Y. Viisanen

Overview of the international project on biogenic aerosol formation in the boreal forest (BIOFOR)

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.

Ternary nucleation of H2SO4, NH3, and H2O in the atmosphere

Classical theory of binary homogeneous nucleation is extended to the ternary system H2SO4-NH3-H2O. For NH3 mixing ratios exceeding about 1 ppt, the presence of NH3 enhances the binary H2SO4-H2O nucleation rate by several orders of magnitude. The Gibbs free energies of formation of the critical H2SO4-NH3-H2O cluster, as calculated by two independent approaches, are in substantial agreement. The finding that the H2SO4-NH3-H2O ternary nucleation rate is independent of relative humidity over a large range of H2SO4 concentrations has wide atmospheric consequences. The limiting component for ternary H2SO4-NH3-H2O nucleation is, as in the binary H2SO4-H2O case, H2SO4; however, the H2SO4 concentration needed to achieve significant nucleation rates is several orders of magnitude below that required in the binary case.

A dedicated study of new particle formation and fate in the coastal environment (PARFORCE): overview of objectives and achievements

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 ∼90% 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 106 cm−3 under clean air conditions, while measured formation rates of detectable particle sizes (i.e., d > 3 nm) were of the order of 104–105 cm−3 s−1. Nucleation rates of new particles were estimated to be, at least, of the order of 105–106 cm−3 s−1 and occurred for sulphuric acid concentrations above 2 × 106 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 106 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 ∼1 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 ∼100%. 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.

Continuous measurements of optical properties of atmospheric aerosols in Mukteshwar, northern India

[1] Particulate pollution of mainly anthropogenic origin is a widely spread phenomenon in southern Asia, influencing climate and causing adverse health effects on humans. In this paper, we analyze continuous measurements of aerosol scattering and absorption properties that were conducted in Mukteshwar, a remote site in the Himalayan Mountains in northern India, during September 2005―September 2007. While aerosol concentrations were somewhat lower than those measured closer to urban areas in India, some optical parameters had a noticeable resemblance to those measured elsewhere in India. The average value of the measured single-scattering albedo was 0.81 at 525 nm, being indicative of a substantial amount of absorbing material. Annually, there were two periods when aerosol scattering and absorption coefficients were relatively low. These were the rainy season during July and August and the winter months December and January when particulate pollution seemed to reside partly below the altitude of the measurement station. During December and January, local cooking and warming of houses by biomass burning, normally not visible in the data, became evident yet weak sources of absorbing material.

Aerosol characteristics of air masses in northern Europe: Influences of location, transport, sinks, and sources

Synoptic-scale air masses at different stations were classified following a definition based on Berliner Wetterkarte. This air mass classification has been related to 1 year of aerosol number siz ...

Tropospheric carbon dioxide concentrations at a northern boreal site in Finland: basic variations and source areas

Abstract Diurnal and annual variations of CO2, O3, SO2, black carbon and condensation nuclei and their source areas were studied by utilizing air parcel trajectories and tropospheric concentration measurements at a boreal GAW site in Pallas, Finland. The average growth trend of CO2 was about 2.5 ppm yr−1 according to a 4-yr measurement period starting in October 1996. The annual cycle of CO2 showed concentration difference of about 19 ppm between the summer minimum and winter maximum. The diurnal cycle was most pronounced during July and August. The variation between daily minimum and maximum was about 5 ppm. There was a diurnal cycle in aerosol concentrations during spring and summer. Diurnal variation in ozone concentrations was weak. According to trajectory analysis the site was equally affected by continental and marine air masses. During summer the contribution of continental air increased, although the southernmost influences decreased. During daytime in summer the source areas of CO2 were mainly located in the northern parts of the Central Europe, while during winter the sources were more evenly distributed. Ozone showed similar source areas during summer, while during winter, unlike CO2, high concentrations were observed in air arriving from the sea. Sulfur dioxide sources were more northern (Kola peninsula and further east) and CO2 sources west-weighted in comparison to sources of black carbon. Source areas of black carbon were similar to source areas of aerosols during winter. Aerosol source area distributions showed signs of marine sources during spring and summer.

