ALBERT

Description: Antifreeze glycopeptides (AFGPs) are a special class of biological antifreeze agents, which possess the property to inhibit ice growth in the body fluids of arctic and antarctic fish and, thus, enable life under these harsh conditions. AFGPs are composed of 4–55 tripeptide units -Ala-Ala-Thr- glycosylated at the threonine side chains. Despite the structural homology among all the fish species, divergence regarding the composition of the amino acids occurs in peptides from natural sources. Although AFGPs were discovered in the early 1960s, the adsorption mechanism of these macromolecules to the surface of the ice crystals has not yet been fully elucidated. Two AFGP diastereomers containing different amino acid configurations were synthesized to study the influence of amino acid stereochemistry on conformation and antifreeze activity. For this purpose, peptides containing monosaccharide-substituted allo-L- and D-threonine building blocks were assembled by solid-phase peptide synthesis (SPPS). The retro-inverso AFGP analogue contained all amino acids in D-configuration, while the allo-L-diastereomer was composed of L-amino acids, like native AFGPs, with replacement of L-threonine by its allo-L-diastereomer. Both glycopeptides were analyzed regarding their conformational properties, by circular dichroism (CD), and their ability to inhibit ice recrystallization in microphysical experiments.

Description: We present the laboratory results of immersion freezing efficiencies of cellulose particles at supercooled temperature (T) conditions. Three types of chemically homogeneous cellulose samples are used as surrogates that represent supermicron and submicron ice-nucleating plant structural polymers. These samples include microcrystalline cellulose (MCC), fibrous cellulose (FC) and nanocrystalline cellulose (NCC). Our immersion freezing dataset includes data from various ice nucleation measurement techniques available at 17 different institutions, including nine dry dispersion and 11 aqueous suspension techniques. With a total of 20 methods, we performed systematic accuracy and precision analysis of measurements from all 20 measurement techniques by evaluating T-binned (1 ∘C) data over a wide T range (−36 ∘C 

