Experimental evidence for excess entropy discontinuities in glass-forming solutions

Glass transition temperatures T_g are investigated in aqueous binary and multi-component solutions consisting of citric acid, calcium nitrate (Ca(NO_3)_2), malonic acid, raffinose, and ammonium bisulfate (NH_4HSO_4) using a differential scanning calorimeter. Based on measured glass transition temperatures of binary aqueous mixtures and fitted binary coefficients, the T_g of multi-component systems can be predicted using mixing rules. However, the experimentally observed T_g in multi-component solutions show considerable deviations from two theoretical approaches considered. The deviations from these predictions are explained in terms of the molar excess mixing entropy difference between the supercooled liquid and glassy state at T_g. The multi-component mixtures involve contributions to these excess mixing entropies that the mixing rules do not take into account

Efflorescence of Ammonium Sulfate and Coated Ammonium Sulfate Particles: Evidence for Surface Nucleation

Using optical microscopy, we investigated the efflorescence of ammonium sulfate (AS) in aqueous AS and in aqueous 1:1 and 8:1 (by dry weight) poly(ethylene glycol)-400 (PEG-400)/AS particles deposited on a hydrophobically coated slide. Aqueous PEG-400/AS particles exposed to decreasing relative humidity (RH) exhibit a liquid−liquid phase separation below 90% RH with the PEG-400-rich phase surrounding the aqueous AS inner phase. Pure aqueous AS particles effloresced in the RH range from 36.3% to 43.7%, in agreement with literature data (31−48% RH). In contrast, aqueous 1:1 (by dry weight) PEG-400/AS particles with diameters of the AS phase from 7.2 to 19.2 μm effloresced between 26.8% and 33.9% RH and aqueous 8:1 (by dry weight) PEG-400/AS particles with diameters of the AS phase from 1.8 to 7.3 μm between 24.3% and 29.3% RH. Such low efflorescence relative humidity (ERH) values have never been reached before for AS particles of this size range. We show that these unprecedented low ERHs of AS in PEG-400/AS particles could not possibly be explained by the presence of low amounts of PEG-400 in the aqueous AS phase, by a potential inhibition of water evaporation via anomalously slow diffusion through the PEG coating, or by different time scales between various experimental techniques. High-speed photography of the efflorescence process allowed the development of the AS crystallization fronts within the particles to be monitored with millisecond time resolution. The nucleation sites were inferred from the initial crystal growth sites. Analysis of the probability distribution of initial sites of 31 and 19 efflorescence events for pure AS and 1:1 (by dry weight) PEG-400/AS particles, respectively, showed that the particle volume can be excluded as the preferred nucleation site in the case of pure AS particles. For aqueous 1:1 (by dry weight) PEG-400/AS particles preferential AS nucleation in the PEG phase and at the PEG/AS/substrate contact line can be excluded. On the basis of this probability analysis of efflorescence events together with the AS ERH values of pure aqueous AS and aqueous PEG-400/AS particles aforementioned, we suggest that in pure aqueous AS particles nucleation starts at the surface of the particles and attribute the lower ERH values observed for aqueous PEG-400/AS particles to the suppression of the surface-induced nucleation process. Our results suggest that surface-induced nucleation is likely to also occur during the efflorescence of atmospheric AS aerosol particles, possibly constituting the dominating nucleation pathway

Climatological and radiative properties of midlatitude cirrus clouds derived by automatic evaluation of lidar measurements