Experimental study of sticking probabilities for condensation of nitric acid — water vapor mixtures

Abstract In the present study condensational droplet growth rates in the binary vapor system HNO 3 –H 2 O were measured over a relatively wide range of vapor activitiesin order to investigate the mass accommodation coefficients in binary vapor mixtures. The measurements on condensational droplet growth rates were performed in an expansion chamber with a sensitive time of the order of 10 s . Droplet growth rates and the corresponding droplet number concentrations were determined by the Constant angle mie scattering (CAMS) method. In the present study the droplet radii cover a range from 0.5 to about 4 μm . The experiments were performed at constant temperature and total pressure near atmospheric conditions. The experimental growth curves determined in the binary vapor system HNO 3 –H 2 O are compared to corresponding model calculations. Thereby the mass and thermal accommodation coefficients can be determined. It can be concluded from the experiments that in binary supersaturated vapor mixtures of HNO 3 –H 2 O the sticking probability for nitric acid molecules is between 1.0 and 0.3 for the case of the sticking probability for the water molecules is set to unity. Especially at very low relative humidities below 75% very good agreement between experiment and theory can be established when the sticking probability of water as well as of nitric acid is regarded to be unity.

Homogeneous nucleation of n-nonane and n-propanol mixtures: A comparison of classical nucleation theory and experiments

The homogeneous nucleation rates for n-nonane-n-propanol vapor mixtures have been calculated as a function of vapor-phase activities at 230 K using the classical nucleation theory (CNT) with both rigorous and approximate kinetic prefactors and compared to previously reported experimental data. The predicted nucleation rates resemble qualitatively the experimental results for low n-nonane gas phase activity. On the high nonane activity side the theoretical nucleation rates are about three orders of magnitude lower than the experimental data when using the CNT with the approximate kinetics. The accurate kinetics improves the situation by reducing the difference between theory and experiments to two orders of magnitude. Besides the nucleation rate comparison and the experimental and predicted onset activities, the critical cluster composition is presented. The total number of molecules is approximated by CNT with reasonable accuracy. Overall, the classical nucleation theory with rigorous kinetic prefactor seems to perform better. The thermodynamic parameters needed to calculate the nucleation rates are revised extensively. Up-to-date estimates of liquid phase activities using universal functional activity coefficient Dortmund method are presented together with the experimental values of surface tensions obtained in the present study.

A theoretical study of binary homogenous nucleation of water-ammonium chloride particles in the atmosphere

Abstract Studies of the nucleation of new particles in the atmosphere are usually concentrated on the formation of sulfuric acid particles. However, there exist also other trace gas species with the nucleation capability in the atmosphere. In this paper the formation of water-ammonium chloride particles via homogenous heteromolecular nucleation in the atmospheric conditions is studied by using classical nucleation theory. This study is focused especially at the high relative humidities (90–99%), that can be found in the atmosphere during cloud or fog processes. The Gibbs free energy for the formation of a stable cluster is found to be insensitive to the variations in relative humidity. Instead, according to the results the nucleation rate is dependent on relative humidity, although the influence of relative humidity on the nucleation rate is relatively weak at the studied relative humidity range. The significant nucleation of stable water-ammonium chloride clusters via the studied path is concluded to be possible only in the polluted atmosphere during cloud processes. In the clean (for example remote sea) areas the significant nucleation of aqueous ammonium chloride particles is found to be highly impropable.

Atmospheric new particle formation at Uto, Baltic Sea 2003-2005

Nearly 3 yr (March 2003–December 2005) of continuous particle number size distribution measurements have been conducted at the island of Utö in the Baltic Sea. The measured particle size range was from 7 to 530 nm. During the measurement period, a total of 103 regional new-particle formation events were observed. The characteristics of the nucleation events at Utö were similar to those reported in the literature in other Nordic sites, though measured condensation sinks were rather high (geometric mean of 3.8 × 10-3 s-1) during event days. Clear evidence was found that new particles nucleate regionally near Utö, rather than are transported from greater distances. However, the Baltic Sea seems to have an inhibiting effect on new-particle formation. The boreal forest areas in the continental Finland were found to have an enhancing effect on the nucleation probability in Utö, suggesting that at least some of the precursor gases for nucleation and/or condensational growth of particles originate from these forests. In addition to regional new-particle formation events, a total of 94 local events were observed in Utö. These are short-lived events with a small footprint area, and can at least partly be tracked down to the emissions of ship traffic operating at Utö.