Development of heterogeneous ice nucleation rate coefficient parameterizations from ambient measurements

Abstract. At the Leipzig Cloud Interaction Simulator (LACIS) experiments investigating homogeneous and heterogeneous nucleation of ice (particularly immersion freezing in the latter case) have been carried out. Here both the physical LACIS setup and the numerical model developed to design experiments at LACIS and interpret their results are presented in detail. Combining results from the numerical model with experimental data, it was found that for the experimental parameter space considered, classical homogeneous ice nucleation theory is able to predict the freezing behavior of highly diluted ammonium sulfate solution droplets, while classical heterogeneous ice nucleation theory, together with the assumption of a constant contact angle, fails to predict the immersion freezing behavior of surrogate mineral dust particles (Arizona Test Dust, ATD). The main reason for this failure is the compared to experimental data apparently overly strong temperature dependence of the nucleation rate coefficient. Assuming, in the numerical model, Classical Nucleation Theory (CNT) for homogeneous ice nucleation and a CNT-based parameterization for the nucleation rate coefficient in the immersion freezing mode, recently published by our group, it was found that even for a relatively effective ice nucleating agent such as pure ATD, there is a temperature range where homogeneous ice nucleation is dominant. The main explanation is the apparently different temperature dependencies of the two freezing mechanisms. Finally, reviewing the assumptions made during the derivation of the parameterization, it was found that the assumption of constant temperature during ice nucleation and the chosen nucleation time were highly justified, underlining the applicability of both the method to determine the fitting coefficients in the parameterization equation, and the validity of the parameterization concept itself.

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Homogeneous and heterogeneous ice nucleation at LACIS: operating principle and theoretical studies

Atmospheric Chemistry and Physics ◽

10.5194/acp-11-1753-2011 ◽

2011 ◽

Vol 11 (4) ◽

pp. 1753-1767 ◽

Cited By ~ 54

Author(s):

S. Hartmann ◽

D. Niedermeier ◽

J. Voigtländer ◽

T. Clauss ◽

R. A. Shaw ◽

...

Keyword(s):

Experimental Data ◽

Numerical Model ◽

Nucleation Rate ◽

Rate Coefficient ◽

Ice Nucleation ◽

Freezing Behavior ◽

Nucleation Theory ◽

Dust Particles ◽

Immersion Freezing ◽

Heterogeneous Ice Nucleation

Abstract. At the Leipzig Aerosol Cloud Interaction Simulator (LACIS) experiments investigating homogeneous and heterogeneous nucleation of ice (particularly immersion freezing in the latter case) have been carried out. Here both the physical LACIS setup and the numerical model developed to design experiments at LACIS and interpret their results are presented in detail. Combining results from the numerical model with experimental data, it was found that for the experimental parameter space considered, classical homogeneous ice nucleation theory is able to predict the freezing behavior of highly diluted ammonium sulfate solution droplets, while classical heterogeneous ice nucleation theory, together with the assumption of a constant contact angle, fails to predict the immersion freezing behavior of surrogate mineral dust particles (Arizona Test Dust, ATD). The main reason for this failure is the compared to experimental data apparently overly strong temperature dependence of the nucleation rate coefficient. Assuming, in the numerical model, Classical Nucleation Theory (CNT) for homogeneous ice nucleation and a CNT-based parameterization for the nucleation rate coefficient in the immersion freezing mode, recently published by our group, it was found that even for a relatively effective ice nucleating agent such as pure ATD, there is a temperature range where homogeneous ice nucleation is dominant. The main explanation is the apparently different temperature dependencies of the two freezing mechanisms. Finally, reviewing the assumptions made during the derivation of the CNT-based parameterization for immersion freezing, it was found that the assumption of constant temperature during ice nucleation and the chosen ice nucleation time were justified, underlining the applicability of the method to determine the fitting coefficients in the parameterization equation.

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Heterogeneous Ice Nucleation Rate Coefficient of Water Droplets Coated by a Nonadecanol Monolayer

The Journal of Physical Chemistry C ◽

10.1021/jp066080w ◽

2007 ◽

Vol 111 (5) ◽

pp. 2149-2155 ◽

Cited By ~ 145

Author(s):

B. Zobrist ◽

T. Koop ◽

B. P. Luo ◽

C. Marcolli ◽

T. Peter

Keyword(s):

Nucleation Rate ◽

Rate Coefficient ◽

Ice Nucleation ◽

Water Droplets ◽

Heterogeneous Ice Nucleation

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Immersion freezing of ice nucleating active protein complexes

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-12-21321-2012 ◽

2012 ◽

Vol 12 (8) ◽

pp. 21321-21353 ◽

Cited By ~ 3

Author(s):

S. Hartmann ◽

S. Augustin ◽

T. Clauss ◽

J. Voigtländer ◽

D. Niedermeier ◽

...

