M. Dal Maso

On the formation, growth and composition of nucleation mode particles

Taking advantage of only the measured aerosol particles spectral evolution as a function of time, a new analytical tool is developed to derive formation and growth properties of nucleation mode aerosols. This method, when used with hygroscopic growth-factors, can also estimate basic composition properties of these recently-formed particles. From size spectra the diameter growth-rate can be obtained, and aerosol condensation and coagulation sinks can be calculated. Using this growth-rate and condensation sink, the concentration of condensable vapours and their source rate can be estimated. Then, combining the coagulation sink together with measured number concentrations and apparent source rates of 3 nm particles, 1 nm particle nucleation rates and concentration can be estimated. To estimate nucleation rates and vapour concentration source rates producing new particle bursts over the Boreal forest regions, three cases from the BIOFOR project were examined using this analytical tool. In this environment, the nucleation mode growth-rate was observed to be 2–3 nm hour−1, which required a condensable vapour concentration of 2.5–4×107 cm−3 and a source rate of approximately 7.5–11×104 cm−3 s−1 to be sustained. The formation rate of 3 nm particles was =1 particle cm−3 s−1 in all three cases. The estimated formation rate of 1 nm particles was 10–100 particles cm−3 s−1, while their concentration was estimated to be between 10,000 and 100,000 particles cm−3. Using hygroscopicity data and mass flux expressions, the mass flux of insoluble vapour is estimated to be of the same order of magnitude as that of soluble vapour, with a soluble to insoluble vapour flux ratio ranging from 0.7 to 1.4 during these nucleation events.

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.

Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

This manuscript presents elemental composition data of highly oxidized compounds as clusters of nitrate ion, NO3-, and biogenic volatile organic compounds, especially a-pinene, oxidation products. The authors present a brief description of the APi-ToF instrument and mass calibration procedure for a large mass range, followed by comparison of mass spectra from Jülich chamber and the Hyytiälä field site along with a hypotheses for the formation mechanism of the highly oxidized compounds. Finally, the authors estimate the concentration of neutral molecules from the observed ion clusters. The data presented is very convincing and the manuscript is suitable for publication in ACP after the following comments are addressed.

Determination of isoprene and α-/β-pinene oxidation products in boreal forest aerosols from Hyytiälä, Finland: diel variations and possible link with particle formation events

Biogenic volatile organic compounds (VOCs), such as isoprene and alpha-/beta-pinene, are photo-oxidized in the atmosphere to non-volatile species resulting in secondary organic aerosol (SOA). The goal of this study was to examine time trends and diel variations of oxidation products of isoprene and alpha-/beta-pinene in order to investigate whether they are linked with meteorological parameters or trace gases. Separate day-night aerosol samples (PM(1)) were collected in a Scots pine dominated forest in southern Finland during 28 July-11 August 2005 and analyzed with gas chromatography/mass spectrometry (GC/MS). In addition, inorganic trace gases (SO(2), CO, NO(x), and O(3)), meteorological parameters, and the particle number concentration were monitored. The median total concentration of terpenoic acids (i.e., pinic acid, norpinic acid, and two novel compounds, 3-hydroxyglutaric acid and 2-hydroxy-4-isopropyladipic acid) was 65 ng m(-3), while that of isoprene oxidation products (i.e., 2-methyltetrols and C(5) alkene triols) was 17.2 ng m(-3). The 2-methyltetrols exhibited day/night variations with maxima during day-time, while alpha-/beta-pinene oxidation products did not show any diel variation. The sampling period was marked by a relatively high condensation sink, caused by pre-existing aerosol particles, and no nucleation events. In general, the concentration trends of the SOA compounds reflected those of the inorganic trace gases, meteorological parameters, and condensation sink. Both the isoprene and alpha-/beta-pinene SOA products were strongly influenced by SO(2), which is consistent with earlier reports that acidity plays a role in SOA formation. The results support previous proposals that oxygenated VOCs contribute to particle growth processes above boreal forest.

