Laboratory-generated mixtures of mineral dust particles with biological substances: characterization of the particle mixing state and immersion freezing behavior

Abstract. Biological particles such as bacteria, fungal spores or pollen are known to be efficient ice nucleating particles. Their ability to nucleate ice is due to ice nucleation active macromolecules (INMs). It has been suggested that these INMs maintain their nucleating ability even when they are separated from their original carriers. This opens the possibility of an accumulation of such INMs in soils, resulting in an internal mixture of mineral dust and INMs. If particles from such soils which contain biological INMs are then dispersed into the atmosphere due to wind erosion or agricultural processes, they could induce ice nucleation at temperatures typical for biological substances, i.e., above −20 up to almost 0 °C, while they might be characterized as mineral dust particles due to a possibly low content of biological material. We conducted a study within the research unit INUIT (Ice Nucleation research UnIT), where we investigated the ice nucleation behavior of mineral dust particles internally mixed with INM. Specifically, we mixed a pure mineral dust sample (illite-NX) with ice active biological material (birch pollen washing water) and quantified the immersion freezing behavior of the resulting particles utilizing the Leipzig Aerosol Cloud Interaction Simulator (LACIS). A very important topic concerning the investigations presented here as well as for atmospheric application is the characterization of the mixing state of aerosol particles. In the present study we used different methods like single-particle aerosol mass spectrometry, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray analysis (EDX), and a Volatility–Hygroscopicity Tandem Differential Mobility Analyser (VH-TDMA) to investigate the mixing state of our generated aerosol. Not all applied methods performed similarly well in detecting small amounts of biological material on the mineral dust particles. Measuring the hygroscopicity/volatility of the mixed particles with the VH-TDMA was the most sensitive method. We found that internally mixed particles, containing ice active biological material, follow the ice nucleation behavior observed for the pure biological particles. We verified this by modeling the freezing behavior of the mixed particles with the Soccerball model (SBM). It can be concluded that a single INM located on a mineral dust particle determines the freezing behavior of that particle with the result that freezing occurs at temperatures at which pure mineral dust particles are not yet ice active.

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The immersion freezing behavior of mineral dust particles mixed with biological substances

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-15-29639-2015 ◽

2015 ◽

Vol 15 (20) ◽

pp. 29639-29671 ◽

Cited By ~ 1

Author(s):

S. Augustin-Bauditz ◽

H. Wex ◽

C. Denjean ◽

S. Hartmann ◽

J. Schneider ◽

...

Keyword(s):

Biological Material ◽

Mineral Dust ◽

Fungal Spores ◽

Birch Pollen ◽

Ice Nucleation ◽

Freezing Behavior ◽

Dust Particles ◽

Nucleation Behavior ◽

Biological Particles ◽

Immersion Freezing

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A new multicomponent heterogeneous ice nucleation model and its application to Snomax bacterial particles and a Snomax–illite mineral particle mixture

Atmospheric Chemistry and Physics ◽

10.5194/acp-17-13545-2017 ◽

2017 ◽

Vol 17 (22) ◽

pp. 13545-13557 ◽

Cited By ~ 11

Author(s):

Hassan Beydoun ◽

Michael Polen ◽

Ryan C. Sullivan

Keyword(s):

