Pasi Aalto

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.

Aerosol formation: atmospheric particles from organic vapours.

Aerosol particles produced over forested areas may affect climate by acting as nuclei for cloud condensation, but their composition (and hence the chemical species that drive their production) remains an open question. Here we show, to our knowledge for the first time, that these newly formed particles (3–5 nm in diameter) are composed primarily of organic species, such as cis-pinonic acid and pinic acid, produced by oxidation of terpenes in organic vapours released from the canopy.

Observations of ultrafine aerosol particle formation and growth in boreal forest

Number size distribution of ambient submicron and ultrafine aerosol particles have been measured on a continuous basis (every 10 minutes) for three quarters of the year 1996, at a forest site in Southern Finland. Continuous monitoring offers additional insight over the diurnal dynamics of the submicron size distribution, including existence of clearly separate size modes as well as events of new particle formation. Selected examples of the measured size distributions are presented, including the particle formation events observed at the measurement site. Typical characteristics of days with particle formation events versus days of no events are discussed.

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.

Physical characterization of aerosol particles during nucleation events

Particle concentrations and size distributions have been measured from different heights inside and above a boreal forest during three BIOFOR campaigns (14 April–22 May 1998, 27 July–21 August 1998 and 20 March–24 April 1999) in Hyytiälä, Finland. Typically, the shape of the background distribution inside the forest exhibited 2 dominant modes: a fine or Aitken mode with a geometric number mean diameter of 44 nm and a mean concentration of 1160 cm−3 and an accumulation mode with mean diameter of 154 nm and a mean concentration of 830 cm−3. A coarse mode was also present, extending up to sizes of 20 μm having a number concentration of 1.2 cm−3, volume mean diameter of 2.0 μm and a geometric standard deviation of 1.9. Aerosol humidity was lower than 50% during the measurements. Particle production was observed on many days, typically occurring in the late morning. Under these periods of new particle production, a nucleation mode was observed to form at diameter of the order of 3 nm and, on most occasions, this mode was observed to grow into Aitken mode sizes over the course of a day. Total concentrations ranged from 410–45 000 cm−3, the highest concentrations occurring on particle production days. A clear gradient was observed between particle concentrations encountered below the forest canopy and those above, with significantly lower concentrations occurring within the canopy. Above the canopy, a slight gradient was observed between 18 m and 67 m, with at maximum 5% higher concentration observed at 67 m during the strongest concentration increases.

Condensation and coagulation sinks and formation of nucleation mode particles in coastal and boreal forest boundary layers

[1]xa0The formation and growth of new particles has been evaluated using a revised version of a simple, but novel, theoretical tool. The concentration of condensable vapors and their source rates has been estimated using the aerosol condensation sink together with the measured particle growth rate. Also, by adding the coagulation sink and the measured formation rate of 3 nm particles, the formation rate of 1 nm particles and their concentration can be estimated. Condensation and coagulation sinks can be obtained from ambient aerosol size distribution data. The method has been applied to analyze the particle formation and growth rates observed during coastal and boreal forest nucleation events. The condensation sinks are typically 4–7 × 10−3 s−1 in the forest and 2 × 10−3 s−1 under coastal conditions, while the coagulation sinks for 1, 2, and 3 nm particles are typically smaller by factors 1.5–2, 5–7, and 11–15, respectively. The measured growth rates are 2–10 nm/h for the boreal forest and range from 15 to 180 nm/h at the coast, corresponding to a vapor concentration of 2–13 × 107 cm−3 and 108 cm−3 to 109 cm−3, respectively. The vapor source rate was 1–2 × 105 cm−3s−1 in the boreal forest and 2–5 × 106 cm−3s−1 in the coastal environment. The estimated formation rate of 1 nm particles in the forest environment was 8–20 cm−3s−1 and 300–10,000 cm−3s−1 at the coast. The concentration of 1 nm particles was estimated to be 2000–5000 and 4 × 104–7 × 106 particles cm−3 in forest and at coast, respectively.

Hygroscopic properties of aerosol particles in the north-eastern Atlantic during ACE-2