Description: The second phase of the Fifth International Ice Nucleation Workshop (FIN-02) involved the gathering of a large number of researchers at the Karlsruhe Institute of Technology's Aerosol Interactions and Dynamics of the Atmosphere (AIDA) facility to promote characterization and understanding of ice nucleation measurements made by a variety of methods used worldwide. Compared to the previous workshop in 2007, participation was doubled, reflecting a vibrant research area. Experimental methods involved sampling of aerosol particles by direct processing ice nucleation measuring systems from the same volume of air in separate experiments using different ice nucleating particle (INP) types, and collections of aerosol particle samples onto filters or into liquid for sharing amongst measurement techniques that post-process these samples. In this manner, any errors introduced by differences in generation methods when samples are shared across laboratories were mitigated. Furthermore, as much as possible, aerosol particle size distribution was controlled so that the size limitations of different methods were minimized. The results presented here use data from the workshop to assess the comparability of immersion freezing measurement methods activating INPs in bulk suspensions, methods that activate INPs in condensation and/or immersion freezing modes as single particles on a substrate, continuous flow diffusion chambers (CFDCs) directly sampling and processing particles well above water saturation to maximize immersion and subsequent freezing of aerosol particles, and expansion cloud chamber simulations in which liquid cloud droplets were first activated on aerosol particles prior to freezing. The AIDA expansion chamber measurements are expected to be the closest representation to INP activation in atmospheric cloud parcels in these comparisons, due to exposing particles freely to adiabatic cooling. The different particle types used as INPs included the minerals illite NX and potassium feldspar (K-feldspar), two natural soil dusts representative of arable sandy loam (Argentina) and highly erodible sandy dryland (Tunisia) soils, respectively, and a bacterial INP (Snomax®). Considered together, the agreement among post-processed immersion freezing measurements of the numbers and fractions of particles active at different temperatures following bulk collection of particles into liquid was excellent, with possible temperature uncertainties inferred to be a key factor in determining INP uncertainties. Collection onto filters for rinsing versus directly into liquid in impingers made little difference. For methods that activated collected single particles on a substrate at a controlled humidity at or above water saturation, agreement with immersion freezing methods was good in most cases, but was biased low in a few others for reasons that have not been resolved, but could relate to water vapor competition effects. Amongst CFDC-style instruments, various factors requiring (variable) higher supersaturations to achieve equivalent immersion freezing activation dominate the uncertainty between these measurements, and for comparison with bulk immersion freezing methods. When operated above water saturation to include assessment of immersion freezing, CFDC measurements often measured at or above the upper bound of immersion freezing device measurements, but often underestimated INP concentration in comparison to an immersion freezing method that first activates all particles into liquid droplets prior to cooling (the PIMCA-PINC device, or Portable Immersion Mode Cooling chAmber–Portable Ice Nucleation Chamber), and typically slightly underestimated INP number concentrations in comparison to cloud parcel expansions in the AIDA chamber; this can be largely mitigated when it is possible to raise the relative humidity to sufficiently high values in the CFDCs, although this is not always possible operationally. Correspondence of measurements of INPs among direct sampling and post-processing systems varied depending on the INP type. Agreement was best for Snomax® particles in the temperature regime colder than −10 ∘C, where their ice nucleation activity is nearly maximized and changes very little with temperature. At temperatures warmer than −10 ∘C, Snomax® INP measurements (all via freezing of suspensions) demonstrated discrepancies consistent with previous reports of the instability of its protein aggregates that appear to make it less suitable as a calibration INP at these temperatures. For Argentinian soil dust particles, there was excellent agreement across all measurement methods; measures ranged within 1 order of magnitude for INP number concentrations, active fractions and calculated active site densities over a 25 to 30 ∘C range and 5 to 8 orders of corresponding magnitude change in number concentrations. This was also the case for all temperatures warmer than −25 ∘C in Tunisian dust experiments. In contrast, discrepancies in measurements of INP concentrations or active site densities that exceeded 2 orders of magnitude across a broad range of temperature measurements found at temperatures warmer than −25 ∘C in a previous study were replicated for illite NX. Discrepancies also exceeded 2 orders of magnitude at temperatures of −20 to −25 ∘C for potassium feldspar (K-feldspar), but these coincided with the range of temperatures at which INP concentrations increase rapidly at approximately an order of magnitude per 2 ∘C cooling for K-feldspar. These few discrepancies did not outweigh the overall positive outcomes of the workshop activity, nor the future utility of this data set or future similar efforts for resolving remaining measurement issues. Measurements of the same materials were repeatable over the time of the workshop and demonstrated strong consistency with prior studies, as reflected by agreement of data broadly with parameterizations of different specific or general (e.g., soil dust) aerosol types. The divergent measurements of the INP activity of illite NX by direct versus post-processing methods were not repeated for other particle types, and the Snomax® data demonstrated that, at least for a biological INP type, there is no expected measurement bias between bulk collection and direct immediately processed freezing methods to as warm as −10 ∘C. Since particle size ranges were limited for this workshop, it can be expected that for atmospheric populations of INPs, measurement discrepancies will appear due to the different capabilities of methods for sampling the full aerosol size distribution, or due to limitations on achieving sufficient water supersaturations to fully capture immersion freezing in direct processing instruments. Overall, this workshop presents an improved picture of present capabilities for measuring INPs than in past workshops, and provides direction toward addressing remaining measurement issues.

Description: The prediction of cloud ice formation in climate models remains a challenge, partly due to the complexity of ice-related processes. Mineral dust is a prominent aerosol in the troposphere and is an important contributor to ice nucleation in mixed-phase clouds, as dust can initiate ice heterogeneously at relatively low supercooling conditions. We characterized the ice nucleation properties of size-segregated mineral dust sampled during dust events in the eastern Mediterranean. The sampling site allowed us to compare the properties of airborne dust from several sources with diverse mineralogy that passed over different atmospheric paths. We focused on particles with six size classes determined by the Micro-Orifice Uniform Deposit Impactor (MOUDI) cutoff sizes: 5.6, 3.2, 1.8, 1.0, 0.6 and 0.3 µm. Ice nucleation experiments were conducted in the Weizmann Supercooled Droplets Observation on a Microarray (WISDOM) setup, whereby the particles are immersed in nanoliter droplets using a microfluidics technique. We observed that the activity of airborne particles depended on their size class; supermicron and submicron particles had different activities, possibly due to different composition. The concentrations of ice-nucleating particles and the density of active sites (ns) increased with the particle size and particle concentration. The supermicron particles in different dust events showed similar activity, which may indicate that freezing was dominated by common mineralogical components. Combining recent data of airborne mineral dust, we show that current predictions, which are based on surface-sampled natural dust or standard mineral dust, overestimate the activity of airborne dust, especially for the submicron class. Therefore, we suggest including information on particle size in order to increase the accuracy of ice formation modeling and thus weather and climate predictions.