Biological Material ◽

Cloud Microphysics ◽

Ice Nucleation ◽

Freezing Behavior ◽

Dust Particles ◽

Critical Surface ◽

Wide Range ◽

Nucleation Model ◽

Immersion Freezing ◽

Heterogeneous Ice Nucleation

Abstract. Some biological particles, such as Snomax, are very active ice nucleating particles, inducing heterogeneous freezing in supercooled water at temperatures above −15 and up to −2 °C. Despite their exceptional freezing abilities, large uncertainties remain regarding the atmospheric abundance of biological ice nucleating particles, and their contribution to atmospheric ice nucleation. It has been suggested that small biological ice nucleating macromolecules or fragments can be carried on the surfaces of dust and other atmospheric particles. This could combine the atmospheric abundance of dust particles with the ice nucleating strength of biological material to create strongly enhanced and abundant ice nucleating surfaces in the atmosphere, with significant implications for the budget and distribution of atmospheric ice nucleating particles, and their consequent effects on cloud microphysics and mixed-phase clouds. The new critical surface area g framework that was developed by Beydoun et al. (2016) is extended to produce a heterogeneous ice nucleation mixing model that can predict the freezing behavior of multicomponent particle surfaces immersed in droplets. The model successfully predicts the immersion freezing properties of droplets containing Snomax bacterial particles across a mass concentration range of 7 orders of magnitude, by treating Snomax as comprised of two distinct distributions of heterogeneous ice nucleating activity. Furthermore, the model successfully predicts the immersion freezing behavior of a low-concentration mixture of Snomax and illite mineral particles, a proxy for the biological material–dust (bio-dust) mixtures observed in atmospheric aerosols. It is shown that even at very low Snomax concentrations in the mixture, droplet freezing at higher temperatures is still determined solely by the second less active and more abundant distribution of heterogeneous ice nucleating activity of Snomax, while freezing at lower temperatures is determined solely by the heterogeneous ice nucleating activity of pure illite. This demonstrates that in this proxy system, biological ice nucleating particles do not compromise their ice nucleating activity upon mixing with dust and no new range of intermediary freezing temperatures associated with the mixture of ice nucleating particles of differing activities is produced. The study is the first to directly examine the freezing behavior of a mixture of Snomax and illite and presents the first multicomponent ice nucleation model experimentally evaluated using a wide range of ice nucleating particle concentration mixtures in droplets.

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Integrating laboratory and field data to quantify the immersion freezing ice nucleation activity of mineral dust particles

Atmospheric Chemistry and Physics ◽

10.5194/acp-15-393-2015 ◽

2015 ◽

Vol 15 (1) ◽

pp. 393-409 ◽

Cited By ~ 157

Author(s):

P. J. DeMott ◽

A. J. Prenni ◽

G. R. McMeeking ◽

R. C. Sullivan ◽

M. D. Petters ◽

...

Keyword(s):

Mineral Dust ◽

Order Approximation ◽

Ice Nucleation ◽

Calibration Factor ◽

Dust Particles ◽

Single Type ◽

Aerosol Layer ◽

Atmospheric Measurements ◽

Immersion Freezing ◽

Nucleation Activity

Abstract. Data from both laboratory studies and atmospheric measurements are used to develop an empirical parameterization for the immersion freezing activity of natural mineral dust particles. Measurements made with the Colorado State University (CSU) continuous flow diffusion chamber (CFDC) when processing mineral dust aerosols at a nominal 105% relative humidity with respect to water (RHw) are taken as a measure of the immersion freezing nucleation activity of particles. Ice active frozen fractions vs. temperature for dusts representative of Saharan and Asian desert sources were consistent with similar measurements in atmospheric dust plumes for a limited set of comparisons available. The parameterization developed follows the form of one suggested previously for atmospheric particles of non-specific composition in quantifying ice nucleating particle concentrations as functions of temperature and the total number concentration of particles larger than 0.5 μm diameter. Such an approach does not explicitly account for surface area and time dependencies for ice nucleation, but sufficiently encapsulates the activation properties for potential use in regional and global modeling simulations, and possible application in developing remote sensing retrievals for ice nucleating particles. A calibration factor is introduced to account for the apparent underestimate (by approximately 3, on average) of the immersion freezing fraction of mineral dust particles for CSU CFDC data processed at an RHw of 105% vs. maximum fractions active at higher RHw. Instrumental factors that affect activation behavior vs. RHw in CFDC instruments remain to be fully explored in future studies. Nevertheless, the use of this calibration factor is supported by comparison to ice activation data obtained for the same aerosols from Aerosol Interactions and Dynamics of the Atmosphere (AIDA) expansion chamber cloud parcel experiments. Further comparison of the new parameterization, including calibration correction, to predictions of the immersion freezing surface active site density parameterization for mineral dust particles, developed separately from AIDA experimental data alone, shows excellent agreement for data collected in a descent through a Saharan aerosol layer. These studies support the utility of laboratory measurements to obtain atmospherically relevant data on the ice nucleation properties of dust and other particle types, and suggest the suitability of considering all mineral dust as a single type of ice nucleating particle as a useful first-order approximation in numerical modeling investigations.

