ALBERT

Description: 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.

Description: It has recently been shown that pore condensation and freezing (PCF) is a mechanism responsible for ice formation under cirrus cloud conditions. PCF is defined as the condensation of liquid water in narrow capillaries below water saturation due to the inverse Kelvin effect, followed by either heterogeneous or homogeneous nucleation depending on the temperature regime and presence of an ice-nucleating active site. By using sol–gel synthesized silica with well-defined pore diameters, morphology and distinct chemical surface-functionalization, the role of the water–silica contact angle and pore width on PCF is investigated. We find that for the pore diameters (2.2–9.2 nm) and water contact angles (15–78∘) covered in this study, our results reveal that the water contact angle plays an important role in predicting the humidity required for pore filling, while the pore diameter determines the ability of pore water to freeze. For T〉235 K and below water saturation, pore diameters and water contact angles were not able to predict the freezing ability of the particles, suggesting an absence of active sites; thus ice nucleation did not proceed via a PCF mechanism. Rather, the ice-nucleating ability of the particles depended solely on chemical functionalization. Therefore, parameterizations for the ice-nucleating abilities of particles in cirrus conditions should differ from parameterizations at mixed-phase clouds conditions. Our results support PCF as the atmospherically relevant ice nucleation mechanism below water saturation when porous surfaces are encountered in the troposphere.

Description: Ice formation in the atmosphere is important for regulating cloud lifetime, Earth's radiative balance and initiating precipitation. Due to the difference in the saturation vapor pressure over ice and water, in mixed-phase clouds (MPCs), ice will grow at the expense of supercooled cloud droplets. As such, MPCs, which contain both supercooled liquid and ice, are particularly susceptible to ice formation. However, measuring and quantifying the concentration of ice-nucleating particles (INPs) responsible for ice formation at temperatures associated with MPCs is challenging due to their very low concentrations in the atmosphere (∼1 in 105 at −30 ∘C). Atmospheric INP concentrations vary over several orders of magnitude at a single temperature and strongly increase as temperature approaches the homogeneous freezing threshold of water. To further quantify the INP concentration in nature and perform systematic laboratory studies to increase the understanding of the properties responsible for ice nucleation, a new drop-freezing instrument, the DRoplet Ice Nuclei Counter Zurich), is developed. The instrument is based on the design of previous drop-freezing assays and uses a USB camera to automatically detect freezing in a 96-well tray cooled in an ethanol chilled bath with a user-friendly and fully automated analysis procedure. Based on an in-depth characterization of DRINCZ, we develop a new method for quantifying and correcting temperature biases across drop-freezing assays. DRINCZ is further validated performing NX-illite experiments, which compare well with the literature. The temperature uncertainty in DRINCZ was determined to be ±0.9 ∘C. Furthermore, we demonstrate the applicability of DRINCZ by measuring and analyzing field-collected snow samples during an evolving synoptic situation in the Austrian Alps. The field samples fall within previously observed ranges for cumulative INP concentrations and show a dependence on air mass origin and upstream precipitation amount.

Description: Surface-collected dust from three different locations around the world was examined with respect to its ice nucleation activity (INA) with the ETH Portable Ice Nucleation Chamber (PINC). Ice nucleation experiments were conducted with particles of 200 and 400 nm in diameter in the temperature range of 233–243 K in both the deposition nucleation and condensation freezing regimes. Several treatments were performed in order to investigate the effect of mineralogical composition, as well as the presence of biological and proteinaceous, organic and soluble compounds on the INA of mineral and soil dust. The INA of untreated dust particles correlated well with the total feldspar and K-feldspar content, corroborating previously published results. The removal of heat-sensitive proteinaceous and organic components from the particle surface with heat decreased the INA of dusts. However, the decrease in the INA was not proportional to the amount of these organic components, indicating that different proteinaceous and organic species have different ice nucleation activities, and the exact speciation is required in order to determine why dusts respond differently to the heating process. The INA of certain dusts increased after the removal of soluble material from the particle surface, demonstrating the low INA of the soluble compounds and/or the exposition of the underlying active sites. Similar to the proteinaceous organic compounds, soluble compounds seem to have different effects on the INA of surface-collected dusts, and a general conclusion about how the presence of soluble material on the particle surface affects its INA is not possible. The investigation of the heated and washed dusts revealed that mineralogy alone is not able to fully explain the observed INA of surface-collected dusts at the examined temperature and relative humidity conditions. The results showed that it is not possible to predict the INA of surface-collected soil dust based on the presence and amount of certain minerals or any particular class of compounds, such as soluble or proteinaceous/organic compounds. Instead, at temperatures of 238–243 K the INA of the untreated, surface-collected soil dust in the condensation freezing mode can be roughly approximated by one of the existing surrogates for atmospheric mineral dust, such as illite NX. Uncertainties associated with mechanical damage and possible changes to the mineralogy during treatments, as well as with the BET surface area and its immediate impact on the number of active sites (ns,BET), are addressed.

