Hygroscopicity of Fresh and Aged Salt Mixtures from Saline Lakes

The high hygroscopicity of salt aerosol particles makes the particles active in aerosol and cloud formations. Inland saline lakes are an important and dynamic source of salt aerosol. The salt particles can be mixed with mineral dust and transported over long distances. During transportation, these particles participate in atmospheric heterogeneous chemistry and further impact the climate and air quality on a global scale. Despite their importance and potential, relatively little research has been done on saline lake salt mixtures from atmospheric perspectives. In this study, we use experimental and model methods to evaluate the hygroscopic properties of saline lake brines, fresh salt aerosol particles, and aged salt aerosol particles. Both original samples and literature data are investigated. The original brine samples are collected from six salt lakes in Shanxi and Qinghai provinces in China. The ionic compositions of the brines are determined and the hygroscopicity measurements are performed on crystallized brines. The experimental results agree well with theoretical deliquescence relative humidity (DRH) values estimated by a thermodynamic model. The correlations between DRHs of different salt components and the correlations between DRHs and ionic concentrations are presented and discussed. Positive matrix factorization (PMF) analysis is performed on the ionic concentrations data and the hygroscopicity results, and the solutions are interpreted and discussed. The fresh and aged salt aerosol particles are analyzed in the same way as the brines, and the comparison shows that the aged salt aerosol particles completely alter their hygroscopic property, i.e., transferring from MgCl2− governed to NH4NO3− governed.

Condensed-phase biogenic–anthropogenic interactions with implications for cold cloud formation

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA–soot biogenic–anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (Tg) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibit a core–shell configuration (i.e.a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respectiveTgand FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.

Water uptake and hygroscopicity of perchlorates and implications for the existence of liquid water in some hyperarid environments

Dependence of deliquescence relative humidity of perchlorates on temperature.

Hygroscopic behavior of atmospherically relevant water-soluble carboxylic salts and their influence on the water uptake of ammonium sulfate

The hygroscopic behavior of atmospherically relevant water-soluble carboxylic salts and their effects on ammonium sulfate were investigated using a hygroscopicity tandem differential mobility analyzer (H-TDMA). No hygroscopic growth is observed for disodium oxalate, while ammonium oxalate shows slight growth (growth factor = 1.05 at 90%). The growth factors at 90% RH for sodium acetate, disodium malonate, disodium succinate, disodium tartrate, diammonium tartrate, sodium pyruvate, disodium maleate, and humic acid sodium salt are 1.79, 1.78, 1.69, 1.54, 1.29, 1.70, 1.78, and 1.19, respectively. The hygroscopic growth of mixtures of organic salts with ammonium sulfate, which are prepared as surrogates of atmospheric aerosols, was determined. A clear shift in deliquescence relative humidity to lower RH with increasing organic mass fraction was observed for these mixtures. Above 80% RH, the contribution to water uptake by the organic salts was close to that of ammonium sulfate for the majority of investigated compounds. The observed hygroscopic growth of the mixed particles at RH above the deliquescence relative humidity of ammonium sulfate agreed well with that predicted using the Zdanovskii-Stokes-Robinson (ZSR) mixing rule. Mixtures of ammonium sulfate with organic salts are more hygroscopic than mixtures with organic acids, indicating that neutralization by gas-phase ammonia and/or association with cations of dicarbonxylic acids may enhance the hygroscopicity of the atmospheric particles.

Derivation of the stoichiometric coefficient of water (ν_w) to account for water uptake by atmospheric aerosols

In this work we derive the effective stoichiometric coefficient of water (vw), introduced by Metzger and Lelieveld, 2007 (ML07), from first principles. We give examples of the application of vw in CPU efficient computations of the Deliquescence Relative Humidity (DRH) and the water uptake of atmospheric aerosols, being important parameters in atmospheric chemistry and climate modeling. We show that the application of vw in a gas/liquid/solid aerosol equilibrium partitioning model (EQSAM3) leads to results that are in excellent agreement with those of widely used thermodynamic (reference) models (E-AIM and ISORROPIA2) for various single salt solutions (NaCl, NH4NO3, (NH4)2SO4, NH4HSO4, NaHSO4) and the corresponding mixed solutions (including (NH4)3H(SO4)2 and Na3H(SO4)2), notwithstanding the distinct different theoretical and numerical concepts on which these models are based.