ALBERT

Description: A differential scanning calorimeter (DSC) was used to explore heterogeneous ice nucleation of emulsified aqueous suspensions of two Arizona test dust (ATD) samples with particle diameters of nominally 0–3 and 0–7 μm, respectively. Aqueous suspensions with ATD concentrations of 0.01–20 wt% have been investigated. The DSC thermograms exhibit a homogeneous and a heterogeneous freezing peak whose intensity ratios vary with the ATD concentration in the aqueous suspensions. Homogeneous freezing temperatures are in good agreement with recent measurements by other techniques. Depending on ATD concentration, heterogeneous ice nucleation occurred at temperatures as high as 256 K or down to the onset of homogeneous ice nucleation (237 K). For ATD-induced ice formation Classical Nucleation Theory (CNT) offers a suitable framework to parameterize nucleation rates as a function of temperature, experimentally determined ATD size, and emulsion droplet volume distributions. The latter two quantities serve to estimate the total heterogeneous surface area present in a droplet, whereas the suitability of an individual heterogeneous site to trigger nucleation is described by the compatibility function (or contact angle) in heterogeneous CNT. The intensity ratio of homogeneous to heterogeneous freezing peaks is in good agreement with the assumption that the ATD particles are randomly distributed amongst the emulsion droplets. The observed dependence of the heterogeneous freezing temperatures on ATD concentrations cannot be described by assuming a constant contact angle for all ATD particles, but requires the ice nucleation efficiency of ATD particles to be (log)normally distributed amongst the particles. Best quantitative agreement is reached when explicitly assuming that high-compatibility sites are rare and that therefore larger particles have on average more and better active sites than smaller ones. This analysis suggests that a particle has to have a diameter of at least 0.1 μm to exhibit on average one active site.

Description: A new process is presented by which water-soluble organics might influence ice nucleation, ice growth, chemical reactions and water uptake of aerosols in the upper troposphere: the formation of glassy aerosol particles. Glasses are disordered amorphous (non-crystalline) solids that form when a liquid is cooled without crystallization until the viscosity increases exponentially and molecular diffusion practically ceases. The glass transition temperatures, Tg, homogeneous ice nucleation temperatures, Thom, and ice melting temperatures, Tm, of various aqueous inorganic, organic and multi-component solutions are investigated with a differential scanning calorimeter. The investigated solutes are: various polyols, glucose, raffinose, levoglucosan, an aromatic compound, sulfuric acid, ammonium bisulphate and mixtures of dicarboxylic acids (M5), of dicarboxylic acids and ammonium sulphate (M5AS), of two polyols, of glucose and ammonium nitrate, and of raffinose and M5AS. The results indicate that aqueous solutions of the investigated inorganic solutes show Tg-values that are too low to be of atmospheric importance. In contrast, aqueous organic and multi-component solutions readily form glasses at low but atmospherically relevant temperatures (≤230 K). To apply the laboratory data to the atmospheric situation, the measured phase transition temperatures were transformed from a concentration to a water activity scale by extrapolating water activities determined between 252 K and 313 K to lower temperatures. The obtained state diagrams reveal that the higher the molar mass of the aqueous organic or multi-component solutes, the higher Tg of their respective solutions at a given water activity. To a lesser extent, Tg also depends on the hydrophilicity of the organic solutes. Therefore, aerosol particles containing larger and more hydrophobic organic molecules (≳150 g mol-1) are more likely to form glasses at intermediate to high relative humidities in the upper troposphere. Our results suggest that the water uptake of aerosols, heterogeneous chemical reactions in aerosol particles, as well as ice nucleation and ice crystal growth can be significantly impeded or even completely inhibited in organic-enriched aerosols at upper tropospheric temperatures with implications for cirrus cloud formation and upper tropospheric relative humidity.

