Organic condensation to freshly nucleated particles contributes substantially to their growth. Here we explore a range of constraints on this process, under the assumption that gas-phase oxidation of organic vapors by hydroxy radical is forming organics with a sufficiently low volatility to condense onto particles in the 2-20 nm size range. To condense but not homogeneously nucleate, vapors need to have saturation concentrations (C*) in the 10(-3) - 10(-2) mu g m(-3) range, and this is exactly the range that gas-phase chemistry is likely to produce. At least half of the observed growth rate of ultrafine particles can be explained by these simple considerations and constraints. Citation: Donahue, N. M., E. R. Trump, J. R. Pierce, and I. Riipinen (2011), Theoretical constraints on pure vapor-pressure driven condensation of organics to ultrafine particles, Geophys. Res. Lett., 38, L16801, doi:10.1029/2011GL048115.

A dimensionless theory for new particle formation (NPF) was developed, using an aerosol population balance model incorporating recent developments in nucleation rates and measured particle growth rates. Based on this theoretical analysis, it was shown that a dimensionless parameter L(Gamma), characterizing the ratio of the particle scavenging loss rate to the particle growth rate, exclusively determined whether or not NPF would occur on a particular day. This parameter determines the probability that a nucleated particle will grow to a detectable size before being lost by coagulation with the pre-existing aerosol. Cluster-cluster coagulation was shown to contribute negligibly to this survival probability under conditions pertinent to the atmosphere. Data acquired during intensive measurement campaigns in Tecamac (MILAGRO), Atlanta (ANARChE), Boulder, and Hyytiala (QUEST II, QUEST IV, and EUCAARI) were used to test the validity of L(Gamma) as an NPF criterion. Measurements included aerosol size distributions down to 3 nm and gas-phase sulfuric acid concentrations. The model was applied to seventy-seven NPF events and nineteen non-events (characterized by growth of pre-existing aerosol without NPF) measured in diverse environments with broad ranges in sulfuric acid concentrations, ultrafine number concentrations, aerosol surface areas, and particle growth rates (nearly two orders of magnitude). Across this diverse data set, a nominal value of L(Gamma)=0.7 was found to determine the boundary for the occurrence of NPF, with NPF occurring when L(Gamma)< 0.7 and being suppressed when L(Gamma)> 0.7. Moreover, nearly 45% of measured L(Gamma) values associated with NPF fell in the relatively narrow range of 0.1 < L(Gamma)< 0.3.

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.

More than 2300 observed cloud layers were analyzed to investigate the impact of aged Saharan dust on heterogeneous ice formation. The observations were performed with a polarization/Raman lidar at the European Aerosol Research Lidar Network site of Leipzig, Germany (51.3 degrees N, 12.4 degrees E) from February 1997 to June 2008. The statistical analysis is based on lidar-derived information on cloud phase (liquid water, mixed phase, ice cloud) and cloud top height, cloud top temperature, and vertical profiles of dust mass concentration calculated with the Dust Regional Atmospheric Modeling system. Compared to dust-free air masses, a significantly higher amount of ice-containing clouds (25%-30% more) was observed for cloud top temperatures from -10 degrees C to -20 degrees C in air masses that contained mineral dust. The midlatitude lidar study is compared with our SAMUM lidar study of tropical stratiform clouds at Cape Verde in the winter of 2008. The comparison reveals that heterogeneous ice formation is much stronger over central Europe and starts at higher temperatures than over the tropical station. Possible reasons for the large difference are discussed.

The European Aerosol Cloud Climate and Air Quality Interactions project EUCAARI is an EU Research Framework 6 integrated project focusing on understanding the interactions of climate and air pollution. EUCAARI works in an integrative and multidisciplinary way from nano-to global scale. EUCAARI brings together several leading European research groups, state-of-the-art infrastructure and some key scientists from third countries to investigate the role of aerosol on climate and air quality. Altogether 48 partners from 25 countries are participating in EUCAARI. During the first 16 months EUCAARI has built operational systems, e. g. established pan-European measurement network for Lagrangian studies and four stations in developing countries. Also an improved understanding of nanoscale processes (like nucleation) has been implemented in global models. Here we present the research methods, organisation, operations and first results of EUCAARI.

