Alexei Kiselev

Soluble Mass, Hygroscopic Growth, and Droplet Activation of Coated Soot Particles during LACIS Experiment in November (LExNo)

The LACIS Experiment in November (LExNo) campaign was conducted in November 2005 at the Atmospheric Composition Change the European Network of Excellence (ACCENT) site Leipzig Aerosol Cloud Interaction Simulator (LACIS). The goal of LExNo was to provide deeper insight into the activation properties of coated soot particles imitating aged combustion aerosol particles. The aerosols were prepared by starting with spark-generated soot particles. In some experiments the soot particles were compacted by exposure to propanol vapor; in others this step was bypassed. The soot was thermally coated with ammonium sulfate, levoglucosan, or a mixture of both ammonium sulfate and levoglucosan. The synthesized particles were investigated using aerosol mass spectrometry, a Hygroscopicity Tandem differential mobility analyzer, two Wyoming static diffusion cloud condensation nuclei (CCN) instruments, a Droplet Measurement Technologies continuous flow CCN instrument, and LACIS. A close correlation between the hygroscopic growth factor at 98% relative humidity and the critical supersaturation of CCN activation was observed. Closure between hygroscopic growth, CCN activation, and chemical composition of the investigated particles was achieved with two different single-parameter Kohler model approaches and with a third approach, a standard Kohler model using as input parameter the soluble mass as determined by aerosol mass spectrometry. (Less)

Active sites in heterogeneous ice nucleation—the example of K-rich feldspars

From dust to ice How does ice form on the surfaces of aerosol particles? The process is important for climate and atmospheric properties but poorly understood at the molecular level, in part because the nature of the sites where ice growth begins is unclear. Kiselev et al. used electron microscopy and computer simulations to study the deposition of aligned ice crystals on feldspar, a major component of mineral dust (see the Perspective by Murray). Surface defects of the feldspar were responsible for its high ice-nucleation efficiency. Science, this issue p. 367; see also p. 346 Atmospheric ice nucleation on feldspar dust occurs at surface defects. Ice formation on aerosol particles is a process of crucial importance to Earth’s climate and the environmental sciences, but it is not understood at the molecular level. This is partly because the nature of active sites, local surface features where ice growth commences, is still unclear. Here we report direct electron-microscopic observations of deposition growth of aligned ice crystals on feldspar, an atmospherically important component of mineral dust. Our molecular-scale computer simulations indicate that this alignment arises from the preferential nucleation of prismatic crystal planes of ice on high-energy (100) surface planes of feldspar. The microscopic patches of (100) surface, exposed at surface defects such as steps, cracks, and cavities, are thought to be responsible for the high ice nucleation efficacy of potassium (K)–feldspar particles.

White-light optical particle spectrometer for in situ measurements of condensational growth of aerosol particles

A new optical particle counter was developed to provide fast in situ sizing of cloud droplets in the Leipzig Aerosol and Cloud Interaction Simulator (LACIS). The new instrument features white light for the illumination of the sampling volume: two off-axis elliptical mirrors, providing a wide angle of collection for light scattered by particles; and an optically defined sampling volume. The smooth unambiguous response characteristic for water droplets allows direct conversion of the measured signal amplitudes into droplet diameters. Preliminary response measurements for dry polystyrol microspheres and water droplets, grown in the LACIS on NaCl particles, have shown good agreement with the corresponding calculated response curves.

Contact freezing efficiency of mineral dust aerosols studied in an electrodynamic balance: quantitative size and temperature dependence for illite particles

Contact freezing has long been discussed as a candidate for cloud ice formation at temperatures warmer than about -25 degrees C, but until now the molecular mechanism underlying this process has remained obscure and little quantitative information about the size and temperature dependent contact freezing properties of the various aerosol species is available. In this contribution, we present the first quantitative measurements of the freezing probability of a supercooled droplet upon a single contact with a size selected illite mineral particle. It is found that this probability is a strong function of temperature and aerosol particle size. For the particles investigated and on the minute time scale of the experiment, contact freezing indeed dominates immersion freezing for all temperatures.

Experimental quantification of contact freezing in an electrodynamic balance

Heterogeneous nucleation of ice in a supercooled water droplet induced by external contact with a dry aerosol particle has long been known to be more effective than freezing induced by the same nucleus immersed in the droplet. However, the experimental quantification of contact freezing is challenging. Here we report an experimental method to determine the temperature-dependent ice nucleation probability of size-selected aerosol particles. The method is based on the suspension of supercooled charged water droplets in a laminar flow of air containing aerosol particles as contact freezing nuclei. The rate of droplet–particle collisions is calculated numerically with account for Coulomb attraction, drag force and induced dipole interaction between charged droplet and aerosol particles. The calculation is verified by direct counting of aerosol particles collected by a levitated droplet. By repeating the experiment on individual droplets for a sufficient number of times, we are able to reproduce the statistical freezing behavior of a large ensemble of supercooled droplets and measure the average rate of freezing events. The freezing rate is equal to the product of the droplet–particle collision rate and the probability of freezing on a single contact, the latter being a function of temperature, size and composition of the contact ice nuclei. Based on these observations, we show that for the types of particles investigated so far, contact freezing is the dominating freezing mechanism on the timescale of our experiment.

