Abstract: Abstract. 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.

Abstract: Abstract. This study investigates the measurement of ice nucleating particle (INP) concentrations and sizing of crystals using continuous flow diffusion chambers (CFDCs). CFDCs have been deployed for decades to measure the formation of INPs under controlled humidity and temperature conditions in laboratory studies and by ambient aerosol populations. These measurements have, in turn, been used to construct parameterizations for use in models by relating the formation of ice crystals to state variables such as temperature and humidity as well as aerosol particle properties such as composition and number. We show here that assumptions of ideal instrument behavior are not supported by measurements made with a commercially available CFDC, the SPectrometer for Ice Nucleation (SPIN), and the instrument on which it is based, the Zurich Ice Nucleation Chamber (ZINC). Non-ideal instrument behavior, which is likely inherent to varying degrees in all CFDCs, is caused by exposure of particles to different humidities and/or temperatures than predicated from instrument theory of operation. This can result in a systematic, and variable, underestimation of reported INP concentrations. We find here variable correction factors from 1.5 to 9.5, consistent with previous literature values. We use a machine learning approach to show that non-ideality is most likely due to small-scale flow features where the aerosols are combined with sheath flows. Machine learning is also used to minimize the uncertainty in measured INP concentrations. We suggest that detailed measurement, on an instrument-by-instrument basis, be performed to characterize this uncertainty.

Abstract: Ice particle formation in tropospheric clouds significantly changes cloud radiative and microphysical properties. Ice nucleation in the troposphere via homogeneous freezing occurs at temperatures lower than −38°C and relative humidity with respect to ice above 140%. In the absence of these conditions, ice formation can proceed via heterogeneous nucleation aided by aerosol particles known as ice nucleating particles (INPs). In this chapter, new developments in identifying the heterogeneous freezing mechanisms, atmospheric relevance, uncertainties, and unknowns about INPs are described. The change in conventional wisdom regarding the requirements of INPs as new studies discover physical and chemical properties of these particles is explained. INP sources and known reasons for their ice nucleating properties are presented. The need for more studies to systematically identify particle properties that facilitate ice nucleation is highlighted. The atmospheric relevance of long-range transport, aerosol aging, and coating studies (in the laboratory) of INPs are also presented. Possible mechanisms for processes that change the ice nucleating potential of INPs and the corresponding challenges in understanding and applying these in models are discussed. How primary ice nucleation affects total ice crystal number concentrations in clouds and the discrepancy between INP concentrations and ice crystal number concentrations are presented. Finally, limitations of parameterizing INPs and of models in representing known and unknown processes related to heterogeneous ice nucleation processes are discussed.

Abstract: Ice nucleation in the atmosphere influences cloud properties, altering precipitation and the radiative balance, ultimately regulating Earth’s climate. An accepted ice nucleation pathway, known as deposition nucleation, assumes a direct transition of water from the vapor to the ice phase, without an intermediate liquid phase. However, studies have shown that nucleation occurs through a liquid phase in porous particles with narrow cracks or surface imperfections where the condensation of liquid below water saturation can occur, questioning the validity of deposition nucleation. We show that deposition nucleation cannot explain the strongly enhanced ice nucleation efficiency of porous compared with nonporous particles at temperatures below −40 °C and the absence of ice nucleation below water saturation at −35 °C. Using classical nucleation theory (CNT) and molecular dynamics simulations (MDS), we show that a network of closely spaced pores is necessary to overcome the barrier for macroscopic ice-crystal growth from narrow cylindrical pores. In the absence of pores, CNT predicts that the nucleation barrier is insurmountable, consistent with the absence of ice formation in MDS. Our results confirm that pore condensation and freezing (PCF), i.e., a mechanism of ice formation that proceeds via liquid water condensation in pores, is a dominant pathway for atmospheric ice nucleation below water saturation. We conclude that the ice nucleation activity of particles in the cirrus regime is determined by the porosity and wettability of pores. PCF represents a mechanism by which porous particles like dust could impact cloud radiative forcing and, thus, the climate via ice cloud formation.

