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.

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 Published by Copernicus Publications on behalf of the European Geosciences Union. N. Hiranuma et al.: A comparison of 17 IN measurement techniquesIN 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 drydispersed 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,...

Abstract. During the measurement campaign FROST (FReezing Of duST), LACIS (Leipzig Aerosol CloudInteraction Simulator) was used to investigate the immersion freezing behavior of size selected, coated and uncoated Arizona Test Dust (ATD) particles with a mobility diameter of 300 nm. Particles were coated with succinic acid (C 4 H 6 O 4 ), sulfuric acid (H 2 SO 4 ) and ammonium sulfate ((NH 4 ) 2 SO 4 ). Ice fractions at mixed-phase cloud temperatures ranging from 233.15 K to 239.15 K (±0.60 K) were determined for all types of particles. In this temperature range, pure ATD particles and those coated with C 4 H 6 O 4 or small amounts of H 2 SO 4 were found to be the most efficient ice nuclei (IN). ATD particles coated with (NH 4 ) 2 SO 4 were the most inefficient IN. Since the supercooled droplets were highly diluted before freezing occurred, a freezing point suppression due to the soluble material on the particles (and therefore in the droplets) cannot explain this observation. Therefore, it is reasonable to assume that the coatings lead to particle surface alterations which cause the differences in the IN abilities. Two different theoretical approaches based on the stochastic and the singular hypotheses were applied to clarify and parameterize the freezing behavior of the particles investigated. Both approaches describe the experimentally determined results, yielding parameters that can subsequently be used to compare our results to those from other studies. HowCorrespondence to: D. Niedermeier (niederm@tropos.de) ever, we cannot clarify at the current state which of the two approaches correctly describes the investigated immersion freezing process. But both approaches confirm the assumption that the coatings lead to particle surface modifications lowering the nucleation efficiency. The stochastic approach interprets the reduction in nucleation rate from coating as primarily due to an increase in the thermodynamic barrier for ice formation (i.e., changes in interfacial free energies). The singular approach interprets the reduction as resulting from a reduced surface density of active sites.

Abstract. 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 nonviable 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, n m , 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 n m 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.

Abstract. 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 ns(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 ns(T) with concentration of ice-nucleating particles in the suspension droplets and correctly predicting the leveling-off of ns(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.