Temperature-dependent formation of NaCl dihydrate in levitated NaCl and sea salt aerosol particles

Recent laboratory studies indicate that the hydrated form of crystalline NaCl is potentially important for atmospheric processes involving depositional ice nucleation on NaCl dihydrate particles under cirrus cloud conditions. However, recent experimental studies reported a strong discrepancy between the temperature intervals where the efflorescence of NaCl dihydrate has been observed. Here we report the measurements of the volume specific nucleation rate of crystalline NaCl in the aqueous solution droplets of pure NaCl suspended in an electrodynamic balance at constant temperature and humidity in the range from 250 K to 241 K. Based on these measurements, we derive the interfacial energy of crystalline NaCl dihydrate in a supersaturated NaCl solution and determined its temperature dependence. Taking into account both temperature and concentration dependence of nucleation rate coefficients, we explain the difference in the observed fractions of NaCl dihydrate reported in the previous studies. Applying the heterogeneous classical nucleation theory model, we have been able to reproduce the 5 K shift of the NaCl dihydrate efflorescence curve observed for the sea salt aerosol particles, assuming the presence of super-micron solid inclusions (hypothetically gypsum or hemihydrate of CaSO4). These results support the notion that the phase transitions in microscopic droplets of supersaturated solution should be interpreted by accounting for the stochastic nature of homogeneous and heterogeneous nucleation and cannot be understood on the ground of bulk phase diagrams alone.

Laser vaporization of cirrus-like ice particles with secondary ice multiplication

Intense laser illumination of cirrus-like ice particles increases the amount of condensed water and modifies the particles’ albedo. We investigate the interaction of ultrashort laser filaments with individual 90-μm ice particles, representative of cirrus particles. The ice particles fragment under laser illumination. By monitoring the evolution of the corresponding ice/vapor system at up to 140,000 frames per second over 30 ms, we conclude that a shockwave vaporization supersaturates the neighboring region relative to ice, allowing the nucleation and growth of new ice particles, supported by laser-induced plasma photochemistry. This process constitutes the first direct observation of filament-induced secondary ice multiplication, a process that strongly modifies the particle size distribution and, thus, the albedo of typical cirrus clouds.

Secondary Ice Formation during Freezing of Levitated Droplets

AbstractThe formation of secondary ice in clouds, that is, ice particles that are created at temperatures above the limit for homogeneous freezing without the direct involvement of a heterogeneous ...

Immersion freezing of clay minerals and bacterial ice nuclei

The immersion mode ice nucleation efficiency of clay minerals and biological aerosols has been investigated using the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber. Both monodisperse and polydisperse populations of (1) various clay dust samples as well as (2) Snomax® (a proxy for bacterial ice nucleators) and (3) hematite are examined in the temperature range between −4°C and −35°C. The temperature dependence of ice formation inferred by the INAS (Ice Nucleation Active Surface-Site) density is investigated and discussed as a function of cooling rate and by comparing to predicted nucleation rates (i.e., classical nucleation theory with θ-probability density function nucleation scheme). To date, we observe that maintaining constant AIDA temperature does not trigger any new ice formation during the immersion freezing experiments with clay dust samples and Snomax®, implying strong temperature dependency (and weak time dependency) within our time scales and conditions of experiments. ...

Composition, Mixing State and Water Affinity of Meteoric Smoke Analogue Nanoparticles Produced in a Non-Thermal Microwave Plasma Source

Abstract The article reports on the composition, mixing state and water affinity of iron silicate particles which were produced in a non-thermal low-pressure microwave plasma reactor. The particles are intended to be used as meteoric smoke particle analogues. We used the organometallic precursors ferrocene (Fe(C5H5)2) and tetraethyl orthosilicate (TEOS, Si(OC2H5)4) in various mixing ratios to produce nanoparticles with radii between 1 nm and 4 nm. The nanoparticles were deposited on sample grids and their stoichiometric composition was analyzed in an electron microscope using energy dispersive X-ray spectroscopy (EDS). We show that the pure silicon oxide and iron oxide particles consist of SiO2 and Fe2O3, respectively. For Fe:(Fe+Si) ratios between 0.2 and 0.8 our reactor produces (in contrast to other particle sources) mixed iron silicates with a stoichiometric composition according to FexSi(1−x)O3 (0≤x≤1). This indicates that the particles are formed by polymerization of FeO3 and SiO3 and that rearrangement to the more stable silicates ferrosilite (FeSiO3) and fayalite (Fe2SiO4) does not occur at these conditions. To investigate the internal mixing state of the particles, the H2O surface desorption energy of the particles was measured. We found that the nanoparticles are internally mixed and that differential coating resulting in a core-shell structure does not occur.