Description: A differential scanning calorimeter (DSC) was used to explore heterogeneous ice nucleation of emulsified aqueous suspensions of two Arizona test dust (ATD) samples with particle diameters of nominally 0–3 and 0–7 μm, respectively. Aqueous suspensions with ATD concentrations of 0.01–20 wt% have been investigated. The DSC thermograms exhibit a homogeneous and a heterogeneous freezing peak whose intensity ratios vary with the ATD concentration in the aqueous suspensions. Homogeneous freezing temperatures are in good agreement with recent measurements by other techniques. Depending on ATD concentration, heterogeneous ice nucleation occurred at temperatures as high as 256 K or down to the onset of homogeneous ice nucleation (237 K). For ATD-induced ice formation Classical Nucleation Theory (CNT) offers a suitable framework to parameterize nucleation rates as a function of temperature, experimentally determined ATD size, and emulsion droplet volume distributions. The latter two quantities serve to estimate the total heterogeneous surface area present in a droplet, whereas the suitability of an individual heterogeneous site to trigger nucleation is described by the compatibility function (or contact angle) in CNT. The intensity ratio of homogeneous to heterogeneous freezing peaks is in good agreement with the assumption that the ATD particles are randomly distributed amongst the emulsion droplets. The observed dependence of the heterogeneous freezing temperatures on ATD concentrations cannot be described by assuming a constant contact angle for all ATD particles, but requires the ice nucleation efficiency of ATD particles to be (log)normally distributed amongst the particles. Best quantitative agreement is reached when explicitly assuming that high-compatibility sites are rare and that therefore larger particles have on average more and better active sites than smaller ones. This analysis suggests that a particle has to have a diameter of at least 0.1 μm to exhibit on average one active site.

Description: Heterogeneous ice freezing points of aqueous solutions containing various immersed solid dicarboxylic acids (oxalic, adipic, succinic, phthalic and fumaric) have been measured with a differential scanning calorimeter. The results show that only the dihydrate of oxalic acid (OAD) acts as a heterogeneous ice nucleus, with an increase in freezing temperature between 2 and 5 K depending on solution composition. In several field campaigns, oxalic acid enriched particles have been detected in the upper troposphere with single particle aerosol mass spectrometry. Simulations with a microphysical box model indicate that the presence of OAD may reduce the ice particle number density in cirrus clouds by up to ~50% when compared to exclusively homogeneous cirrus formation without OAD. Using the ECHAM4 climate model we estimate the global net radiative effect caused by this heterogeneous freezing to result in a cooling as high as −0.3 Wm−2.

Description: The ice nucleation ability of volcanic ash particles collected close to the Icelandic volcano Eyjafjallajökull during its eruptions in April and May 2010 is investigated experimentally, in the immersion and deposition modes, and applied to atmospheric conditions by comparison with airborne measurements and microphysical model calculations. The number of ash particles which are active as ice nuclei (IN) is strongly temperature dependent, with a very small minority being active in the immersion mode at temperatures of 250–263 K. Average ash particles show only a moderate effect on ice nucleation, by inducing freezing at temperatures between 236 K and 240 K (i.e. approximately 3–4 K higher than temperatures required for homogeneous ice nucleation, measured with the same instrument). By scaling the results to aircraft and lidar measurements of the conditions in the ash plume days down wind of the eruption, and by applying a simple microphysical model, it was found that the IN active in the immersion mode in the range 250–263 K generally occurred in atmospheric number densities at the lower end of those required to have an impact on ice cloud formation. However, 3–4 K above the homogeneous freezing point, immersion mode IN number densities a few days down wind of the eruption were sufficiently high to have a moderate influence on ice cloud formation. The efficiency of IN in the deposition mode was found to be poor except at very cold conditions (