Keyword(s):

Pseudomonas Syringae ◽

Nucleation Rate ◽

Protein Complex ◽

Protein Complexes ◽

Ice Nucleation ◽

Temperature Range ◽

Immersion Freezing ◽

New Perspective ◽

Lower Temperature ◽

Heterogeneous Ice Nucleation

Abstract. Biological particles, e.g. bacteria and their Ice Nucleating Active (INA) protein complexes, might play an important role for the ice formation in atmospheric mixed-phase clouds. Therefore, the immersion freezing behavior of INA protein complexes generated from a SnomaxTM solution/suspension was investigated as function of temperature in a range of −5 °C to −38 °C at the Leipzig Aerosol Cloud Interaction Simulator (LACIS). The immersion freezing of droplets containing small numbers of INA protein complexes occurs in a temperature range of −7 °C and −10 °C. The experiments performed in the lower temperature range, where all droplets freeze which contain at least one INA protein complex, are used to determine the average number of INA protein complexes present, assuming that the INA protein complexes are Poisson distributed over the droplet ensemble. Knowing the average number of INA protein complexes, the heterogeneous ice nucleation rate and rate coefficient of a single INA protein complex is determined by using the newly-developed CHESS model (stoCHastic model of idEntical poiSSon distributed ice nuclei). Therefore, we assume the ice nucleation process to be of stochastic nature, and a parameterization of the INA protein complex's nucleation rate. Analyzing the results of immersion freezing experiments from literature (SnomaxTM and Pseudomonas syringae bacteria), to results gained in this study, demonstrates that first, a similar temperature dependence of the heterogeneous ice nucleation rate for a single INA protein complex was found in all experiments, second, the shift of the ice fraction curves to higher temperatures can be explained consistently by a higher average number of INA protein complexes being present in the droplet ensemble, and finally the heterogeneous ice nucleation rate of one single INA protein complex might be also applicable for intact Pseudomonas syringae bacteria cells. The results obtained in this study allow a new perspective on the interpretation of immersion freezing experiments considering INA protein complexes and the derived simple parameterization of the heterogeneous ice nucleation rate can be used in cloud resolving models for studying the effect of bacteria induced ice nucleation.

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Ice nucleation from aqueous NaCl droplets with and without marine diatoms

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-11-8291-2011 ◽

2011 ◽

Vol 11 (3) ◽

pp. 8291-8336 ◽

Cited By ~ 7

Author(s):

P. A. Alpert ◽

J. Y. Aller ◽

D. A. Knopf

Keyword(s):

Surface Area ◽

Water Activity ◽

Nucleation Rate ◽

Particle Production ◽

Ice Nucleation ◽

Nucleation Theory ◽

Rate Coefficients ◽

Freezing Temperatures ◽

Aqueous Volume ◽

Heterogeneous Ice Nucleation

Abstract. Ice formation in the atmosphere by homogeneous and heterogeneous nucleation is one of the least understood processes in cloud microphysics and climate. Here we describe our investigation of the marine environment as a potential source of atmospheric IN by experimentally observing homogeneous ice nucleation from aqueous NaCl droplets and comparing against heterogeneous ice nucleation from aqueous NaCl droplets containing intact and fragmented diatoms. Homogeneous and heterogeneous ice nucleation are studied as a function of temperature and water activity, aw. Additional analyses are presented on the dependence of diatom surface area and aqueous volume on heterogeneous freezing temperatures, ice nucleation rates, ωhet, ice nucleation rate coefficients, Jhet, and differential and cumulative ice nuclei spectra, k(T) and K(T), respectively. Homogeneous freezing temperatures and corresponding nucleation rate coefficients are in agreement with the water activity based homogeneous ice nucleation theory within experimental and predictive uncertainties. Our results confirm, as predicted by classical nucleation theory, that a stochastic interpretation can be used to describe this nucleation process. Heterogeneous ice nucleation initiated by intact and fragmented diatoms can be adequately represented by a modified water activity based ice nucleation theory. A horizontal shift in water activity, Δaw, het = 0.2303, of the ice melting curve can describe median heterogeneous freezing temperatures. Individual freezing temperatures showed no dependence on available diatom surface area and aqueous volume. Determined at median diatom freezing temperatures for aw from 0.8 to 0.99, ωhet ~ 0.11+0.06−0.05 s−1, Jhet ~ 1.0+1.16−0.61 × 104 cm−2 s−1, and K ~ 6.2+3.5−4.1 × 104 cm−2. The experimentally derived ice nucleation rates and nuclei spectra allow us to estimate ice particle production which we subsequently use for a comparison with observed ice crystal concentrations typically found in cirrus and polar marine mixed-phase clouds. Differences in application of time-dependent and time-independent analyses to predict ice particle production are discussed.