Abstract: Abstract. Ice nucleation abilities of surface collected mineral dust particles from the Sahara (SD) and Asia (AD) are investigated for the temperature (T) range 253–233 K and for supersaturated relative humidity (RH) conditions in the immersion freezing regime. The dust particles were also coated with a proxy of secondary organic aerosol (SOA) from the dark ozonolysis of α-pinene to better understand the influence of atmospheric coatings on the immersion freezing ability of mineral dust particles. The measurements are conducted on polydisperse particles in the size range 0.01–3 µm with three different ice nucleation chambers. Two of the chambers follow the continuous flow diffusion chamber (CFDC) principle (Portable Ice Nucleation Chamber, PINC) and the Colorado State University CFDC (CSU-CFDC), whereas the third was the Aerosol Interactions and Dynamics in the Atmosphere (AIDA) cloud expansion chamber. From observed activated fractions (AFs) and ice nucleation active site (INAS) densities, it is concluded within experimental uncertainties that there is no significant difference between the ice nucleation ability of the particular SD and AD samples examined. A small bias towards higher INAS densities for uncoated versus SOA-coated dusts is found but this is well within the 1σ (66 % prediction bands) region of the average fit to the data, which captures 75 % of the INAS densities observed in this study. Furthermore, no systematic differences are observed between SOA-coated and uncoated dusts in both SD and AD cases, regardless of coating thickness (3–60 nm). The results suggest that any differences observed are within the uncertainty of the measurements or differences in cloud chamber parameters such as size fraction of particles sampled, and residence time, as well as assumptions in using INAS densities to compare polydisperse aerosol measurements which may show variable composition with particle size. Coatings with similar properties to that of the SOA in this work and with coating thickness up to 60 nm are not expected to impede or enhance the immersion mode ice nucleation ability of mineral dust particles.

Abstract: Abstract. This study aims at quantifying the ice nucleation properties of desert dust in the Saharan Air Layer (SAL), the warm, dry and dust-laden layer that expands from North Africa to the Americas. By measuring close to the dust's emission source, before aging processes during the transatlantic advection potentially modify the dust properties, the study fills a gap between in situ measurements of dust ice nucleating particles (INPs) far away from the Sahara and laboratory studies of ground-collected soil. Two months of online INP concentration measurements are presented, which were part of the two CALIMA campaigns at the Izaña observatory in Tenerife, Spain (2373 m a.s.l.), in the summers of 2013 and 2014. INP concentrations were measured in the deposition and condensation mode at temperatures between 233 and 253 K with the Portable Ice Nucleation Chamber (PINC). Additional aerosol information such as bulk chemical composition, concentration of fluorescent biological particles as well as the particle size distribution was used to investigate observed variations in the INP concentration. The concentration of INPs was found to range between 0.2 std L−1 in the deposition mode and up to 2500 std L−1 in the condensation mode at 240 K. It correlates well with the abundance of aluminum, iron, magnesium and manganese (R: 0.43–0.67) and less with that of calcium, sodium or carbonate. These observations are consistent with earlier results from laboratory studies which showed a higher ice nucleation efficiency of certain feldspar and clay minerals compared to other types of mineral dust. We find that an increase of ammonium sulfate, linked to anthropogenic emissions in upwind distant anthropogenic sources, mixed with the desert dust has a small positive effect on the condensation mode INP per dust mass ratio but no effect on the deposition mode INP. Furthermore, the relative abundance of biological particles was found to be significantly higher in INPs compared to the ambient aerosol. Overall, this suggests that atmospheric aging processes in the SAL can lead to an increase in ice nucleation ability of mineral dust from the Sahara. INP concentrations predicted with two common parameterization schemes, which were derived mostly from atmospheric measurements far away from the Sahara but influenced by Asian and Saharan dust, were found to be higher based on the aerosol load than we observed in the SAL, further suggesting aging effects of INPs in the SAL.

Abstract: Abstract. The relation between the mineralogical characteristics of size-selected feldspar particles from 50 to 800 nm and their ability to act as ice-nucleating particles (INPs) in the immersion mode is presented. Five polymorph members of K-feldspar (two microclines, orthoclase, adularia and sanidine) and four plagioclase samples (three labradorites and a pericline sample) are tested. Microcline was found to be the most active INP in the immersion mode consistent with previous findings. Samples were selected for their differences in typical feldspar properties such as crystal structure, bulk and trace elemental composition, and ordering of the crystal lattice. The properties mentioned are related to the temperature of feldspar crystallization from the magma during formation. Properties characteristic of low-temperature feldspar formation coincide with an increased ability to nucleate ice. Amongst the samples investigated, ice nucleation is most efficient on the crystallographically ordered, triclinic K-feldspar species microcline, while the intermediate and disordered monoclinic K-feldspar polymorphs orthoclase and sanidine nucleate ice at lower temperatures. The ice nucleation ability of disordered triclinic Na∕Ca-feldspar is comparable to disordered K-feldspar. The conditions of feldspar rock formation also leave a chemical fingerprint with varying abundance of trace elements in the samples. X-ray fluorescence spectroscopy analysis was conducted to determine metal oxide and trace elemental composition of the feldspar samples. The analysis revealed a correlation of trace metal abundance with median freezing temperatures (T50) of the K-feldspar samples allowing us to sort them for their ice nucleation efficiency according to the abundance of specific trace elements. A pronounced size dependence of ice nucleation activity for the feldspar samples is observed, with the activity of smaller-sized particles scaling with surface area or being even higher compared to larger particles. The size dependence varies for different feldspar samples. In particular, microcline exhibited immersion freezing even for 50 nm particles which is unique for heterogeneous ice nucleation of mineral dusts. This suggests that small microcline particles that are susceptible to long-range transport can affect cloud properties via immersion freezing far away from the source. The measurements generally imply that temperatures at which feldspars can affect cloud glaciation depend on the transported particle size in addition to the abundance of these particles.