Description: The international research project RECONCILE has addressed central questions regarding polar ozone depletion, with the objective to quantify some of the most relevant yet still uncertain physical and chemical processes and thereby improve prognostic modelling capabilities to realistically predict the response of the ozone layer to climate change. This overview paper outlines the scope and the general approach of RECONCILE, and it provides a summary of observations and modelling in 2010 and 2011 that have generated an in many respects unprecedented dataset to study processes in the Arctic winter stratosphere. Principally, it summarises important outcomes of RECONCILE including (i) better constraints and enhanced consistency on the set of parameters governing catalytic ozone destruction cycles, (ii) a better understanding of the role of cold binary aerosols in heterogeneous chlorine activation, (iii) an improved scheme of polar stratospheric cloud (PSC) processes that includes heterogeneous nucleation of nitric acid trihydrate (NAT) and ice on non-volatile background aerosol leading to better model parameterisations with respect to denitrification, and (iv) long transient simulations with a chemistry-climate model (CCM) updated based on the results of RECONCILE that better reproduce past ozone trends in Antarctica and are deemed to produce more reliable predictions of future ozone trends. The process studies and the global simulations conducted in RECONCILE show that in the Arctic, ozone depletion uncertainties in the chemical and microphysical processes are now clearly smaller than the sensitivity to dynamic variability.

Description: Emulsion and bulk freezing experiments were performed to investigate immersion ice nucleation on clay minerals in pure water, using various kaolinites, montmorillonites, illites as well as natural dust from the Hoggar Mountains in the Saharan region. Differential scanning calorimeter measurements were performed on three different kaolinites (KGa-1b, KGa-2 and K-SA), two illites (Illite NX and Illite SE) and four natural and acid-treated montmorillonites (SWy-2, STx-1b, KSF and K-10). The emulsion experiments provide information on the average freezing behaviour characterized by the average nucleation sites. These experiments revealed one to sometimes two distinct heterogeneous freezing peaks, which suggest the presence of a low number of qualitatively distinct average nucleation site classes. We refer to the peak at the lowest temperature as "standard peak" and to the one occurring in only some clay mineral types at higher temperatures as "special peak". Conversely, freezing in bulk samples is not initiated by the average nucleation sites, but by a very low number of "best sites". The kaolinites and montmorillonites showed quite narrow standard peaks with onset temperatures 238 K

Description: Significant reductions in stratospheric ozone occur inside the polar vortices each spring when chlorine radicals produced by heterogeneous reactions on cold particle surfaces in winter destroy ozone mainly in two catalytic cycles, the ClO dimer cycle and the ClO/BrO cycle. Chlorofluorocarbons (CFCs), which are responsible for most of the chlorine currently present in the stratosphere, have been banned by the Montreal Protocol and its amendments, and the ozone layer is predicted to recover to 1980 levels within the next few decades. During the same period, however, climate change is expected to alter the temperature, circulation patterns and chemical composition in the stratosphere, and possible geo-engineering ventures to mitigate climate change may lead to additional changes. To realistically predict the response of the ozone layer to such influences requires the correct representation of all relevant processes. The European project RECONCILE has comprehensively addressed remaining questions in the context of polar ozone depletion, with the objective to quantify the rates of some of the most relevant, yet still uncertain physical and chemical processes. To this end RECONCILE used a broad approach of laboratory experiments, two field missions in the Arctic winter 2009/10 employing the high altitude research aircraft M55-Geophysica and an extensive match ozone sonde campaign, as well as microphysical and chemical transport modelling and data assimilation. Some of the main outcomes of RECONCILE are as follows: (1) vortex meteorology: the 2009/10 Arctic winter was unusually cold at stratospheric levels during the six-week period from mid-December 2009 until the end of January 2010, with reduced transport and mixing across the polar vortex edge; polar vortex stability and how it is influenced by dynamic processes in the troposphere has led to unprecedented, synoptic-scale stratospheric regions with temperatures below the frost point; in these regions stratospheric ice clouds have been observed, extending over 〉106km2 during more than 3 weeks. (2) Particle microphysics: heterogeneous nucleation of nitric acid trihydrate (NAT) particles in the absence of ice has been unambiguously demonstrated; conversely, the synoptic scale ice clouds also appear to nucleate heterogeneously; a variety of possible heterogeneous nuclei has been characterised by chemical analysis of the non-volatile fraction of the background aerosol; substantial formation of solid particles and denitrification via their sedimentation has been observed and model parameterizations have been improved. (3) Chemistry: strong evidence has been found for significant chlorine activation not only on polar stratospheric clouds (PSCs) but also on cold binary aerosol; laboratory experiments and field data on the ClOOCl photolysis rate and other kinetic parameters have been shown to be consistent with an adequate degree of certainty; no evidence has been found that would support the existence of yet unknown chemical mechanisms making a significant contribution to polar ozone loss. (4) Global modelling: results from process studies have been implemented in a prognostic chemistry climate model (CCM); simulations with improved parameterisations of processes relevant for polar ozone depletion are evaluated against satellite data and other long term records using data assimilation and detrended fluctuation analysis. Finally, measurements and process studies within RECONCILE were also applied to the winter 2010/11, when special meteorological conditions led to the highest chemical ozone loss ever observed in the Arctic. In addition to quantifying the 2010/11 ozone loss and to understand its causes including possible connections to climate change, its impacts were addressed, such as changes in surface ultraviolet (UV) radiation in the densely populated northern mid-latitudes.