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Ice nucleation from aqueous NaCl droplets with and without marine diatoms

Atmospheric Chemistry and Physics ◽

10.5194/acp-11-5539-2011 ◽

2011 ◽

Vol 11 (12) ◽

pp. 5539-5555 ◽

Cited By ~ 60

Author(s):

P. A. Alpert ◽

J. Y. Aller ◽

D. A. Knopf

Keyword(s):

Surface Area ◽

Water Activity ◽

Nucleation Rate ◽

Particle Production ◽

Ice Nucleation ◽

Nucleation Theory ◽

Rate Coefficients ◽

Freezing Temperatures ◽

Aqueous Volume ◽

Heterogeneous Ice Nucleation

Abstract. Ice formation in the atmosphere by homogeneous and heterogeneous nucleation is one of the least understood processes in cloud microphysics and climate. Here we describe our investigation of the marine environment as a potential source of atmospheric IN by experimentally observing homogeneous ice nucleation from aqueous NaCl droplets and comparing against heterogeneous ice nucleation from aqueous NaCl droplets containing intact and fragmented diatoms. Homogeneous and heterogeneous ice nucleation are studied as a function of temperature and water activity, aw. Additional analyses are presented on the dependence of diatom surface area and aqueous volume on heterogeneous freezing temperatures, ice nucleation rates, ωhet, ice nucleation rate coefficients, Jhet, and differential and cumulative ice nuclei spectra, k(T) and K(T), respectively. Homogeneous freezing temperatures and corresponding nucleation rate coefficients are in agreement with the water activity based homogeneous ice nucleation theory within experimental and predictive uncertainties. Our results confirm, as predicted by classical nucleation theory, that a stochastic interpretation can be used to describe the homogeneous ice nucleation process. Heterogeneous ice nucleation initiated by intact and fragmented diatoms can be adequately represented by a modified water activity based ice nucleation theory. A horizontal shift in water activity, Δaw, het = 0.2303, of the ice melting curve can describe median heterogeneous freezing temperatures. Individual freezing temperatures showed no dependence on available diatom surface area and aqueous volume. Determined at median diatom freezing temperatures for aw from 0.8 to 0.99, ωhet~0.11+0.06−0.05 s−1, Jhet~1.0+1.16−0.61×104 cm−2 s−1, and K~6.2+3.5−4.1 ×104 cm−2. The experimentally derived ice nucleation rates and nuclei spectra allow us to estimate ice particle production which we subsequently use for a comparison with observed ice crystal concentrations typically found in cirrus and polar marine mixed-phase clouds. Differences in application of time-dependent and time-independent analyses to predict ice particle production are discussed.

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Efficiency of immersion mode ice nucleation on surrogates of mineral dust

Atmospheric Chemistry and Physics ◽

10.5194/acp-7-5081-2007 ◽

2007 ◽

Vol 7 (19) ◽

pp. 5081-5091 ◽

Cited By ~ 217

Author(s):

C. Marcolli ◽

S. Gedamke ◽

T. Peter ◽

B. Zobrist

Keyword(s):

Contact Angle ◽

Active Sites ◽

Quantitative Agreement ◽

Ice Nucleation ◽

Nucleation Theory ◽

Classical Nucleation Theory ◽

Aqueous Suspensions ◽

Freezing Temperatures ◽

Good Agreement ◽

Heterogeneous Ice Nucleation

Abstract. A differential scanning calorimeter (DSC) was used to explore heterogeneous ice nucleation of emulsified aqueous suspensions of two Arizona test dust (ATD) samples with particle diameters of nominally 0–3 and 0–7 μm, respectively. Aqueous suspensions with ATD concentrations of 0.01–20 wt% have been investigated. The DSC thermograms exhibit a homogeneous and a heterogeneous freezing peak whose intensity ratios vary with the ATD concentration in the aqueous suspensions. Homogeneous freezing temperatures are in good agreement with recent measurements by other techniques. Depending on ATD concentration, heterogeneous ice nucleation occurred at temperatures as high as 256 K or down to the onset of homogeneous ice nucleation (237 K). For ATD-induced ice formation Classical Nucleation Theory (CNT) offers a suitable framework to parameterize nucleation rates as a function of temperature, experimentally determined ATD size, and emulsion droplet volume distributions. The latter two quantities serve to estimate the total heterogeneous surface area present in a droplet, whereas the suitability of an individual heterogeneous site to trigger nucleation is described by the compatibility function (or contact angle) in CNT. The intensity ratio of homogeneous to heterogeneous freezing peaks is in good agreement with the assumption that the ATD particles are randomly distributed amongst the emulsion droplets. The observed dependence of the heterogeneous freezing temperatures on ATD concentrations cannot be described by assuming a constant contact angle for all ATD particles, but requires the ice nucleation efficiency of ATD particles to be (log)normally distributed amongst the particles. Best quantitative agreement is reached when explicitly assuming that high-compatibility sites are rare and that therefore larger particles have on average more and better active sites than smaller ones. This analysis suggests that a particle has to have a diameter of at least 0.1 μm to exhibit on average one active site.