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Heterogeneous ice nucleation on dust particles sourced from nine deserts worldwide – Part 2: Deposition nucleation and condensation freezing

Atmospheric Chemistry and Physics ◽

10.5194/acp-19-1059-2019 ◽

2019 ◽

Vol 19 (2) ◽

pp. 1059-1076 ◽

Cited By ~ 9

Author(s):

Yvonne Boose ◽

Philipp Baloh ◽

Michael Plötze ◽

Johannes Ofner ◽

Hinrich Grothe ◽

...

Keyword(s):

Active Sites ◽

Mineral Dust ◽

Atmospheric Transport ◽

Chemical Imaging ◽

Ice Nucleation ◽

Dust Particles ◽

Full Potential ◽

Nucleation Behavior ◽

Crystal Water ◽

Desert Dust

Abstract. Mineral dust particles from deserts are amongst the most common ice nucleating particles in the atmosphere. The mineralogy of desert dust differs depending on the source region and can further fractionate during the dust emission processes. Mineralogy to a large extent explains the ice nucleation behavior of desert aerosol, but not entirely. Apart from pure mineral dust, desert aerosol particles often exhibit a coating or are mixed with small amounts of biological material. Aging on the ground or during atmospheric transport can deactivate nucleation sites, thus strong ice nucleating minerals may not exhibit their full potential. In the partner paper of this work, it was shown that mineralogy determines most but not all of the ice nucleation behavior in the immersion mode found for desert dust. In this study, the influence of semi-volatile organic compounds and the presence of crystal water on the ice nucleation behavior of desert aerosol is investigated. This work focuses on the deposition and condensation ice nucleation modes at temperatures between 238 and 242 K of 18 dust samples sourced from nine deserts worldwide. Chemical imaging of the particles' surface is used to determine the cause of the observed differences in ice nucleation. It is found that, while the ice nucleation ability of the majority of the dust samples is dominated by their quartz and feldspar content, in one carbonaceous sample it is mostly caused by organic matter, potentially cellulose and/or proteins. In contrast, the ice nucleation ability of an airborne Saharan sample is found to be diminished, likely by semi-volatile species covering ice nucleation active sites of the minerals. This study shows that in addition to mineralogy, other factors such as organics and crystal water content can alter the ice nucleation behavior of desert aerosol during atmospheric transport in various ways.

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Influence of organic and biogenic substances on the ice nucleation properties of mineral dust particles

10.5194/egusphere-egu2020-19183 ◽

2020 ◽

Author(s):

Kristian Klumpp ◽

Claudia Marcolli ◽

Thomas Peter

Keyword(s):

Amino Acids ◽

Organic Acids ◽

Mineral Dust ◽

Particle Surface ◽

Ice Nucleation ◽

Dust Particles ◽

Biogenic Substances ◽

Immersion Freezing ◽

Mixed Phase Clouds ◽

Ice Nucleation Activity

The formation of ice in mixed phase clouds occurs in the presence of aerosol particles with the ability to nucleate ice on their surface. These ice-nucleating particles (INPs) represent usually a small fraction of particles in an atmospheric aerosol. One of the main particle types which act as INPs are mineral dust particles. Among other factors, the accumulation of semivolatile substances on the particle surface can alter the ice nucleation properties of such particles.In recent immersion freezing experiments, we investigated the influence of organic acids, amino acids and polyols on the highly ice nucleation active K-feldspar microcline. Microcline dust was suspended in solutions of the above-mentioned substances and frozen in a differential scanning calorimeter (DSC). These experiments give us insight into the ice nucleation characteristics of the particles in the presence of the tested organic and biogenic substances. Our measurements show an overall decrease in ice nucleation activity of microcline in the presence of organic acids and amino acids.

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The WeIzmann Supercooled Droplets Observation on a Microarray (WISDOM) and application for ambient dust

Atmospheric Measurement Techniques ◽

10.5194/amt-11-233-2018 ◽

2018 ◽

Vol 11 (1) ◽

pp. 233-248 ◽

Cited By ~ 21

Author(s):

Naama Reicher ◽

Lior Segev ◽

Yinon Rudich

Keyword(s):