Measurements of the hygroscopic properties of sub-micrometer atmospheric aerosol particles were performed with hygroscopic tandem differential mobility analysers (H-TDMA) at 5 sites in the subtropical north-eastern Atlantic during the second Aerosol Characterization Experiment (ACE-2) from 16 June to 25 July 1997. Four of the sites were in the marine boundary layer and one was, at least occasionally, in the lower free troposphere. The hygroscopic diameter growth factors of individual aerosol particles in the dry particle diameter range 10−440 nm were generally measured for changes in relative humidity (RH) from <10% to 90%. In the marine boundary layer, growth factors at 90% RH were dependent on location, air mass type and particle size. The data was dominated by a unimodal growth distribution of more-hygroscopic particles, although a bimodal growth distribution including less-hygroscopic particles was observed at times, most often in the more polluted air masses. In clean marine air masses the more-hygroscopic growth factors ranged from about 1.6 to 1.8 with a consistent increase in growth factor with increasing particle size. There was also a tendency toward higher growth factors as sodium to sulphate molar ratio increased with increasing sea-salt contribution at higher wind speeds. During outbreaks of European pollution in the ACE-2 region, the growth factors of the largest particles were reduced, but only slightly. Growth factors at all sizes in both clean and polluted air masses were markedly lower at the Sagres, Portugal site due to more proximate continental influences. The frequency of occurrence of less-hygroscopic particles with a growth factor of ca. 1.15 was greatest during polluted conditions at Sagres. The free tropospheric 50 nm particles were predominately less-hygroscopic, with an intermediate growth factor of 1.4, but more-hygroscopic particles with growth factors of about 1.6 were also frequent. While these particles probably originate from within the marine boundary layer, the less-hygroscopic particles are probably more characteristic of lower free tropospheric air masses. For those occasions when measurements were made at 90% and an intermediate 60% or 70% RH, the growth factor G(RH) of the more-hygroscopic particles could be modelled empirically by a power law expression. For the ubiquitous more-hygroscopic particles, the expressions G(RH)=(1-RH/100)-0.210 for 50 nm Aitken mode particles and G(RH)=(1-RH/100)-0.233 for 166 nm accumulation mode particles are recommended for clean marine air masses in the north-eastern Atlantic within the range 0

ONE-YEAR DATA OF SUBMICRON SIZE MODES OF TROPOSPHERIC BACKGROUND AEROSOL IN SOUTHERN FINLAND

Number size distributions of submicron atmospheric aerosol were measured between February 1, 1996 and January 31, 1997 at a forest site in Southern Finland. Over 50,000 10-min spectra in the size range 3–500 nm were obtained by two parallel DMPSs. The spectra were fitted with two or three lognormal distributions. The occurrence and evolution of different size modes are described, and the seasonal variation of the modes are discussed. Particle formation with subsequent growth is observed to take place in the vicinity of the site mostly during spring time. Particle growth leads to a strong connection between the mean sizes and concentrations of nucleation and Aitken mode particles in spring. During winter time, the modes are more separate and stable in particle size. Also the average concentration of nucleation mode particles (Dp<20 nm) is usually less in winter time, but still a clear nucleation mode is frequently observed. The characteristic features of summer and autumn are not as distinguishable as they are for winter and spring.

Hygroscopic and CCN properties of aerosol particles in boreal forests

The measurements of the hygroscopic and cloud condensation nuclei (CCN) properties of sub-micrometer atmospheric aerosol particles were performed with two tandem differential mobility analysers (TDMA) and a CCN counter at the Hyytiälä forest field station in south-central Finland during the BIOFOR campaign. The TDMAs were used to measure hygroscopic diameter growth factors of individual aerosol particles in the dry particle diameter range 10–365 nm when taken from the dry state (relative humidity RH <5%) to RH=90%. The CCN counter was used to study the activation of aerosol particles when exposed to supersaturated conditions. The measurements show clear diurnal pattern of particle solubility. The pattern was strongest for particles in nucleation and Aitken modes. The lowest growth factor (soluble fraction) values were detected during late evening and early morning and the maximum was observed during noon-afternoon. The highest soluble fractions were determined for nucleation mode particles. The response of hygroscopic growth to changes of relative humidity suggests that the soluble compounds are either fully soluble or deliquescent well before 70% RH. The hygroscopic growth was investigated additionally by a detailed model using the size-resolved composition from the impactor samples. The comparison between different instruments shows good consistency. We found good agreement for the 20 nm growth factors measured with two TDMAs, not only on average but also regarding the temporal variation. The similar conclusion was drawn for comparison of TDMA with CCNC for Aitken mode particles with dry sizes 50 and 73 nm. Differences between wet and dry spectra measured using APS and CSASP spectrometer probes were used to derive growth factors for coarse mode particles. Growth factors for coarse mode particles (Dp ca. 2 μm) ranged between 1.0 and 1.6. Agreement between the evolution of growth factors with time for both accumulation and coarse modes was observed regularly. However, similar portions of the data set also indicated clear differences and consequently different chemical compositions between both modes. When the differences between both modes were observed, the coarse mode always behaved in a less hygroscopic manner, with growth factors near one.

Biogenic iodine emissions and identification of end-products in coastal ultrafine particles during nucleation bursts

[1]xa0Ultrafine particles sampled during new particle formation bursts observed in the coastal zone were studied with transmission electron microscopy (TEM) and elemental analysis using energy-dispersive X ray (EDX). It was observed that both iodine and sulphur were present in the new particles with diameter below 10 mn. Gaseous emissions of halogen compounds from seaweeds were also measured at the same location during low-tide particle nucleation episodes. Based on the presence of iodine in the particle phase during low-tide nucleation bursts, and the significant emission of iodine compounds from the seaweeds during these periods, it is apparent that part of the biogenic iodine species emitted from the seaweeds end up in the ultrafine particulate phase. It was not possible to quantitatively determine the iodine content in the particles; however, in most cases the relative contribution from iodine and sulphate was similar, while some cases indicated no sulphate. On larger sized particles the contribution of sulphate was significantly higher than iodine. It appears that the condensable species leading to the appearance of new particles in the coastal atmosphere is an iodine species. Whether or not this iodine species also participates in the nucleation of new stable clusters could not be completely verified.