Multiwavelength lidar, Sun photometer, and radiosonde observations were conducted at Ouarzazate ( 30.9 degrees N, 6.9 degrees W, 1133 m above sea level, asl), Morocco, in the framework of the Saharan Mineral Dust Experiment (SAMUM) in May-June 2006. The field site is close to the Saharan desert. Information on the depolarization ratio, backscatter and extinction coefficients, and lidar ratio of the dust particles, estimates of the available concentration of atmospheric ice nuclei at cloud level, profiles of temperature, humidity, and the horizontal wind vector as well as backward trajectory analysis are used to study cases of cloud formation in the dust with focus on heterogeneous ice formation. Surprisingly, most of the altocumulus clouds that form at the top of the Saharan dust layer, which reaches into heights of 4-7 km asl and has layer top temperatures of -8 degrees C to -18 degrees C, do not show any ice formation. According to the lidar observations the presence of a high number of ice nuclei (1-20 cm(-3)) does not automatically result in the obvious generation of ice particles, but the observations indicate that cloud top temperatures must typically reach values as low as -20 degrees C before significant ice production starts. Another main finding is that liquid clouds are obviously required before ice crystals form via heterogeneous freezing mechanisms, and, as a consequence, that deposition freezing is not an important ice nucleation process. An interesting case with cloud seeding in the free troposphere above the dust layer is presented in addition. Small water clouds formed at about -30 degrees C and produced ice virga. These virga reached water cloud layers several kilometers below the initiating cloud cells and caused strong ice production in these clouds at temperatures as high as -12 degrees C to -15 degrees C.

Aerosol size distributions have been measured at the Swedish background station Aspvreten (58.8degrees N, 17.4degrees E). Different states of the aerosol were determined using a novel application of cluster analysis. The analysis resulted in eight different clusters capturing different stages of the aerosol lifecycle. The atmospheric aerosol size distributions were interpreted as belonging to fresh, intermediate and aged types of size distribution. With aid of back trajectory analysis we present statistics concerning the relation of source area and different meteorological parameters using a non-Lagrangian approach. Source area is argued to be important although not sufficient to describe the observed aerosol properties. Especially processing by clouds and precipitation is shown to be crucial for the evolution of the aerosol size distribution. As much as 60% of the observed size distributions present features that are likely to be related to cloud processes or wet deposition. The lifetime properties of different sized aerosols are discussed by means of measured variability of the aerosol size distribution. Processing by clouds and precipitation is shown to be especially crucial in the size range 100 nm and larger. This indicates an approximate limit for activation in clouds to 100 nm in this type of environment. The aerosol lifecycle is discussed. Size distributions indicating signs of recent new particle formation ( similar to 30% of the observed size distributions) represent the first stage in the lifecycle. Aging of the aerosol size distribution may follow two branches: either growth by condensation and coagulation or processing by non-precipitating clouds. In both cases mass is accumulated. Wet removal is the main process capable of removing aerosol mass. Wet deposition is argued to be an important mechanism in reaching a state where nucleation may occur (i.e. sufficiently low aerosol surface area) in environments similar to the one studied.

Size distribution measurements performed at five different stations have been investigated during a one-year period between 01 June 2000 and 31 May 2001 with focus on diurnal, seasonal and geographical differences of size distribution properties. The stations involved cover a large geographical area ranging from the Finnish Lapland (67degrees N) down to southern Sweden (56degrees N) in the order Varrio, Pallas, Hyytiala, Aspvreten and Vavihill. The shape of the size distribution is typically bimodal during winter with a larger fraction of accumulation mode particles compared to the other seasons. Highest Aitken mode concentration is found during summer and spring during the year of study. The maximum of nucleation events occur during the spring months at all stations. Nucleation events occur during other months as well, although not as frequently. Large differences were found between different categories of stations. Northerly located stations such as Pallas and Varrio presented well-separated Aitken and accumulation modes, while the two modes often overlap significantly at the two southernmost stations Vavihill and Aspvreten. A method to cluster trajectories was used to analyse the impact of long-range transport on the observed aerosol properties. Clusters of trajectories arriving from the continent were clearly associated with size distributions shifted towards the accumulation mode. This feature was more pronounced the further south the station was located. Marine- or Arctic-type clusters were associated with large variability in the nuclei size ranges. A quasi-lagrangian approach was used to investigate transport related changes in the aerosol properties. Typically, an increase in especially Aitken mode concentrations was observed when advection from the north occurs, i.e. allowing more continental influence on the aerosol when comparing the different measurement sites. When trajectory clusters arrive to the stations from SW, a gradual decrease in number concentration is experienced in all modes as latitude of measurement site increases.

