayer model CACHE were carried out to investigate the diurnal course of BVOC fluxes and chemical degradation of terpenes.

2010, Kulmala, M., Riipinen, I., Nieminen, T., Hulkkonen, M., Sogacheva, L., Manninen, H.E., Paasonen, P., Petäjä, T., Dal Maso, M., Aalto, P.P., Viljanen, A., Usoskin, I., Vainio, R., Mirme, S., Mirme, A., Minikin, A., Petzold, A., Hõrrak, U., Plaß-Dülmer, C., Birmili, W., Kerminen, V.-M.

Aerosol particles affect the Earth's radiative balance by directly scattering and absorbing solar radiation and, indirectly, through their activation into cloud droplets. Both effects are known with considerable uncertainty only, and translate into even bigger uncertainties in future climate predictions. More than a decade ago, variations in galactic cosmic rays were suggested to closely correlate with variations in atmospheric cloud cover and therefore constitute a driving force behind aerosol-cloud-climate interactions. Later, the enhancement of atmospheric aerosol particle formation by ions generated from cosmic rays was proposed as a physical mechanism explaining this correlation. Here, we report unique observations on atmospheric aerosol formation based on measurements at the SMEAR II station, Finland, over a solar cycle (years 1996–2008) that shed new light on these presumed relationships. Our analysis shows that none of the quantities related to aerosol formation correlates with the cosmic ray-induced ionisation intensity (CRII). We also examined the contribution of ions to new particle formation on the basis of novel ground-based and airborne observations. A consistent result is that ion-induced formation contributes typically significantly less than 10% to the number of new particles, which would explain the missing correlation between CRII and aerosol formation. Our main conclusion is that galactic cosmic rays appear to play a minor role for atmospheric aerosol formation events, and so for the connected aerosol-climate effects as well.

2005, Vaattovaara, P., Räsänen, M., Kühn, T., Joutsensaari, J., Laaksonen, A.

New particle formation and growth has a very important role in many climate processes. However, the overall knowlegde of the chemical composition of atmospheric nucleation mode (particle diameter, d<20 nm) and the lower end of Aitken mode particles (d≤50 nm) is still insufficient. In this work, we have applied the UFO-TDMA (ultrafine organic tandem differential mobility analyzer) method to shed light on the presence of an organic fraction in the nucleation mode size class in different atmospheric environments. The basic principle of the organic fraction detection is based on our laboratory UFO-TDMA measurements with organic and inorganic compounds. Our laboratory measurements indicate that the usefulness of the UFO-TDMA in the field experiments would arise especially from the fact that atmospherically the most relevant inorganic compounds do not grow in subsaturated ethanol vapor, when particle size is 10 nm in diameter and saturation ratio is about 86% or below it. Furthermore, internally mixed particles composed of ammonium bisulfate and sulfuric acid with sulfuric acid mass fraction ≤33% show no growth at 85% saturation ratio. In contrast, 10 nm particles composed of various oxidized organic compounds of atmospheric relevance are able to grow in those conditions. These discoveries indicate that it is possible to detect the presence of organics in atmospheric nucleation mode sized particles using the UFO-TDMA method. In the future, the UFO-TDMA is expected to be an important aid to describe the composition of atmospheric newly-formed particles.