Description: In situ cloud observations at mountain-top research stations regularly measure ice crystal number concentrations (ICNCs) orders of magnitudes higher than expected from measurements of ice nucleating particle (INP) concentrations. Thus, several studies suggest that mountain-top in situ cloud microphysical measurements are influenced by surface processes, e.g., blowing snow, hoar frost or riming on snow-covered trees, rocks and the snow surface. This limits the relevance of such measurements for the study of microphysical properties and processes in free-floating clouds. This study assesses the impact of surface processes on in situ cloud observations at the Sonnblick Observatory in the Hohen Tauern region, Austria. Vertical profiles of ICNCs above a snow-covered surface were observed up to a height of 10 m. The ICNC decreases at least by a factor of 2 at 10 m if the ICNC at the surface is larger than 100 L−1. This decrease can be up to 1 order of magnitude during in-cloud conditions and reached its maximum of more than 2 orders of magnitudes when the station was not in cloud. For one case study, the ICNC for regular and irregular ice crystals showed a similar relative decrease with height. This suggests that either surface processes produce both irregular and regular ice crystals or other effects modify the ICNCs near the surface. Therefore, two near-surface processes are proposed to enrich ICNCs near the surface. Either sedimenting ice crystals are captured in a turbulent layer above the surface or the ICNC is enhanced in a convergence zone because the cloud is forced over a mountain. These two processes would also have an impact on ICNCs measured at mountain-top stations if the surrounding surface is not snow covered. Conclusively, this study strongly suggests that ICNCs measured at mountain-top stations are not representative of the properties of a cloud further away from the surface.

Description: 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.

Description: Ice nucleation by different types of soot particles is systematically investigated over the temperature range from 218 to 253 K relevant for both mixed-phase (MPCs) and cirrus clouds. Soot types were selected to represent a range of physicochemical properties associated with combustion particles. Their ice nucleation ability was determined as a function of particle size using relative humidity (RH) scans in the Horizontal Ice Nucleation Chamber (HINC). We complement our ice nucleation results by a suite of particle characterization measurements, including determination of particle surface area, fractal dimension, temperature-dependent mass loss (ML), water vapor sorption and inferred porosity measurements. Independent of particle size, all soot types reveal absence of ice nucleation below and at water saturation in the MPC regime (T〉235 K). In the cirrus regime (T≤235 K), soot types show different freezing behavior depending on particle size and soot type, but the freezing is closely linked to the soot particle properties. Specifically, our results suggest that if soot aggregates contain mesopores (pore diameters of 2–50 nm) and have sufficiently low water–soot contact angles, they show ice nucleation activity and can contribute to ice formation in the cirrus regime at RH well below homogeneous freezing of solution droplets. We attribute the observed ice nucleation to a pore condensation and freezing (PCF) mechanism. Nevertheless, soot particles without cavities of the right size and/or too-high contact angles nucleate ice only at or well above the RH required for homogeneous freezing conditions of solution droplets. Thus, our results imply that soot particles able to nucleate ice via PCF could impact the microphysical properties of ice clouds.

Description: Wintertime mixed-phase orographic cloud (MPC) measurements were conducted at the Storm Peak Laboratory (SPL) during the Storm Peak Lab Cloud Property Validation Experiment (StormVEx) and Isotopic Fractionation in Snow (IFRACS) programs in 2011 and 2014, respectively. The data include 92 h of simultaneous measurements of supercooled liquid cloud droplet and ice particle size distributions (PSDs). Average cloud droplet number concentration (CDNC), droplet size (NMD), and liquid water content (LWC) were similar in both years, while ice particle concentration (Ni) and ice water content (IWC) were higher during IFRACS. The consistency of the liquid cloud suggests that SPL is essentially a cloud chamber that produces a consistent cloud under moist, westerly flow during the winter. A variable cloud condensation nuclei (CCN)-related inverse relationship between CDNC and NMD strengthened when the data were stratified by LWC. Some of this variation is due to changes in cloud base height below SPL. While there was a weak inverse correlation between LWC and IWC in the data as a whole, a stronger relationship was demonstrated for a case study on 9 February 2014 during IFRACS. A minimum LWC of 0.05 g m−3 showed that the cloud was not completely glaciated on this day. Erosion of the droplet distribution at high IWC was attributed to the Wegener–Bergeron–Findeisen process as the high IWC was accompanied by a 10-fold increase in Ni. A relationship between large cloud droplet concentration (25–35 µm) and small ice particles (75–200 µm) under cold (-8 ∘C) conditions during IFRACS suggests primary ice particle production by contact or immersion freezing. The effect of blowing snow was evaluated from the relationship between wind speed and Ni and by comparing the relative (percent) ice particle PSDs at high and low wind speeds. These were similar, contrary to expectation for blowing snow. However, the correlation between wind speed and ice crystal concentration may support this explanation for high crystal concentrations at the surface. Secondary processes could have contributed to high crystal concentrations but there was no direct evidence to support this. Further experimental work is needed to resolve these issues.

Description: 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.