Active Surface ◽

Ice Nucleation ◽

Saharan Dust ◽

Dust Particles ◽

Active Surface Site ◽

Immersion Freezing ◽

Measurement Uncertainties ◽

Homogeneous Freezing ◽

Validation Experiments

Abstract. The WeIzmann Supercooled Droplets Observation on Microarray (WISDOM) is a new setup for studying ice nucleation in an array of monodisperse droplets for atmospheric implications. WISDOM combines microfluidics techniques for droplets production and a cryo-optic stage for observation and characterization of freezing events of individual droplets. This setup is designed to explore heterogeneous ice nucleation in the immersion freezing mode, down to the homogeneous freezing of water (235 K) in various cooling rates (typically 0.1–10 K min−1). It can also be used for studying homogeneous freezing of aqueous solutions in colder temperatures. Frozen fraction, ice nucleation active surface site densities and freezing kinetics can be obtained from WISDOM measurements for hundreds of individual droplets in a single freezing experiment. Calibration experiments using eutectic solutions and previously studied materials are described. WISDOM also allows repeatable cycles of cooling and heating for the same array of droplets. This paper describes the WISDOM setup, its temperature calibration, validation experiments and measurement uncertainties. Finally, application of WISDOM to study the ice nucleating particle (INP) properties of size-selected ambient Saharan dust particles is presented.

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Ice nucleation by surrogates for atmospheric mineral dust and mineral dust/sulfate particles at cirrus temperatures

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-5-3391-2005 ◽

2005 ◽

Vol 5 (3) ◽

pp. 3391-3436 ◽

Cited By ~ 9

Author(s):

C. M. Archuleta ◽

P. J. DeMott ◽

S. M. Kreidenweis

Keyword(s):

Sulfuric Acid ◽

Relative Humidity ◽

Mineral Dust ◽

Aerosol Particles ◽

Diffusion Chamber ◽

Ice Nucleation ◽

Dust Particles ◽

Nucleation Behavior ◽

Ice Nuclei ◽

Homogeneous Freezing

Abstract. This study examines the potential role of some types of mineral dust and mineral dust with sulfuric acid coatings as heterogeneous ice nuclei at cirrus temperatures. Commercially-available nanoscale powder samples of aluminum oxide, alumina-silicate and iron oxide were used as surrogates for atmospheric mineral dust particles, with and without multilayer coverage of sulfuric acid. A sample of Asian dust aerosol particles was also studied. Measurements of ice nucleation were made using a continuous-flow ice-thermal diffusion chamber (CFDC) operated to expose size-selected aerosol particles to temperatures between −45 and −60°C and a range of relative humidity above ice-saturated conditions. Pure metal oxide particles supported heterogeneous ice nucleation at lower relative humidities than those required to homogeneously freeze sulfuric acid solution particles at sizes larger than about 50 nm. The ice nucleation behavior of the same metal oxides coated with sulfuric acid indicate heterogeneous freezing at lower relative humidities than those calculated for homogeneous freezing of the diluted particle coatings. The effect of soluble coatings on the ice activation relative humidity varied with the respective uncoated core particle types, but for all types the heterogeneous freezing rates increased with particle size for the same thermodynamic conditions. For a selected size of 200 nm, the natural mineral dust particles were the most effective ice nuclei tested, supporting heterogeneous ice formation at an ice relative humidity of approximately 135%, irrespective of temperature. Modified homogeneous freezing parameterizations and theoretical formulations are shown to have application to the description of heterogeneous freezing of mineral dust-like particles with soluble coatings.

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A comprehensive laboratory study on the immersion freezing behavior of illite NX particles: a comparison of 17 ice nucleation measurement techniques

Atmospheric Chemistry and Physics ◽

10.5194/acp-15-2489-2015 ◽

2015 ◽

Vol 15 (5) ◽

pp. 2489-2518 ◽

Cited By ~ 123

Author(s):

N. Hiranuma ◽

S. Augustin-Bauditz ◽

H. Bingemer ◽

C. Budke ◽

J. Curtius ◽

...

Keyword(s):