Description: Predictions of cloud ice formation in climate models remain a challenge, partly due to the complexity of ice-related processes. Mineral dust is a prominent aerosol in the troposphere and is known to be an important contributor to ice nucleation in mixed phase clouds, as dust can initiate ice heterogeneously at relatively low supercooling conditions. We characterized the ice nucleation properties of size-segregated mineral dust sampled during dust events in the Eastern Mediterranean. The sampling site allowed us to compare between the properties of airborne dust from several sources with diverse mineralogy that passed over different atmospheric paths. We focused on particles with six size-classes, determined by the Micro-Orifice Uniform Deposit Impactor (MOUDI) cut-off sizes: 5.6, 3.2, 1.8, 1.0, 0.6 and 0.3 µm. Ice nucleation experiments were conducted in the WeIzmann Supercooled Droplets Observation on Microarray (WISDOM) setup, where the particles are immersed in nanoliter droplets using a microfluidics technique. We observed that the activity of airborne particles depended on their size-class, where supermicron and submicron particles had different activities, possibly due to different composition. The concentrations of ice nucleating particles and the density of active sites (ns) increased with the particle size and particle concentration. The supermicron particles in different dust events showed similar activity, which may indicate that freezing was dominated by common mineralogical components. Combining recent data of airborne mineral dust, we show that current predictions, which are based on natural dust or standard mineral dust, overestimate the activity of airborne dust, especially for the submicron class, and therefore we suggest to include information of particle size in order to increase the accuracy of ice formation and, thus, weather and climate predictions.