Description: Emulsion and bulk freezing experiments were performed to investigate immersion ice nucleation on clay minerals in pure water, using various kaolinites, montmorillonites, illites as well as natural dust from the Hoggar Mountains in the Saharan region. DSC (differential scanning calorimeter) measurements were performed on the kaolinites KGa-1b and KGa-2 from the Clay Mineral Society and kaolinite from Sigma-Aldrich; the montmorillonites SWy-2 and STx-1b from the Clay Mineral Society and the acid treated montmorillonites KSF and K-10 from Sigma Aldrich; the illites NX and SE from Arginotec. The emulsion experiments provide information on the average freezing behaviour characterized by the average nucleation sites. These experiments revealed one to two distinct heterogeneous freezing peaks, which suggest the presence of a low number of qualitatively distinct average nucleation site classes. We refer to the peak at the lowest temperature as "standard peak" and to the one at higher temperatures as "special peak". Conversely, freezing in bulk samples is not initiated by the average nucleation sites, but by a very low number of "best sites". The kaolinites showed quite narrow standard peaks with onset temperatures 239 K 〈 Tonstd 〈 242 K and best sites with averaged median freezing temperature Tmedbest = 257 K. Only the kaolinite from Sigma Aldrich featured a special peak with freezing onset at 248 K. The illites showed broad standard peaks with freezing onsets at 244 K 〈 Tonstd 〈 246 K and best sites with averaged median freezing temperature Tmedbest = 262 K. Montmorillonites had standard peaks with onsets 238 K 〈 Tonstd 〈 240 K and best sites with Tmedbest=257 K. SWy-2, M K10, and KSF featured special peaks with onsets at Tonspcl=247, 240, and 242 K, respectively. M K10 and KSF both from Sigma Aldrich had less intense standard peaks compared to the ones from the Clay Mineral Society suggesting that a fraction of the standard sites are lost by the acid treatment. The acid treatment had however, no evident effect on best sites. Our investigations demonstrate that immersion freezing temperatures of clay minerals strongly depend on the amount of clay mineral present per droplet and on the exact type (location of collection and pre-treatment) of the clay mineral. We suggest that apparently contradictory results obtained by different groups with different setups can indeed be brought into good agreement when only clay minerals of the same type and amount per droplet are compared. The natural sample from the Hoggar Mountains, a region whose dusts have been shown to be composed mainly of illite, showed very similar freezing characteristics to the illites with freezing peak onsets 247 K 〈 Tonstd 〈 248 K for the average and Tmedbest = 261 K for the best sites. Relating the concentration of best IN to the dust concentration in the atmosphere suggested that the best IN in the Hoggar sample would be common enough downwind of their source region to account for ambient IN number densities in the temperature range of 250–260 K at least during dust events.