Oxidation products of biogenic emissions contribute to nucleation of atmospheric particles.

Atmospheric new-particle formation affects climate and is one of the least understood atmospheric aerosol processes. The complexity and variability of the atmosphere has hindered elucidation of the fundamental mechanism of new-particle formation from gaseous precursors. We show, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere. The experiments reveal a nucleation mechanism involving the formation of clusters containing sulfuric acid and oxidized organic molecules from the very first step. Inclusion of this mechanism in a global aerosol model yields a photochemically and biologically driven seasonal cycle of particle concentrations in the continental boundary layer, in good agreement with observations.

Quantitative characterization of critical nanoclusters nucleated on large single molecules.

First order phase transitions involve nucleation, formation of nanoscale regions of a new phase within a metastable parent phase. Using the heterogeneous nucleation theorem we show how clusters formed by nucleation on single molecules evolve from the gas phase and determine the critical size beyond which condensation starts to form aerosol particles. Our experiments reveal the activation of molecules into droplets to happen via formation of critical clusters substantially larger than the seed molecule. The nanosized critical clusters were found to be well predicted by the Kelvin-Thomson relation pointing directly to the key step in the phase transition.

Development of a model to compute the extension of life supporting zones for Earth-like exoplanets.

A radiative convective model to calculate the width and the location of the life supporting zone (LSZ) for different, alternative solvents (i.e. other than water) is presented. This model can be applied to the atmospheres of the terrestrial planets in the solar system as well as (hypothetical, Earth-like) terrestrial exoplanets. Cloud droplet formation and growth are investigated using a cloud parcel model. Clouds can be incorporated into the radiative transfer calculations. Test runs for Earth, Mars and Titan show a good agreement of model results with observations.

Experiments on the temperature dependence of heterogeneous nucleation on nanometer-sized NaCl and Ag particles.

Experimental investigations on the activation of NaCl and Ag aerosol particles by heterogeneous nucleation of n-propanol vapor at well-defined vapor saturation ratios are presented. Particular emphasis is placed on the temperature dependence of this process from -11 to +14 °C. Aerosols are generated in a tube furnace and electrostatically classified at mean geometric mobility equivalent diameters between 3.6 and 11 nm. Activation probabilities are measured by means of expansion chamber experiments, and onset n-propanol saturation ratios are subsequently determined. The experiments with Ag particles do not produce any unexpected results. The results for NaCl particles, however, show a temperature trend of the onset saturation ratios that is opposite to that predicted by classical nucleation theory. This stresses the important role that surface properties play in heterogeneous nucleation processes. By tentatively assuming a temperature-dependent contact angle, we are able to theoretically reproduce this reversed temperature trend. In addition, the shrinkage of NaCl condensation particles is investigated for varying amounts of n-propanol vapor, and contact angle measurements are performed at temperatures ranging from -7 to +30 °C.

Heterogeneous nucleation experiments bridging the scale from molecular ion clusters to nanoparticles.

Generation, investigation, and manipulation of nanostructured materials are of fundamental and practical importance for several disciplines, including materials science and medicine. Recently, atmospheric new particle formation in the nanometer-size range has been found to be a global phenomenon. Still, its detailed mechanisms are mostly unknown, largely depending on the incapability to generate and measure nanoparticles in a controlled way. In our experiments, an organic vapor (n-propanol) condenses on molecular ions, as well as on charged and uncharged inorganic nanoparticles, via initial activation by heterogeneous nucleation. We found a smooth transition in activation behavior as a function of size and activation to occur well before the onset of homogeneous nucleation. Furthermore, nucleation enhancement for charged particles and a substantial negative sign preference were quantitatively detected.

Heterogeneous multicomponent nucleation theorems for the analysis of nanoclusters.

In this paper we present a new form of the nucleation theorems applicable to heterogeneous nucleation. These heterogeneous nucleation theorems allow, for the first time, direct determination of properties of nanoclusters formed on pre-existing particles from measured heterogeneous nucleation probabilities. The theorems can be used to analyze the size (first theorem) and the energetics (second theorem) of heterogeneous clusters independent of any specific nucleation model. We apply the first theorem to the study of small water and n-propanol clusters formed at the surface of 8 nm silver particles. According to the experiments the size of the two-component critical clusters is found to be below 90 molecules, and only less than 20 molecules for pure water, less than 300 molecules for pure n-propanol. These values are drastically smaller than the ones predicted by the classical nucleation theory, which clearly indicates that the nucleating clusters are too small to be quantitatively described using a macroscopic theory.

Mass and thermal accommodation during gas-liquid condensation of water.

In this Letter we report, for the first time, direct and simultaneous determinations of mass and thermal accommodation coefficients for water vapor condensation in air, based on the observation of droplet growth kinetics in an expansion cloud chamber. Our experiments exclude values below 0.85 for the thermal and below 0.4 for the mass accommodation coefficients at temperatures ranging from 250 to 290 K. Both coefficients are likely to be 1 for all studied conditions. Previously available experimental data on the mass accommodation coefficient for water span about 3 orders of magnitude. Our results provide new and firm insight to cloud microphysics and consequently to the global radiative balance.