Influence of the Neutralization Degree on the Ice Nucleation Ability of Ammoniated Sulfate Particles

Previous laboratory measurements suggest that ammonium sulfate crystals (AS, (NH4)2 SO4) are efficient ice-nucleating particles under cirrus conditions. Sulfate particles not completely neutralized by ammonium are less well studied and include two other solids, ammonium bisulfate (AHS, NH4HSO4 ) and letovicite (LET, (NH 4)3H(SO4)2). In this work, we have obtained the first comprehensive data set for the heterogeneous ice nucleation ability of crystallized particles in the AS–LET–AHS system as a function of their degree of neutralization at a temperature of about 220 K. Quantitative data on nucleation onsets, ice-active fractions, and ice nucleation active surface site densities were derived from expansion cooling experiments in a large cloud chamber and measurements with two continuous flow diffusion chambers. We found a strong dependence of the efficiency and the mode of heterogenous ice nucleation on the degree of neutralization. Ice formation for AS, mixed AS/LET, and LET crystals occurred by the deposition nucleation or pore condensation and freezing mode. The lowest nucleation onset was observed for AS, where 0.1% of the particles became ice-active at an ice saturation ratio of 1.25. This threshold gradually increased to 1.35 for LET, and abruptly further to 1.45 for mixed LET/AHS crystals, which partially deliquesced and induced ice formation via immersion freezing. Pure AHS crystals did not form due to the inhibition of efflorescence. Our data allow for a more sophisticated treatment of ice formation in the AS–LET–AHS system in future model simulations, which have so far only considered the available data for AS alone

Activation of intact bacteria and bacterial fragments mixed with agar as cloud droplets and ice crystals in cloud chamber experiments

Abstract. Biological particles, including bacteria and bacterial fragments, have been of much interest due to the special ability of some to nucleate ice at modestly low temperatures. This paper presents results from a recent study conducted on two strains of cultivated bacteria which suggest that bacterial fragments mixed with agar, and not whole bacterial cells, serve as cloud condensation nuclei (CCN). Due to the absence of whole bacteria cells in droplets, they are unable to serve as ice nucleating particles (INPs) in the immersion mode under the experimental conditions. Experiments were conducted at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud chamber at the Karlsruhe Institute of Technology (KIT) by injecting bacteria-containing aerosol samples into the cloud chamber and inducing cloud formation by expansion over a temperature range of −5 to −12 °C. Cloud droplets and ice crystals were sampled through a pumped counterflow virtual impactor inlet (PCVI) and their residuals were characterized with a single particle mass spectrometer (miniSPLAT). The size distribution of the overall aerosol was bimodal, with a large particle mode composed of intact bacteria and a mode of smaller particles composed of agar mixed with bacterial fragments that were present in higher concentrations. Results from three expansions with two bacterial strains indicate that the cloud droplet residuals had virtually the same size distribution as the smaller particle size mode and had mass spectra that closely matched those of agar and bacterial fragments. The characterization of ice residuals that were sampled through an ice-selecting PCVI (IS-PCVI) also shows that the same particles that activate to form cloud droplets, bacteria fragments mixed with agar, were the only particle type observed in ice residuals. </jats:p

A new method for operating a continuous-flow diffusion chamber to investigate immersion freezing: assessment and performance study

Glaciation in mixed-phase clouds predominantly occurs through the immersion-freezing mode where ice-nucleating particles (INPs) immersed within supercooled droplets induce the nucleation of ice. Model representations of this process currently are a large source of uncertainty in simulating cloud radiative properties, so to constrain these estimates, continuous-flow diffusion chamber (CFDC)-style INP devices are commonly used to assess the immersion-freezing efficiencies of INPs. This study explored a new approach to operating such an ice chamber that provides maximum activation of particles without droplet breakthrough and correction factor ambiguity to obtain high-quality INP measurements in a manner that previously had not been demonstrated to be possible. The conditioning section of the chamber was maintained at -20 degrees C and water relative humidity (RHO conditions of 113 % to maximize the droplet activation, and the droplets were supercooled with an independently temperature-controlled nucleation section at a steady cooling rate (0.5 degrees C min(-1)) to induce the freezing of droplets and evaporation of unfrozen droplets. The performance of the modified compact ice chamber (MCIC) was evaluated using four INP species: K-feldspar, illite-NX, Argentinian soil dust, and airborne soil dusts from an arable region that had shown ice nucleation over a wide span of supercooled temperatures. Dry-dispersed and size-selected K-feldspar particles were generated in the laboratory. Illite-NX and soil dust particles were sampled during the second phase of the Fifth International Ice Nucleation Workshop (FIN-02) campaign, and airborne soil dust particles were sampled from an ambient aerosol inlet. The measured ice nucleation efficiencies of model aerosols that had a surface active site density (n(s)) metric were higher but mostly agreed within 1 order of magnitude compared to results reported in the literature

