Showing papers by "Tuukka Petäjä published in 2006"

Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms

Abstract: . We have investigated the formation and early growth of atmospheric secondary aerosol particles building on atmospheric measurements. The measurements were part of the QUEST 2 campaign which took place in spring 2003 in Hyytiala (Finland). During the campaign numerous aerosol particle formation events occurred of which 15 were accompanied by gaseous sulphuric acid measurements. Our detailed analysis of these 15 events is focussed on nucleation and early growth (to a diameter of 3 nm) of fresh particles. It revealed that new particle formation seems to be a function of the gaseous sulphuric acid concentration to the power from one to two when the time delay between the sulphuric acid and particle number concentration is taken into account. From the time delay the growth rates of freshly nucleated particles from 1 nm to 3 nm were determined. The mean growth rate was 1.2 nm/h and it was clearly correlated with the gaseous sulphuric acid concentration. We tested two nucleation mechanisms – recently proposed cluster activation and kinetic type nucleation – as possible candidates to explain the observed dependences, and determined experimental nucleation coefficients. We found that some events are dominated by the activation mechanism and some by the kinetic mechanism. Inferred coefficients for the two nucleation mechanisms are the same order of magnitude as chemical reaction coefficients in the gas phase and they correlate with the product of gaseous sulphuric acid and ammonia concentrations. This indicates that besides gaseous sulphuric acid also ammonia has a role in nucleation.

Detecting charging state of ultra-fine particles: instrumental development and ambient measurements

Abstract: . The importance of ion-induced nucleation in the lower atmosphere has been discussed for a long time. In this article we describe a new instrumental setup – Ion-DMPS – which can be used to detect contribution of ion-induced nucleation on atmospheric new particle formation events. The device measures positively and negatively charged particles with and without a bipolar charger. The ratio between "charger off" to "charger on" describes the charging state of aerosol particle population with respect to equilibrium. Values above one represent more charges than in an equilibrium (overcharged state), and values below unity stand for undercharged situation, when there is less charges in the particles than in the equilibrium. We performed several laboratory experiments to test the operation of the instrument. After the laboratory tests, we used the device to observe particle size distributions during atmospheric new particle formation in a boreal forest. We found that some of the events were clearly dominated by neutral nucleation but in some cases also ion-induced nucleation contributed to the new particle formation. We also found that negative and positive ions (charged particles) behaved in a different manner, days with negative overcharging were more frequent than days with positive overcharging.

Hygroscopic properties of ultrafine aerosol particles in the boreal forest: diurnal variation, solubility and the influence of sulfuric acid

Abstract: The hygroscopic growth of aerosol particles present in a boreal forest was measured at a relative humid- ity of 88%. Simultaneously the gas phase concentration of sulfuric acid, a very hygroscopic compound, was monitored. The focus was mainly on days with new particle formation by nucleation. The measured hygroscopic growth factors (GF) correlated positively with the gaseous phase sulfuric acid concentrations. The smaller the particles, the stronger the correlation, with r=0.20 for 50 nm and r=0.50 for 10 nm particles. The increase in GF due to condensing sulfuric acid is expected to be larger for particles with initially smaller masses. During new particle formation, the changes in solu- bility of the new particles were calculated during their growth to Aitken mode sizes. As the modal diameter increased, the solubility of the particles decreased. This indicated that the initial particle growth was due to more hygroscopic com- pounds, whereas the later growth during the evening and night was mainly caused by less hygroscopic or even hy- drophobic compounds. For all the measured sizes, a diur- nal variation in GF was observed both during days with and without particle formation. The GF was lowest at around midnight, with a mean value of 1.12-1.24 depending on par- ticle size and if new particle formation occurred during the day, and increased to 1.25-1.34 around noon. This can be tentatively explained by day- and nighttime gas-phase chem- istry; different vapors will be present depending on the time of day, and through condensation these compounds will alter the hygroscopic properties of the particles in different ways.

Sub-micron atmospheric aerosols in the surroundings of Marseille and Athens: physical characterization and new particle formation

Abstract: . The properties of atmospheric aerosol particles in Marseille and Athens were investigated. The studies were performed in Marseille, France, during July 2002 and in Athens, Greece, during June 2003. The aerosol size distribution and the formation and growth rates of newly formed particles were characterized using Differential Mobility Particle Sizers. Hygroscopic properties were observed using a Hygroscopic Tandem Differential Mobility Analyzer setup. During both campaigns, the observations were performed at suburban, almost rural sites, and the sites can be considered to show general regional background behavior depending on the wind direction. At both sites there were clear pattern for both aerosol number concentration and hygroscopic properties. Nucleation mode number concentration increased during the morning hours indicating new particle formation, which was observed during more than 30% of the days. The observed formation rate was typically more than 1 cm−3 s−1, and the growth rate was between 1.2–9.9 nm h−1. Based on hygroscopicity measurements in Athens, the nucleation mode size increase was due to condensation of both water insoluble and water soluble material. However, during a period of less anthropogenic influence, the growth was to a larger extent due to water insoluble components. When urban pollution was more pronounced, growth due to condensation of water soluble material dominated.

Non-volatile residuals of newly formed atmospheric particles in the boreal forest

Abstract: The volatility of sub-micrometer atmospheric aerosol particles was studied in a rural background environment in Finland using a combination of a heating tube and a scanning mobility particle sizer. The analysis focused on nano-particles formed from nucleation bursts which were subsequently observed during their growth in the diameter range between 5 and 60 nm. During the 6 days of new particle formation shown in detail, the concentrations of newly formed particles increased up to 10 000 cm?3. The number of nucleation mode particles measured after volatilization in the heating tube at 280°C was up to 90% of the total number under ambient conditions. Taking into account the absolute accuracy of the size distribution measurements, all ambient particles found in the rural atmosphere could have a non-volatile core after volatilization at 280°C. As the regional new particle formation events developed over time as a result of further vapor condensation, the newly formed particles grew at an average growth rate of 2.4±0.3 nm h?1. Importantly, the non-volatile cores of nucleation mode particles were also observed to grow over time, however, at a lower average growth rate of 0.6±0.3 nm h?1. One implication of the volatility analysis is that the newly formed particles, which have reached ambient diameters of 15 nm, are unlikely to consist of sulfuric acid, ammonium sulfate, and water alone. A relatively constant ratio between the growth rate of the ambient particles as well as their non-volatile cores indicates that non-volatile matter is formed only gradually in the growing particles. The non-volatile fraction of the particles showed some correlation with the ambient temperature. The composition and formation mechanism of this non-volatile material in nucleation mode particles are, to date, not known.

Detection Efficiency of a Water-Based TSI Condensation Particle Counter 3785

Abstract: In this article we present observations on the detection efficiency of a recently developed TSI 3785 Water Condensation Particle Counter (WCPC). The instrument relies on activation of sampled particles by water condensation. The supersaturation is generated by directing a saturated airflow into a “growth tube,” in which the mass transfer of water vapor is faster than heat transfer. This results in supersaturated conditions with respect to water vapor in the centerline of a “growth tube.” In this study, the cut-off diameter, that is, the size, where 50% of the sampled particles are successfully activated, varied from 4 to 14 nm for silver particles as a function of temperature difference between the saturator and the growth tube. The solubility of the sampled particles to water played an important role in the detection efficiency. Cut-off diameters for ammonium sulphate and sodium chloride particles were 5.1 and 3.6–3.8 nm, respectively at nominal operation conditions. Corresponding cut-off diameter for hy...