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Simulating the influence of primary biological aerosol particles on clouds by heterogeneous ice nucleation

Atmospheric Chemistry and Physics ◽

10.5194/acp-18-15437-2018 ◽

2018 ◽

Vol 18 (20) ◽

pp. 15437-15450 ◽

Cited By ~ 4

Author(s):

Matthias Hummel ◽

Corinna Hoose ◽

Bernhard Pummer ◽

Caroline Schaupp ◽

Janine Fröhlich-Nowoisky ◽

...

Keyword(s):

Pseudomonas Syringae ◽

Aerosol Particles ◽

Fungal Spores ◽

Ice Nucleation ◽

Ice Crystals ◽

Atmospheric Measurements ◽

Cloud Ice ◽

Biological Aerosol Particles ◽

Ice Phase ◽

Heterogeneous Ice Nucleation

Abstract. Primary ice formation, which is an important process for mixed-phase clouds with an impact on their lifetime, radiative balance, and hence the climate, strongly depends on the availability of ice-nucleating particles (INPs). Supercooled droplets within these clouds remain liquid until an INP immersed in or colliding with the droplet reaches its activation temperature. Only a few aerosol particles are acting as INPs and the freezing efficiency varies among them. Thus, the fraction of supercooled water in the cloud depends on the specific properties and concentrations of the INPs. Primary biological aerosol particles (PBAPs) have been identified as very efficient INPs at high subzero temperatures, but their very low atmospheric concentrations make it difficult to quantify their impact on clouds. Here we use the regional atmospheric model COSMO–ART to simulate the heterogeneous ice nucleation by PBAPs during a 1-week case study on a domain covering Europe. We focus on three highly ice-nucleation-active PBAP species, Pseudomonas syringae bacteria cells and spores from the fungi Cladosporium sp. and Mortierella alpina. PBAP emissions are parameterized in order to represent the entirety of bacteria and fungal spores in the atmosphere. Thus, only parts of the simulated PBAPs are assumed to act as INPs. The ice nucleation parameterizations are specific for the three selected species and are based on a deterministic approach. The PBAP concentrations simulated in this study are within the range of previously reported results from other modeling studies and atmospheric measurements. Two regimes of PBAP INP concentrations are identified: a temperature-limited and a PBAP-limited regime, which occur at temperatures above and below a maximal concentration at around −10 ∘C, respectively. In an ensemble of control and disturbed simulations, the change in the average ice crystal concentration by biological INPs is not statistically significant, suggesting that PBAPs have no significant influence on the average state of the cloud ice phase. However, if the cloud top temperature is below −15 ∘C, PBAP can influence the cloud ice phase and produce ice crystals in the absence of other INPs. Nevertheless, the number of produced ice crystals is very low and it has no influence on the modeled number of cloud droplets and hence the cloud structure.

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Roles of Surface Energy and Temperature in Heterogeneous Ice Nucleation

The Journal of Physical Chemistry C ◽

10.1021/acs.jpcc.7b02848 ◽

2017 ◽

Vol 121 (21) ◽

pp. 11552-11559 ◽

Cited By ~ 12

Author(s):

Chu Li ◽

Xiang Gao ◽

Zhigang Li

Keyword(s):

Surface Energy ◽

Ice Nucleation ◽

Heterogeneous Ice Nucleation

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Heterogeneous ice nucleation of viscous secondary organic aerosol produced from ozonolysis of <i>α</i>-pinene

Atmospheric Chemistry and Physics ◽

10.5194/acp-16-6495-2016 ◽

2016 ◽

Vol 16 (10) ◽

pp. 6495-6509 ◽

Cited By ~ 33

Author(s):

Karoliina Ignatius ◽

Thomas B. Kristensen ◽

Emma Järvinen ◽

Leonid Nichman ◽

Claudia Fuchs ◽

...

Keyword(s):

Secondary Organic Aerosol ◽

Solid Phase ◽

Particle Surface ◽

Amorphous Solid ◽

Organic Aerosol ◽

Ice Nucleation ◽

Cloud Formation ◽

Particle Surface Area ◽

Semi Solid ◽

Heterogeneous Ice Nucleation

Abstract. There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from −38 to −10 °C at 5–15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between −39.0 and −37.2 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle budget.

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