Description: The second phase of the Fifth International Ice Nucleation Workshop (FIN-02) involved the gathering of a large number of researchers at the Karlsruhe Institute of Technology's Aerosol Interactions and Dynamics of the Atmosphere (AIDA) facility to promote characterization and understanding of ice nucleation measurements made by the variety of methods used worldwide. Compared to the previous workshop in 2007, participation was doubled, reflecting a vibrant research area. Experimental methods involved sampling of aerosol particles by online ice nucleation measuring systems from the same volume of air in separate experiments using different ice nucleating particle (INP) types, and collections of aerosol particle samples onto filters or into liquid for sharing amongst offline measurement techniques. In this manner, any errors introduced by differences in generation methods when samples are shared across laboratories were mitigated. Furthermore, as much as possible, aerosol particle size distribution was controlled so that the size limitations of different methods were minimized. The results presented here use data from the workshop to assess the comparability of offline immersion freezing measurement methods activating INPs in bulk suspensions, offline methods that activate INPs in condensation and/or immersion freezing modes as single particles on a substrate, online continuous flow diffusion chambers (CFDCs) operating well above water saturation to maximize immersion and subsequent freezing of aerosol particles, and expansion cloud chamber simulations in which liquid cloud droplets were first activated on aerosol particles prior to freezing. The AIDA expansion chamber measurements are expected to be the closest representation to INP activation in atmospheric cloud parcels in these comparisons, due to exposing particles freely to adiabatic cooling. The different particle types used as INPs included the minerals illite NX and K-feldspar, two natural soil dusts representative of arable sandy loam (Argentina) and highly erodible sandy dryland (Tunisia) soils, respectively, and a bacterial INP (Snomax®). Considered together, the agreement among offline immersion freezing measurements of the numbers and fractions of particles active at different temperatures following bulk collection of particles into liquid was excellent, with possible temperature uncertainties inferred to be a key factor in determining INP uncertainties. Collection onto filters versus directly into liquid in impingers made little difference. For offline methods that activated single particles on a substrate at a controlled humidity at or above water saturation, agreement with immersion freezing methods was good in most cases, but was biased low in a few others for reasons that have not been resolved, but could relate to water vapor competition effects. Amongst CFDC-style instruments, various factors requiring (variable) higher supersaturations to achieve equivalent immersion freezing activation dominate the uncertainty between these measurements, and for comparison with bulk immersion freezing methods. When operated above water saturation to include assessment of immersion freezing, CFDC measurements often measured at or above the upper bound of immersion freezing device measurements, but often underestimated INP concentration in comparison to an immersion freezing method that first activates all particles into liquid droplets prior to cooling (the PIMCA-PINC device), and typically slightly underestimated INP number concentrations in comparison to cloud parcel expansions in the AIDA chamber; this can be largely mitigated when it is possible to raise the relative humidity to sufficiently high values in the CFDCs, although this is not always possible operationally. Correspondence of measurements of INPs among online and offline systems varied depending on the INP type. Agreement was best for Snomax® particles in the temperature regime colder than −10°C, where their ice nucleation activity is nearly maximized and changes very little with temperature. At warmer than −10°C, Snomax® INP measurements (all via freezing of suspensions) demonstrated discrepancies consistent with previous reports of the instability of its protein aggregates that appear to make it less suitable as a calibration INP at these temperatures. For Argentinian soil dust particles, there was excellent agreement across online and offline methods; measures ranged within one order of magnitude for INP number concentrations, active fractions and calculated active site densities over a 25 to 30°C range and 5 to 8 orders of corresponding magnitude change in number concentrations. This was also the case for all temperatures warmer than −25°C in Tunisian dust experiments. In contrast, discrepancies in measurements of INP concentrations or active site densities exceeded two orders of magnitude across a broad temperature range for illite NX, and divergent activation spectra between online and offline measurements found at warmer than −25°C in a previous study were replicated. Discrepancies also exceeded two orders of magnitude at temperatures of −20 to −25°C for K-feldspar, but these coincided with the range of temperatures where INP concentrations increase rapidly at approximately an order of magnitude per 2°C cooling for K-feldspar. These few discrepancies did not outweigh the overall positive outcomes of the workshop activity, nor the future utility of this data set or future similar efforts for resolving remaining measurement issues. Measurements of the same materials were repeatable over the time of the workshop and demonstrated strong consistency with prior studies, as reflected by agreement of data broadly with parameterizations of different specific or general (e.g., soil dust) aerosol types. The divergent measurements of the INP activity of illite NX by online and offline methods was not repeated for other particle types, and the Snomax® data demonstrated that, at least for a biological INP type, there is no expected measurement bias between bulk offline versus online freezing methods to as warm as −10°C. Since particle size ranges were limited for this workshop, it can be expected that for atmospheric populations of INPs, measurement discrepancies will appear due to the different capabilities of methods for sampling the full aerosol size distribution, or due to limitations on achieving sufficient water supersaturations to fully capture immersion freezing in online instruments. Overall, this workshop presents an improved picture of present capabilities for measuring INPs than in past workshops, and provides direction toward addressing remaining measurement issues.

Description: We present the laboratory results of immersion freezing efficiencies of cellulose particles at supercooled temperature (T) conditions. Three types of chemically homogeneous cellulose samples are used as surrogates that represent supermicron and submicron ice nucleating plant structural polymers. These samples include micro-crystalline cellulose (MCC), fibrous cellulose (FC) and nano-crystalline cellulose (NCC). Our experimental data show that particles resembling the MCC lab particle occur also in the atmosphere. Our immersion freezing dataset includes data from various ice nucleation measurement techniques available at seventeen different institutions, including nine dry dispersion and eleven aqueous suspension techniques. With a total of twenty methods, we performed systematic accuracy and precision analysis of measurements from all twenty measurement techniques by evaluating T-binned (1 °C) data over a wide T range (−36 °C