Yrjö Viisanen

Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation

Atmospheric aerosols exert an important influence on climate through their effects on stratiform cloud albedo and lifetime and the invigoration of convective storms. Model calculations suggest that almost half of the global cloud condensation nuclei in the atmospheric boundary layer may originate from the nucleation of aerosols from trace condensable vapours, although the sensitivity of the number of cloud condensation nuclei to changes of nucleation rate may be small. Despite extensive research, fundamental questions remain about the nucleation rate of sulphuric acid particles and the mechanisms responsible, including the roles of galactic cosmic rays and other chemical species such as ammonia. Here we present the first results from the CLOUD experiment at CERN. We find that atmospherically relevant ammonia mixing ratios of 100 parts per trillion by volume, or less, increase the nucleation rate of sulphuric acid particles more than 100–1,000-fold. Time-resolved molecular measurements reveal that nucleation proceeds by a base-stabilization mechanism involving the stepwise accretion of ammonia molecules. Ions increase the nucleation rate by an additional factor of between two and more than ten at ground-level galactic-cosmic-ray intensities, provided that the nucleation rate lies below the limiting ion-pair production rate. We find that ion-induced binary nucleation of H2SO4–H2O can occur in the mid-troposphere but is negligible in the boundary layer. However, even with the large enhancements in rate due to ammonia and ions, atmospheric concentrations of ammonia and sulphuric acid are insufficient to account for observed boundary-layer nucleation.

Molecular understanding of sulphuric acid–amine particle nucleation in the atmosphere

Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei. Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes. Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases. However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere. It is thought that amines may enhance nucleation, but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid–amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid–dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation.

Oxidation products of biogenic emissions contribute to nucleation of atmospheric particles.

Out of the Air New-particle formation from gaseous precursors in the atmosphere is a complex and poorly understood process with importance in atmospheric chemistry and climate. Laboratory studies have had trouble reproducing the particle formation rates that must occur in the natural world. Riccobono et al. (p. 717) used the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN to recreate a realistic atmospheric environment. Sulfuric acid and oxidized organic vapors in typical natural concentrations caused particle nucleation at similar rates to those observed in the lower atmosphere. Experiments in the CLOUD chamber at CERN reproduce particle nucleation rates observed in the lower atmosphere. Atmospheric new-particle formation affects climate and is one of the least understood atmospheric aerosol processes. The complexity and variability of the atmosphere has hindered elucidation of the fundamental mechanism of new-particle formation from gaseous precursors. We show, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere. The experiments reveal a nucleation mechanism involving the formation of clusters containing sulfuric acid and oxidized organic molecules from the very first step. Inclusion of this mechanism in a global aerosol model yields a photochemically and biologically driven seasonal cycle of particle concentrations in the continental boundary layer, in good agreement with observations.

Diurnal and annual characteristics of particle mass and number concentrations in urban, rural and Arctic environments in Finland

Abstract In order to be able to detect annual and diurnal variation the nucleation, Aitken and accumulation mode aerosol number concentrations were investigated. In this study particulate matter and aerosol number concentrations based on three years (1999–2001) measurements in four different places, Helsinki, Hyytiala, Pallas and Varrio in Finland were utilized. Mean PM10 concentration was found to be in urban, urban background, disturbed rural and rural conditions 18.7, 15.3, 10.2 and 6.9 μg m −3 . PM2.5 concentrations in urban, urban background and rural conditions were 9.6, 8.2 and 5.8 μg m −3 . PM1 concentration in rural area were 4.1 μg m −3 . Total number concentrations between 10 and 500 nm in urban, rural and arctic background were 16660, 2110 and about 920 cm −3 , respectively. Annual cycle of different particle sizes was also investigated. Particle mass was found to have maximum during the spring and autumn. Nucleation mode particle concentrations had their maximum both in urban and rural conditions in spring and autumn. For Aitken mode a similar variation was found. Accumulation mode particles were found to have the highest concentrations during summer and the lowest concentrations during winter. In urban conditions local sources drive over natural variability, but a natural cycle can still be seen. Diurnal variation was found to be associated with traffic in urban conditions. In rural conditions, diurnal variation of nucleation mode particles were connected to new particle formation. It was also found, that there is no correlation between ultrafine ( nm ) and larger (>90 nm ) particles.

Aerosol size distribution measurements at four Nordic field stations : identification, analysis and trajectory analysis of new particle formation bursts

We analyzed aerosol size distributions from the Finnish measuring stations at Hyytiälä, Värriö and Pallas and the Swedish station at Aspvreten over a period of several years.We identified occurrences of new particle formation bursts and obtained characteristics for the bursts from the size distribution data. In addition, we analyzed the directions from which air masses leading to new particle formation arrived.We found that new particle formation occurs over the whole area covered by the measurement stations. The Northern Atlantic is dominating as a source for air leading to new particle formation at all of the analyzed stations. The formation occurrence had a similar annual variation at all the stations, with peaks in springtime and autumn and minima in winter and summer. The ratio of event days to non-event days had a North-South dependence, with northern stations having lower event ratios. Particle growth rates ranged from 0.5 to 15 nm/h, with the mean growth rate being slightly higher at the southern stations. Southern stations also had a stronger particle source, on average 0.5 cm-3 s-1, compared to the northern stations (0.1 cm-3 s-1). Based on our analysis, it is evident that new particle formation occurs often in whole Nordic boreal forest area when air is transported from the North Atlantic, and that the same process or processes are very probably responsible for the formation over the whole area.