Pre-activation of ice-nucleating particles by the pore condensation and freezing mechanism

In spite of the resurgence in ice nucleation research a comparatively small number of studies deal with the phenomenon of pre-activation in heterogeneous ice nucleation. Fifty years ago, it was shown that various mineral dust and volcanic ash particles can be pre-activated to become nuclei for ice crystal formation even at temperatures as high as 270-271 K. Pre-activation was achieved under ice-subsaturated conditions without any preceding macroscopic ice growth by just temporarily cooling the particles to temperatures below 228 K. A two-step mechanism involving capillary condensation of supercooled water and subsequent homogeneous freezing was proposed to account for the particles\u27 enhanced ice nucleation ability at high temperatures. This work reinvestigates the efficiency of the proposed pre-activation mechanism in temperature-cycling experiments performed in a large cloud chamber with suspended particles. We find the efficiency to be highest for the clay mineral illite as well as for highly porous materials like zeolite and diatomaceous earth, whereas most aerosols generated from desert dust surface samples did not reveal a measurable pre-activation ability. The pre-activation efficiency is linked to particle pores in a certain size range. As estimated by model calculations, only pores with diameters between about 5 and 8 nm contribute to pre-activation under ice-subsaturated conditions. This range is set by a combination of requirements from the negative Kelvin effect for condensation and a critical size of ice embryos for ice nucleation and melting. In contrast to the early study, pre-activation is only observed for temperatures below 260 K. Above that threshold, the particles\u27 improved ice nucleation ability disappears due to the melting of ice in the pores

High-resolution optical constants of crystalline ammonium nitrate for infrared remote sensing of the Asian Tropopause Aerosol Layer

Infrared spectroscopic observations have shown that crystalline ammonium nitrate (AN) particles are an abundant constituent of the upper tropospheric aerosol layer which is formed during the Asian summer monsoon period, the so-called Asian Tropopause Aerosol Layer (ATAL). At upper tropospheric temperatures, the thermodynamically stable phase of AN is different from that at 298 K, meaning that presently available room-temperature optical constants of AN, that is, the real and imaginary parts of the complex refractive index, cannot be applied for the quantitative analysis of these infrared measurements. In this work, we have retrieved the first low-temperature data set of optical constants for crystalline AN in the 800–6000 cm−1 wavenumber range with a spectral resolution of 0.5 cm−1. The optical constants were iteratively derived from an infrared extinction spectrum of 1µm sized AN particles suspended in a cloud chamber at 223 K. The uncertainties of the new data set were carefully assessed in a comprehensive sensitivity analysis. We show that our data accurately fit aircraft-borne infrared measurements of ammonium nitrate particles in the ATAL

Volatility of Secondary Organic Aerosol from β-Caryophyllene Ozonolysis over a Wide Tropospheric Temperature Range

We investigated secondary organic aerosol (SOA) from β-caryophyllene oxidation generated over a wide tropospheric temperature range (213–313 K) from ozonolysis. Positive matrix factorization (PMF) was used to deconvolute the desorption data (thermograms) of SOA products detected by a chemical ionization mass spectrometer (FIGAERO-CIMS). A nonmonotonic dependence of particle volatility (saturation concentration at 298 K, C298K*) on formation temperature (213–313 K) was observed, primarily due to temperature-dependent formation pathways of β-caryophyllene oxidation products. The PMF analysis grouped detected ions into 11 compound groups (factors) with characteristic volatility. These compound groups act as indicators for the underlying SOA formation mechanisms. Their different temperature responses revealed that the relevant chemical pathways (e.g., autoxidation, oligomer formation, and isomer formation) had distinct optimal temperatures between 213 and 313 K, significantly beyond the effect of temperature-dependent partitioning. Furthermore, PMF-resolved volatility groups were compared with volatility basis set (VBS) distributions based on different vapor pressure estimation methods. The variation of the volatilities predicted by different methods is affected by highly oxygenated molecules, isomers, and thermal decomposition of oligomers with long carbon chains. This work distinguishes multiple isomers and identifies compound groups of varying volatilities, providing new insights into the temperature-dependent formation mechanisms of β-caryophyllene-derived SOA particles