Cirrus, i.e., high, thin clouds that are fully glaciated, play an important role in the Earth's radiation budget as they interact with both long- and shortwave radiation and affect the water vapor budget of the upper troposphere and stratosphere. Here, we present a climatology of midlatitude cirrus clouds measured with the same type of ground-based lidar at three midlatitude research stations: at the Swiss high alpine Jungfraujoch station (3580 m a.s.l.), in Zürich (Switzerland, 510 m a.s.l.), and in Jülich (Germany, 100 m a.s.l.). The analysis is based on 13 000 h of measurements from 2010 to 2014. To automatically evaluate this extensive data set, we have developed the Fast LIdar Cirrus Algorithm (FLICA), which combines a pixel-based cloud-detection scheme with the classic lidar evaluation techniques. We find mean cirrus optical depths of 0.12 on Jungfraujoch and of 0.14 and 0.17 in Zürich and Jülich, respectively. Above Jungfraujoch, subvisible cirrus clouds (τ < 0.03) have been observed during 6 % of the observation time, whereas above Zürich and Jülich fewer clouds of that type were observed. Cirrus have been observed up to altitudes of 14.4 km a.s.l. above Jungfraujoch, whereas they have only been observed to about 1 km lower at the other stations. These features highlight the advantage of the high-altitude station Jungfraujoch, which is often in the free troposphere above the polluted boundary layer, thus enabling lidar measurements of thinner and higher clouds. In addition, the measurements suggest a change in cloud morphology at Jungfraujoch above ∼ 13 km, possibly because high particle number densities form in the observed cirrus clouds, when many ice crystals nucleate in the high supersaturations following rapid uplifts in lee waves above mountainous terrain. The retrieved optical properties are used as input for a radiative transfer model to estimate the net cloud radiative forcing, CRFNET, for the analyzed cirrus clouds. All cirrus detected here have a positive CRFNET. This confirms that these thin, high cirrus have a warming effect on the Earth's climate, whereas cooling clouds typically have cloud edges too low in altitude to satisfy the FLICA criterion of temperatures below −38 °C. We find CRFNET = 0.9 W m−2 for Jungfraujoch and 1.0 W m−2 (1.7 W m−2) for Zürich (Jülich). Further, we calculate that subvisible cirrus (τ < 0.03) contribute about 5 %, thin cirrus (0.03 < τ < 0.3) about 45 %, and opaque cirrus (0.3 < τ) about 50 % of the total cirrus radiative forcing

Measured solid state and subcooled liquid vapour pressures of nitroaromatics using Knudsen effusion mass spectrometry

Knudsen effusion mass spectrometry (KEMS) was used to measure the solid state saturation vapour pressure (PsatS) of a range of atmospherically relevant nitroaromatic compounds over the temperature range from 298 to 328 K. The selection of species analysed contained a range of geometric isomers and differing functionalities, allowing for the impacts of these factors on saturation vapour pressure (Psat) to be probed. Three subsets of nitroaromatics were investigated: nitrophenols, nitrobenzaldehydes and nitrobenzoic acids. The PsatS values were converted to subcooled liquid saturation vapour pressure (PsatL) values using experimental enthalpy of fusion and melting point values measured using differential scanning calorimetry (DSC). The PsatL values were compared to those estimated by predictive techniques and, with a few exceptions, were found to be up to 7 orders of magnitude lower. The large differences between the estimated PsatL and the experimental values can be attributed to the predictive techniques not containing parameters to adequately account for functional group positioning around an aromatic ring, or the interactions between said groups. When comparing the experimental PsatS of the measured compounds, the ability to hydrogen bond (H bond) and the strength of the H bond formed appear to have the strongest influence on the magnitude of the Psat, with steric effects and molecular weight also being major factors. Comparisons were made between the KEMS system and data from diffusion-controlled evaporation rates of single particles in an electrodynamic balance (EDB). The KEMS and the EDB showed good agreement with each other for the compounds investigated

Expiratory Aerosol pH: The Overlooked Driver of Airborne Virus Inactivation

Respiratory viruses, including influenza virus and SARS-CoV-2, are transmitted by the airborne route. Air filtration and ventilation mechanically reduce the concentration of airborne viruses and are necessary tools for disease mitigation. However, they ignore the potential impact of the chemical environment surrounding aerosolized viruses, which determines the aerosol pH. Atmospheric aerosol gravitates toward acidic pH, and enveloped viruses are prone to inactivation at strong acidity levels. Yet, the acidity of expiratory aerosol particles and its effect on airborne virus persistence have not been examined. Here, we combine pH-dependent inactivation rates of influenza A virus (IAV) and SARS-CoV-2 with microphysical properties of respiratory fluids using a biophysical aerosol model. We find that particles exhaled into indoor air (with relative humidity ≥ 50%) become mildly acidic (pH ∼ 4), rapidly inactivating IAV within minutes, whereas SARS-CoV-2 requires days. If indoor air is enriched with nonhazardous levels of nitric acid, aerosol pH drops by up to 2 units, decreasing 99%-inactivation times for both viruses in small aerosol particles to below 30 s. Conversely, unintentional removal of volatile acids from indoor air may elevate pH and prolong airborne virus persistence. The overlooked role of aerosol acidity has profound implications for virus transmission and mitigation strategies