EXPERIMENTS ON GAS-LIQUID NUCLEATION OF SULFURIC ACID AND WATER

We present measurements of binary homogeneous nucleation of sulfuric acid and water vapors at 298 K at two different relative humidities (38.2% and 52.3%), H2SO4 vapor concentrations ranging from about 1⋅1010 to 3⋅1010 molecules/cc. The experimental setup consisted of a turbulent mixing unit combined with a flow chamber where the nucleation took place. Particular attention was paid to the generation of sulfuric acid vapor. The measured nucleation rates vary between about 2 and 3000 cm−3 s−1. The results are compared with other measurements found in the literature. Our experimental rates are in agreement with predictions of the revised classical nucleation theory incorporating the hydration effect.

Atmospheric aerosol over Finnish Arctic: source analysis by the multilinear engine and the potential source contribution function

Week-long samples of total suspended particles were collected between 1964 and 1978 from Kevo at the Finnish Arctic and analyzed for a number of chemical species. The chemical composition data was analyzed using a mixed 2-way/3-way model. The results of receptor modeling were connected with the back trajectory data in a Potential Source Contribution Function analysis to determine the likely source areas. Nine sources, namely silver emissions, coal/oil shale combustion, biomass burning, non-ferrous smelters (two sources), crustal elements from remote sources, excess silicon from local sources, sea salt particles and biogenic sulfur emissions from marine algae were found. Although the emissions from industrial areas in the Kola Peninsula had an effect on the concentration of anthropogenic pollutants at Kevo, the highest concentrations during winter were transported from the sources in the mid-latitudes. The yearly strength of the biogenic sulfur emissions showed no dependence on the Northern Hemisphere temperature anomaly and thus, a climatic feedback loop could not be confirmed.

Annual and interannual variation in boreal forest aerosol particle number and volume concentration and their connection to particle formation

We investigated size-resolved submicrometre aerosol particle number and volume concentration time series as well as aerosol dynamic parameters derived from Differential Mobility Particle Sizer (DMPS) measurements at five background stations in the Nordic boreal forest area. The stations in question were Aspvreten, Hyytiälä and Utö in southern Finland and Sweden, and Värriö and Pallas in the Finnish Lapland. The objective of our investigation was to identify and quantify annual and interannual variation observable in the time series. We found that the total number and mass concentrations were much lower at the Lapland stations than at the southern stations and that the total particle number was strongly correlated to particle formation event frequency. The annual total number concentration followed the annual distribution of particle formation events at the southern stations but much less clearly at the Lapland stations. The volume concentration was highest during summer, in line with higher condensation growth rates; this is in line with the assumption that a large part of the particle volume is produced by oxidized plant emissions. The decrease of sulphate emissions in Europe was not visible in our data set. Aerosol dynamic parameters such as condensation sink, condensation sink diameter and the power law exponent linking coagulation losses and condensation sink are presented to characterize the submicron Nordic background aerosol.

Homogeneous nucleation of n-pentanol in a laminar flow diffusion chamber

Nucleation rate isotherms of n-pentanol were measured in laminar flow diffusion chamber. n-pentanol was chosen for nucleating vapor and helium for carrier gas as a part of a world wide joint experiment on homogeneous nucleation. Experimental temperature range was from 260 to 290 K. Experimental nucleation rate range was from 103 to 107 cm−3 s−1. The results were compared to the classical nucleation theory and experimental data found in literature. Experimental results were three orders of magnitude higher than predicted by the theory. The difference was constant over the whole experimental range. The saturation ratio dependency of nucleation rate was well predicted by the theory. The number of molecules in the critical clusters was quite consistent with the theory. The results were in reasonable agreement with data found in literature.

The Helsinki Testbed: A Mesoscale Measurement, Research, and Service Platform

Abstract The Finnish Meteorological Institute and Vaisala have established a mesoscale weather observational network in southern Finland. The Helsinki Testbed is an open research and quasi-operational program designed to provide new information on observing systems and strategies, mesoscale weather phenomena, urban and regional modeling, and end-user applications in a high-latitude (~60°N) coastal environment. The Helsinki Testbed and related programs feature several components: observing system design and implementation, small-scale data assimilation, nowcasting and short-range numerical weather prediction, public service, and commercial development of applications. Specifically, the observing instrumentation focuses on meteorological observations of meso-gamma-scale phenomena that are often too small to be detected adequately by traditional observing networks. In particular, more than 40 telecommunication masts (40 that are 120 m high and one that is 300 m high) are instrumented at multiple heights. Oth...