Cooling Rate ◽

Surface Area ◽

Mineral Dust ◽

Measurement Techniques ◽

Ice Nucleation ◽

Measurement Methods ◽

Dust Particles ◽

Immersion Freezing ◽

Nucleation Activity ◽

Ice Nucleation Activity

Abstract. Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice-nucleating particles. However, an intercomparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques. Within the framework of INUIT (Ice Nuclei Research Unit), we distributed an illite-rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature (T), cooling rate and nucleation time. A total of 17 measurement methods were involved in the data intercomparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while 10 other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing data set was evaluated using the ice nucleation active surface-site density, ns, to develop a representative ns(T) spectrum that spans a wide temperature range (−37 °C < T < −11 °C) and covers 9 orders of magnitude in ns. In general, the 17 immersion freezing measurement techniques deviate, within a range of about 8 °C in terms of temperature, by 3 orders of magnitude with respect to ns. In addition, we show evidence that the immersion freezing efficiency expressed in ns of illite NX particles is relatively independent of droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature dependence and weak time and size dependence of the immersion freezing efficiency of illite-rich clay mineral particles enabled the ns parameterization solely as a function of temperature. We also characterized the ns(T) spectra and identified a section with a steep slope between −20 and −27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below −27 °C. While the agreement between different instruments was reasonable below ~ −27 °C, there seemed to be a different trend in the temperature-dependent ice nucleation activity from the suspension and dry-dispersed particle measurements for this mineral dust, in particular at higher temperatures. For instance, the ice nucleation activity expressed in ns was smaller for the average of the wet suspended samples and higher for the average of the dry-dispersed aerosol samples between about −27 and −18 °C. Only instruments making measurements with wet suspended samples were able to measure ice nucleation above −18 °C. A possible explanation for the deviation between −27 and −18 °C is discussed. Multiple exponential distribution fits in both linear and log space for both specific surface area-based ns(T) and geometric surface area-based ns(T) are provided. These new fits, constrained by using identical reference samples, will help to compare IN measurement methods that are not included in the present study and IN data from future IN instruments.

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A new multi-component heterogeneous ice nucleation model and its application to Snomax bacterial particles and a Snomax-illte mineral particle mixture

10.5194/acp-2017-372 ◽

2017 ◽

Author(s):

Hassan Beydoun ◽

Michael Polen ◽

Ryan C. Sullivan

Keyword(s):

Cloud Microphysics ◽

Ice Nucleation ◽

Freezing Behavior ◽

Dust Particles ◽

Mineral Particle ◽

Critical Surface ◽

Wide Range ◽

Nucleation Model ◽

Immersion Freezing ◽

Heterogeneous Ice Nucleation

Abstract. Some biological particles, such as Snomax, are very active ice nucleating particles, inducing heterogeneous freezing in supercooled water at temperatures above −15° C and up to −2° C. Despite their exceptional freezing abilities, large uncertainties remain regarding the atmospheric abundance of biological ice nucleating particles, and their contribution to atmospheric ice nucleation. It has been suggested that small biological ice nucleating macromolecules or fragments can be carried on the surfaces of dust and other atmospheric particles. This could combine the atmospheric abundance of dust particles with the ice nucleating strength of biological material to create strongly enhanced and abundant ice nucleating surfaces in the atmosphere, with significant implications for the budget and distribution of atmospheric ice nucleating particles, and their consequent effects on cloud microphysics and mixed-phase clouds. The new critical surface area “g” framework that was developed by Beydoun et al. (2016), is extended to produce a heterogeneous ice nucleation mixing model that can predict the freezing behavior of multi-component particle surfaces immersed in droplets. The model successfully predicts the immersion freezing properties of droplets containing Snomax bacterial particles across a mass concentration range of seven orders of magnitude, by treating Snomax as comprised of two distinct distributions of heterogeneous ice nucleating activity. Furthermore, the model successfully predicts the immersion freezing behavior of a low concentration mixture of Snomax and illite mineral particles, a proxy for the biological-dust mixtures observed in atmospheric aerosols. It is shown that even at very low Snomax concentrations in the mixture, droplet freezing at higher temperatures is still determined solely by the second less active and more abundant distribution of heterogeneous ice nucleating activity of Snomax, while freezing at lower temperatures is determined solely by the heterogeneous ice nucleating activity of pure illite. This demonstrates that in this proxy system, biological ice nucleating particles do not compromise their ice nucleating activity upon mixing with dust and no new range of intermediary freezing temperatures associated with the mixture of ice nucleating particles of differing activities is produced. The study is the first to directly examine the freezing behavior of a mixture of Snomax and illite and presents the first multi-component ice nucleation model experimentally evaluated using a wide range of ice nucleating particle concentration mixtures in droplets.

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The Leipzig Cloud Interaction Simulator (LACIS): operating principle and theoretical studies concerning homogeneous and heterogeneous ice nucleation

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-10-25577-2010 ◽

2010 ◽

Vol 10 (11) ◽

pp. 25577-25617

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 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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