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

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, n_s, to develop a representative n_s(T) spectrum that spans a wide temperature range (−37 °C < T < −11 °C) and covers 9 orders of magnitude in n_s. 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 n_s. In addition, we show evidence that the immersion freezing efficiency expressed in n_s 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 n_s parameterization solely as a function of temperature. We also characterized the n_s(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 n_s 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 n_s(T) and geometric surface area-based n_s(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.

Seven different instruments and measurement methods were used to examine the immersion freezing of bacterial ice nuclei from Snomax® (hereafter Snomax), a product containing ice-active protein complexes from non-viable Pseudomonas syringae bacteria. The experimental conditions were kept as similar as possible for the different measurements. Of the participating instruments, some examined droplets which had been made from suspensions directly, and the others examined droplets activated on previously generated Snomax particles, with particle diameters of mostly a few hundred nanometers and up to a few micrometers in some cases. Data were obtained in the temperature range from −2 to −38 °C, and it was found that all ice-active protein complexes were already activated above −12 °C. Droplets with different Snomax mass concentrations covering 10 orders of magnitude were examined. Some instruments had very short ice nucleation times down to below 1 s, while others had comparably slow cooling rates around 1 K min−1. Displaying data from the different instruments in terms of numbers of ice-active protein complexes per dry mass of Snomax, nm, showed that within their uncertainty, the data agree well with each other as well as to previously reported literature results. Two parameterizations were taken from literature for a direct comparison to our results, and these were a time-dependent approach based on a contact angle distribution (Niedermeier et al., 2014) and a modification of the parameterization presented in Hartmann et al. (2013) representing a time-independent approach. The agreement between these and the measured data were good; i.e., they agreed within a temperature range of 0.6 K or equivalently a range in nm of a factor of 2. From the results presented herein, we propose that Snomax, at least when carefully shared and prepared, is a suitable material to test and compare different instruments for their accuracy of measuring immersion freezing.

The 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 ice nucleus, is one of the longest-standing puzzles in cloud physics. Here, we present comprehensive laboratory investigations on the formation of small ice particles upon the freezing of drizzle-sized cloud droplets levitated in an electrodynamic balance. Four different categories of secondary ice formation (bubble bursting, jetting, cracking, and breakup) could be detected, and their respective frequencies of occurrence as a function of temperature and droplet size are given. We find that bubble bursting occurs more often than droplet splitting. While we do not observe the shattering of droplets into many large fragments, we find that the average number of small secondary ice particles released during freezing is strongly dependent on droplet size and may well exceed unity for droplets larger than 300 μm in diameter. This leaves droplet fragmentation as an important secondary ice process effective at temperatures around −10°C in clouds where large drizzle droplets are present.

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...

A recently designed droplet freezing assay was used to study the freezing of up to 1500 identical 0.2 nL water droplets containing suspensions of one Na/Ca-rich feldspar and three K-rich and one Na/Ca-rich feldspar particles. Three types of experiments have been conducted: cooling ramp, isothermal freezing at a constant temperature, and freeze–thaw cycles. The observed freezing behavior has been interpreted with the help of a model based on the classical nucleation theory (soccer ball model (SBM); Niedermeier et al., 2015). By applying the model to the different freezing experiments conducted with the same ice-nucleating material, the unique sets of model parameters for specific feldspar suspensions could be derived. The SBM was shown to adequately describe the observed cooling rate dependence, the ice-nucleating active sites (INAS) surface density n_s(T) in a wide temperature range, and the shift of the freezing curves towards lower temperature with dilution. Moreover, the SBM was capable of reproducing the variation of INAS surface density n_s(T) with concentration of ice-nucleating particles in the suspension droplets and correctly predicting the leveling-off of n_s(T) at low temperature. The freeze–thaw experiments have clearly shown that the heterogeneous freezing induced even by very active ice-nucleating species still possesses a stochastic nature, with the degree of randomness increasing towards homogeneous nucleation. A population of the high-temperature INAS has been identified in one of the K-rich feldspar samples. The freezing of 0.8 wt % suspension droplets of this particular feldspar was observed already at −5 °C. These high-temperature active sites could be deactivated by treating the sample with hydrogen peroxide but survived heating up to 90 °C. Given a high mass concentration of these high-temperature active sites (2.9 × 10⁸ g⁻¹) and a very low value of contact angle (0.56 rad) the possibility of biological contamination of the sample was concluded to be unlikely but could not be completely ruled out. The freezing efficacy of all feldspar samples has been shown to reduce only slightly after suspension in water for over 5 months.