[1] A dedicated study into the formation of new particles, New Particle Formation and Fate in the Coastal Environment (PARFORCE), was conducted over a period from 1998 to 1999 at the Mace Head Atmospheric Research Station on the western coast of Ireland. Continuous measurements of new particle formation were taken over the 2-year period while two intensive field campaigns were also conducted, one in September 1998 and the other in June 1999. New particle events were observed on similar to90% of days and occurred throughout the year and in all air mass types. These events lasted for, typically, a few hours, with some events lasting more than 8 hours, and occurred during daylight hours coinciding with the occurrence of low tide and exposed shorelines. During these events, peak aerosol concentrations often exceeded 10(6) cm(-3) under clean air conditions, while measured formation rates of detectable particle sizes (i.e., d > 3 nm) were of the order of 10(4)-10(5) cm(-3) s(-1). Nucleation rates of new particles were estimated to be, at least, of the order of 10(5)-10(6) cm(-3) s(-1) and occurred for sulphuric acid concentrations above 2 x 10(6) molecules cm(-3); however, no correlation existed between peak sulphuric acid concentrations, low tide occurrence, or nucleation events. Ternary nucleation theory of the H2SO4-H2O-NH3 system predicts that nucleation rates far in excess of 10(6) cm(-3) s(-1) can readily occur for the given sulphuric acid concentrations; however, aerosol growth modeling studies predict that there is insufficient sulphuric acid to grow new particles (of similar to1 nm in size) into detectable sizes of 3 nm. Hygroscopic growth factor analysis of recently formed 8-nm particles illustrate that these particles must comprise some species significantly less soluble than sulphate aerosol. The nucleation-mode hygroscopic data, combined with the lack of detectable VOC emissions from coastal biota, the strong emission of biogenic halocarbon species, and the fingerprinting of iodine in recently formed (7 nm) particles suggest that the most likely species resulting in the growth of new particles to detectable sizes is an iodine oxide as suggested by previous laboratory experiments. It remains an open question whether nucleation is driven by self nucleation of iodine species, a halocarbon derivative, or whether first, stable clusters are formed through ternary nucleation of sulphuric acid, ammonia, and water vapor, followed by condensation growth into detectable sizes by condensation of iodine species. Airborne measurements confirm that nucleation occurs all along the coastline and that the coastal biogenic aerosol plume can extend many hundreds of kilometers away from the source. During the evolution of the coastal plume, particle growth is observed up to radiatively active sizes of 100 nm. Modeling studies of the yield of cloud-condensation nuclei suggest that the cloud condensation nuclei population can increase by similar to100%. Given that the production of new particles from coastal biogenic sources occurs at least all along the western coast of Europe, and possibly many other coastlines, it is suggested that coastal aerosols contribute significantly to the natural background aerosol population.

[1] Nucleation mode aerosol was characterized during coastal nucleation events at Mace Head during intensive New Particle Formation and Fate in the Coastal Environment (PARFORCE) field campaigns in September 1998 and June 1999. Nucleation events were observed almost on a daily basis during the occurrence of low tide and solar irradiation. In September 1998, average nucleation mode particle concentrations were 8600 cm(-3) during clean air events and 2200 cm(-3) during polluted events. By comparison, during June 1999, mean nucleation mode concentrations were 27,000 cm(-3) during clean events and 3350 cm(-3) during polluted conditions. Peak concentrations often reached 500,000-1,000,000 cm(-3) during the most intense events and the duration of the events ranged from 2 to 8 hours with a mean of 4.5 hours. Source rates for detectable particle sizes (d > 3 nm) were estimated to be between 10(4) and 10(6) cm(-3) s(-1) and initial growth rates of new particles were as high as 0.1-0.35 nm s(-1) at the tidal source region. Recently formed 8 nm particles were subjected to hygroscopic growth and were found to have a growth factor of 1.0-1.1 for humidification at 90% relative humidity. The low growth factors implicate a condensable gas with very low solubility leading to detectable particle formation. It is not clear if this condensable gas also leads to homogeneous nucleation; however, measured sulphuric acid and ammonia concentration suggest that ternary nucleation of thermodynamically stable sulphate clusters is still likely to occur. In clear air, significant particle production (>10(5) cm(-3)) was observed with sulphuric acid gas-phase concentration as low as 2 x 10(6) molecules cm(-3) and under polluted conditions as high as 1.2 x 10(8) molecules cm(-3).