Abstract: Abstract. An organic aerosol particle has a lifetime of approximately 1 week in the atmosphere during which it will be exposed to sunlight. However, the effect of photochemistry on the propensity of organic matter to participate in the initial cloud-forming steps is difficult to predict. In this study, we quantify on a molecular scale the effect of photochemical exposure of naturally occurring dissolved organic matter (DOM) and of a fulvic acid standard on its cloud condensation nuclei (CCN) and ice nucleation (IN) activity. We find that photochemical processing, equivalent to 4.6 d in the atmosphere, of DOM increases its ability to form cloud droplets by up to a factor of 2.5 but decreases its ability to form ice crystals at a loss rate of −0.04 ∘CT50 h−1 of sunlight at ground level. In other words, the ice nucleation activity of photooxidized DOM can require up to 4 ∘C colder temperatures for 50 % of the droplets to activate as ice crystals under immersion freezing conditions. This temperature change could impact the ratio of ice to water droplets within a mixed-phase cloud by delaying the onset of glaciation and by increasing the supercooled liquid fraction of the cloud, thereby modifying the radiative properties and the lifetime of the cloud. Concurrently, a photomineralization mechanism was quantified by monitoring the loss of organic carbon and the simultaneous production of organic acids, such as formic, acetic, oxalic and pyruvic acids, CO and CO2. This mechanism explains and predicts the observed increase in CCN and decrease in IN efficiencies. Indeed, we show that photochemical processing can be a dominant atmospheric ageing process, impacting CCN and IN efficiencies and concentrations. Photomineralization can thus alter the aerosol–cloud radiative effects of organic matter by modifying the supercooled-liquid-water-to-ice-crystal ratio in mixed-phase clouds with implications for cloud lifetime, precipitation patterns and the hydrological cycle.Highlights. During atmospheric transport, dissolved organic matter (DOM) within aqueous aerosols undergoes photochemistry. We find that photochemical processing of DOM increases its ability to form cloud droplets but decreases its ability to form ice crystals over a simulated 4.6 d in the atmosphere. A photomineralization mechanism involving the loss of organic carbon and the production of organic acids, CO and CO2 explains the observed changes and affects the liquid-water-to-ice ratio in clouds.

Abstract: Abstract. Ice crystal formation in atmospheric clouds has a strong effect on precipitation, cloud lifetime, cloud radiative properties, and thus the global energy budget. Primary ice formation above 235 K is initiated by nucleation on seed aerosol particles called ice-nucleating particles (INPs). Instruments that measure the ice-nucleating potential of aerosol particles in the atmosphere need to be able to accurately quantify ambient INP concentrations. In the last decade several instruments have been developed to investigate the ice-nucleating properties of aerosol particles and to measure ambient INP concentrations. Therefore, there is a need for intercomparisons to ensure instrument differences are not interpreted as scientific findings.In this study, we intercompare the results from parallel measurements using four online ice nucleation chambers. Seven different aerosol types are tested including untreated and acid-treated mineral dusts (microcline, which is a K-feldspar, and kaolinite), as well as birch pollen washing waters. Experiments exploring heterogeneous ice nucleation above and below water saturation are performed to cover the whole range of atmospherically relevant thermodynamic conditions that can be investigated with the intercompared chambers. The Leipzig Aerosol Cloud Interaction Simulator (LACIS) and the Portable Immersion Mode Cooling chAmber coupled to the Portable Ice Nucleation Chamber (PIMCA-PINC) performed measurements in the immersion freezing mode. Additionally, two continuous-flow diffusion chambers (CFDCs) PINC and the Spectrometer for Ice Nuclei (SPIN) are used to perform measurements below and just above water saturation, nominally presenting deposition nucleation and condensation freezing.The results of LACIS and PIMCA-PINC agree well over the whole range of measured frozen fractions (FFs) and temperature. In general PINC and SPIN compare well and the observed differences are explained by the ice crystal growth and different residence times in the chamber. To study the mechanisms responsible for the ice nucleation in the four instruments, the FF (from LACIS and PIMCA-PINC) and the activated fraction, AF (from PINC and SPIN), are compared. Measured FFs are on the order of a factor of 3 higher than AFs, but are not consistent for all aerosol types and temperatures investigated. It is shown that measurements from CFDCs cannot be assumed to produce the same results as those instruments exclusively measuring immersion freezing. Instead, the need to apply a scaling factor to CFDCs operating above water saturation has to be considered to allow comparison with immersion freezing devices. Our results provide further awareness of factors such as the importance of dispersion methods and the quality of particle size selection for intercomparing online INP counters.