Heikki Lihavainen

The Role of Sulfuric Acid in Atmospheric Nucleation

Little Things Do Matter Gas-phase sulfuric acid is important during atmospheric particle formation, but the mechanisms by which it forms new particles are unclear. Laboratory studies of the binary nucleation of sulfuric acid with water produce particles at rates that are many orders of magnitude too small to explain the concentration of sulfuric acid particles found in the atmosphere. Sipilä et al. (p. 1243) now show that gas-phase sulfuric acid does, in fact, undergo nucleation in the presence of water at a rate fast enough to account for the observed abundance of sulfuric acid particles in the atmosphere. These particles, which contain 1 to 2 sulfuric acid molecules each, were not detectable previously, owing to their small size, with diameters as small as 1.5 nanometers. Gas-phase sulfuric acid and water react fast enough to account for the concentration of atmospheric sulfuric acid particles. Nucleation is a fundamental step in atmospheric new-particle formation. However, laboratory experiments on nucleation have systematically failed to demonstrate sulfuric acid particle formation rates as high as those necessary to account for ambient atmospheric concentrations, and the role of sulfuric acid in atmospheric nucleation has remained a mystery. Here, we report measurements of new particles (with diameters of approximately 1.5 nanometers) observed immediately after their formation at atmospherically relevant sulfuric acid concentrations. Furthermore, we show that correlations between measured nucleation rates and sulfuric acid concentrations suggest that freshly formed particles contain one to two sulfuric acid molecules, a number consistent with assumptions that are based on atmospheric observations. Incorporation of these findings into global models should improve the understanding of the impact of secondary particle formation on climate.

Aerosols in polar regions: A historical overview based on optical depth and in situ observations

Large sets of filtered actinometer, filtered pyrheliometer and Sun photometer measurements have been carried out over the past 30 years by various groups at different Arctic and Antarctic sites and ...

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.

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.

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.

Homogeneous nucleation rate measurements of 1-butanol in helium: A comparative study of a thermal diffusion cloud chamber and a laminar flow diffusion chamber

Isothermal homogeneous nucleation rates of 1-butanol were measured both in a thermal diffusion cloud chamber and in a laminar flow diffusion chamber built recently at the Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, Prague, Czech Republic. The chosen system 1-butanol-helium can be studied reasonably well in both devices, in the overlapping range of temperatures. The results were compared with those found in the literature and those measured by Lihavainen in a laminar flow diffusion chamber of a similar design. The same isotherms measured with the thermal diffusion cloud chamber occur at highest saturation ratios of the three devices. Isotherms measured with the two laminar flow diffusion chambers are reasonably close together; the measurements by Lihavainen occur at lowest saturation ratios. The temperature dependences observed were similar in all three devices. The molecular content of critical clusters was calculated using the nucleation theorem and compared with the Kelvin equation. Both laminar flow diffusion chambers provided very similar sizes slightly above the Kelvin equation, whereas the thermal diffusion cloud chamber suggests critical cluster sizes significantly smaller. The results found elsewhere in the literature were in reasonable agreement with our results.

The carrier gas pressure effect in a laminar flow diffusion chamber, homogeneous nucleation of n-butanol in helium

Homogeneous nucleation rate isotherms of n-butanol+helium were measured in a laminar flow diffusion chamber at total pressures ranging from 50 to 210 kPa to investigate the effect of carrier gas pressure on nucleation. Nucleation temperatures ranged from 265 to 280 K and the measured nucleation rates were between 10(2) and 10(6) cm(-3) s(-1). The measured nucleation rates decreased as a function of increasing pressure. The pressure effect was strongest at pressures below 100 kPa. This negative carrier gas effect was also temperature dependent. At nucleation temperature of 280 K and at the same saturation ratio, the maximum deviation between nucleation rates measured at 50 and 210 kPa was about three orders of magnitude. At nucleation temperature of 265 K, the effect was negligible. Qualitatively the results resemble those measured in a thermal diffusion cloud chamber. Also the slopes of the isothermal nucleation rates as a function of saturation ratio were different as a function of total pressure, 50 kPa isotherms yielded the steepest slopes, and 210 kPa isotherms the shallowest slopes. Several sources of inaccuracies were considered in the interpretation of the results: uncertainties in the transport properties, nonideal behavior of the vapor-carrier gas mixture, and shortcomings of the used mathematical model. Operation characteristics of the laminar flow diffusion chamber at both under-and over-pressure were determined to verify a correct and stable operation of the device. We conclude that a negative carrier gas pressure effect is seen in the laminar flow diffusion chamber and it cannot be totally explained with the aforementioned reasons.

Homogeneous water nucleation in a laminar flow diffusion chamber

Homogeneous nucleation rates of water at temperatures between 240 and 270 K were measured in a laminar flow diffusion chamber at ambient pressure and helium as carrier gas. Being in the range of 10(2)-10(6) cm(-3) s(-1), the experimental results extend the nucleation rate data from literature consistently and fill a pre-existing gap. Using the macroscopic vapor pressure, density, and surface tension for water we calculate the nucleation rates predicted by classic nucleation theory (CNT) and by the empirical correction function of CNT by Wolk and Strey [J. Phys. Chem. B 105, 11683 (2001)]. As in the case of other systems (e.g., alcohols), CNT predicts a stronger temperature dependence than experimentally observed, whereas the agreement with the empirical correction function is good for all data sets. Furthermore, the isothermal nucleation rate curves allow us to determine the experimental critical cluster sizes by use of the nucleation theorem. A comparison with the critical cluster sizes calculated by use of the Gibbs-Thomson equation is remarkably good for small cluster sizes, for bigger ones the Gibbs-Thomson equation overestimates the cluster sizes.

Observational signature of the direct radiative effect by natural boreal forest aerosols and its relation to the corresponding first indirect effect

By using a screened set of long-term aerosol measurement data, the contribution of natural boreal forest aerosols to the direct radiative effect (DRE) was observed at a remote continental site in n ...