Characterization of new particle formation events at a background site in Southern Sweden: relation to air mass history

Particle formation events were analysed from aerosol number size distribution data collected at a background station in southern Sweden between February 2001 and May 2004. Events occurred on about 36% of all days and were favoured by high global radiation values. The clearest events (class I, 20% of all days) were observed when the formation rate of activated hypothetical clusters around 1 nm diameter, J1 was higher than 10(180*CondS-0.60), where CondS is the condensation sink (in s-1). The median condensable vapour concentration, observed formation rate at 3 nm, and growth rate during class I events were 3.0 × 107 cm-3, 1.1 cm-3 s-1 and 2.1 nm h-1, respectively. On 7% of all days, it was possible to observe growth of the newly formed particles exceeding 30 nm geometric mean diameter during event days in the evening, which is important for the regional particle population, and thereby the climate. A trajectory analysis revealed that cleaner air masses were relatively more important for the contribution of Aitken mode particles than polluted ones. Class I events were registered on 36% of all days when trajectories had passed over the open sea, indicating that ship traffic can contribute to particle formation and growth.

The natural aerosol over Northern Europe and its relation to anthropogenic emissions—implications of important climate feedbacks

Abstract We use a recently developed parametrization to estimate the regional particle field in the summer time troposphere over Scandinavia that would result if the forest were the only source of particles. The calculated field is compared with available observational data. It is concluded that the needle leaf forest above 58.N alone is capable of producing aerosol mass concentrations corresponding to 12.50% of todays values in the boundary layer over Scandinavia. We also demonstrate that the forest itself could produce up to 200 CCN per cubic centimetre on average over Scandinavia and further show that an increase in temperature by 5.8 .C compared to todays average temperature could increase this CCN population by 40%. The study shows that we are able to approximate the natural aerosol field resulting from biogenic emissions over the boreal forest in the northern hemispheric region. This information provide an important contribution in the evaluation of the climate effect caused by anthropogenic emissions of particles over the forest and also opens the possibility to better address the climate feedbacks believed to be associated with the boreal region.

New aerosol particle formation in different synoptic situations at Hyytiälä, Southern Finland

We examine the meteorological conditions favourable for new particle formation as a contribution to clarifying the responsible processes. Synoptic weather maps and satellite images over Southern Finland for 2003–2005 were examined, focusing mainly on air mass types, atmospheric frontal passages, and cloudiness. Arctic air masses are most favourable for new aerosol particle formation in the boreal forest. New particle formation tends to occur on days after passage of a cold front and on days without frontal passages. Cloudiness, often associated with frontal passages, decreases the amount of solar radiation, reducing the growth of new particles. When cloud cover exceeds 3–4 octas, particle formation proceeds at a slower rate or does not occur at all. During 2003–2005, the conditions that favour particle formation at Hyytiälä (Arctic air mass, post-cold-frontal passage or no frontal passage and cloudiness less than 3–4 octas) occur on 198 d. On 105 (57%) of those days, new particle formation occurred, indicating that these meteorological conditions alone can favour, but are not sufficient for, new particle formation and growth. In contrast, 53 d (28%) were classified as undefined days; 30 d (15%) were non-event days, where no evidence of increasing particle concentration and growth has been noticed.

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.

On particle formation prediction in continental boreal forest using micrometeorological parameters

[1] It has been hypothesized that biogenic aerosol formation in the southern Finland troposphere can be predicted using micrometeorological parameters and knowing preexisting aerosol surface area in the previous publication. There the concurrence of nucleation beginning with the rapid growth of convective boundary layer was demonstrated. In this work a nucleation probability term is introduced using statistical correlation between the particle formation and micrometeorological parameters. More refined analysis presented here demonstrates the increasing probability of nucleation mode aerosol presence with the increasing heat flux, temperature standard deviation, and vertical wind speed variance. Diurnal maximal values of the parameters mentioned are larger on days with nucleation event than on days without although these values are not significantly different during the convective layer growth. What distinguishes days with nucleation events is the size of condensation sink, which is significantly smaller on days with events than on days without. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0315 Atmospheric Composition and Structure: Biosphere/atmosphere interactions; 0325 Atmospheric Composition and Structure: Evolution of the atmosphere; 3322 Meteorology and Atmospheric Dynamics: Land/atmosphere interactions; KEYWORDS: nucleation in troposphere, forecasting particle formation, mixing layer, heat flux

Characteristics of the three years continuous data on new particle formation events observed at a boreal forest site

We have analyzed 184 formation events of new atmospheric aerosol particles, observed at a boreal forest site in Hyytiala, Southern Finland. Recognition, selection and classification of the formation events is based on continuous experimental size distribution data of submicron particles from a period of Jan 31st 1996–Sept 18th 1999 (1327 days). The apparent particle formation rates vary in the range of 0.001-1 particles/(cm3 s). The ultrafine particle growth rates vary in the range of 1–17 nm/h.