Influence of particle size and shape on the backscattering linear depolarisation ratio of small ice crystals - cloud chamber measurements in the context of contrail and cirrus microphys

The article presents the laser scattering and depolarisation instrument SIMONE that is installed at the large aerosol and cloud chamber facility AIDA of the Karlsruhe Institute of Technology. SIMONE uses a 488 nm cw laser to probe simulated atmospheric clouds by measuring the scattered light from the 1.8° and 178.2° directions. At 178.2°, the scattered light is analysed for the linear polarisation state to deduce the particle linear depolarisation ratio δp which is a common measurement parameter of atmospheric lidar applications. The optical setup and the mathematical formalism of the depolarisation detection concept are given. SIMONE depolarisation measurements in spheroidal hematite aerosol and supercooled liquid clouds are used to validate the instrument. SIMONE data from a series of AIDA ice nucleation experiments at temperatures between 195 and 225 K were analysed in terms of the impact of the ice particle microphysics on δp. We found strong depolarisation values of up to 0.4 in case of small growing and sublimating ice particles with volume equivalent diameters of only a few micrometers. Modelling runs with the T-matrix method showed that the measured depolarisation ratios can be accurately reproduced assuming spheroidal and cylindrical particles with a size distribution that has been constrained by IR extinction spectroscopy. Based on the T-matrix modelling runs, we demonstrate that in case of small ice crystals the SIMONE depolarisation results are representative for the lidar depolarisation ratio which is measured at exact backscattering direction of 180°. The relevance of our results for the interpretation of recent lidar observations in cirrus and contrails is discussed. In view of our results, the high depolarisation ratios observed by the spaceborne lidar CALIOP in the tropical upper troposphere might be a hint for the presence of small (sublimating) ice particles in the outflows of deep convective systems

Complex plant-derived organic aerosol as ice-nucleating particles – more than the sums of their parts?

Quantifying the impact of complex organic particles on the formation of ice crystals in clouds remains challenging, mostly due to the vast number of different sources ranging from sea spray to agricultural areas. In particular, there are many open questions regarding the ice nucleation properties of organic particles released from terrestrial sources such as decaying plant material. In this work, we present results from laboratory studies investigating the immersion freezing properties of individual organic compounds commonly found in plant tissue and complex organic aerosol particles from vegetated environments, without specifically investigating the contribution from biological particles, which may contribute to the overall ice nucleation efficiency observed at high temperatures. To characterize the ice nucleation properties of plant-related aerosol samples for temperatures between 242 and 267 K, we used the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud chamber and the Ice Nucleation SpEctrometer of the Karlsruhe Institute of Technology (INSEKT), which is a droplet freezing assay. Individual plant components (polysaccharides, lignin, soy and rice protein) were mostly less ice active, or similarly ice active, compared to microcrystalline cellulose, which has been suggested by recent studies to be a proxy for quantifying the primary cloud ice formation caused by particles originating from vegetation. In contrast, samples from ambient sources with a complex organic matter composition (agricultural soils and leaf litter) were either similarly ice active or up to 2 orders of magnitude more ice active than cellulose. Of all individual organic plant components, only carnauba wax (i.e., lipids) showed a similarly high ice nucleation activity as that of the samples from vegetated environments over a temperature range between 245 and 252 K. Hence, based on our experimental results, we suggest considering cellulose as being representative for the average ice nucleation activity of plant-derived particles, whereas lignin and plant proteins tend to provide a lower limit. In contrast, complex biogenic particles may exhibit ice nucleation activities which are up to 2 orders of magnitude higher than observed for cellulose, making ambient plant-derived particles a potentially important contributor to the population of ice-nucleating particles in the troposphere, even though major uncertainties regarding their transport to cloud altitude remain