Mijung Song

Liquid–liquid phase separation in atmospherically relevant particles consisting of organic species and inorganic salts

Laboratory studies of liquid–liquid phase separation in particles containing organic species and inorganic salts of atmospheric relevance are reviewed. The oxygen-to-carbon elemental ratio (O:C) of the organic component appears to be the most useful parameter for estimating, to a first approximation, the occurrence of liquid–liquid phase separation and the separation relative humidity (SRH) in these particles. A trend of decreasing SRH for increasing O:C was found for simple organic–inorganic mixtures (<11 species). Phase separation in particles composed of laboratory-produced secondary organic material and sulphate species and in ambient particles is generally consistent with this trend. A further constraint is that liquid–liquid phase separation was always observed for O:C < 0.5 and was never observed for O:C ≥ 0.8. For organic materials of intermediate O:C ranging from 0.5 to 0.8, phase separation in simple organic–inorganic mixtures was influenced by the organic functional groups represented. The organic-to-inorganic mass ratio (OIR) affected the occurrence of liquid–liquid phase separation in a small number of cases. A dependence on salt type was observed with 87% of the studied organics exhibiting the following trend in SRH values: (NH4)2SO4 ≥ NH4HSO4 ≥ NaCl ≥ NH4NO3, consistent with previous salting-out studies and the Hofmeister series. Liquid–liquid phase separation does not appear to be strongly influenced by the number of species making up the organic material. The morphology of phase separated particles appears to depend on composition, including O:C of the organic material, the inorganic salt and the OIR.

Liquid-liquid phase separation in aerosol particles:Dependence on O:C, organic functionalities, and compositional complexity

Atmospheric aerosol particles may undergo liquid-liquid phase separation (LLPS) when exposed to varying relative humidity. In this study we investigated the occurrence of LLPS for mixtures consisting of up to ten organic compounds, ammonium sulfate, and water in relationship with the organic oxygen-to-carbon (O:C) ratio. LLPS always occurred for O:C 0.80, and depended on the specific types and compositions of organic functional groups in the regime 0.56 < O:C < 0.80. In the intermediate regime, mixtures with a high share of aromatic compounds shifted the limit of occurrence of LLPS to lower O:C ratios. The number of mixture components and the spread of the O:C range did not notably influence the conditions for LLPS to occur. Since in ambient aerosols O:C range typically between 0.2 and 1.0, LLPS is expected to be a common feature of tropospheric aerosols.

Morphologies of mixed organic/inorganic/aqueous aerosol droplets

Despite major progress in the understanding of properties of tropospheric aerosol particles, it remains challenging to understand their physical state and morphology. To obtain more detailed knowledge of the phases, phase transitions and morphologies of internally mixed organic/inorganic aerosol particles, we evaluated liquid-liquid phase separation (LLPS), deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH) of 33 organic/ammonium sulfate (AS)/H2O systems from our own and literature data. The organic fraction consists of single compounds or mixtures with up to ten aliphatic and/or aromatic components with carboxylic acid, hydroxyl, carbonyl, ether, and ester functionalities, covering O : C ratios between 0.29 and 1.33. Thirteen out of these 33 systems did not show LLPS for any of the studied organic-to-inorganic mixing ratios, sixteen underwent LLPS showing core-shell morphology, and four showed both core-shell and partially engulfed configurations depending on the organic-to-inorganic ratio and RH. In all cases the organic fractions of the systems with partially engulfed configurations consisted of dicarboxylic acids. AS in mixed organic/AS/H2O particles deliquesced between 70 and 84% RH. AS effloresced below 58% RH or remained in a one-liquid-phase state. AS in droplets with LLPS always showed efflorescence with ERH between 30 and 50% RH, providing clear evidence that the presence of LLPS facilitates AS efflorescence. Spreading coefficients of the organic-rich phase on the AS-rich phase for systems containing polyethylene glycol 400 (PEG-400) and a mixture of dicarboxylic acids are in agreement with the optically observed morphologies of droplets deposited on the hydrophobic substrate. Analysis of high resolution elastic Mie resonance spectra allowed the detection of LLPS for single levitated droplets consisting of PEG-400/AS/ H2O, whereas LLPS was difficult to detect in (2-methylglutaric acid + 3-methylglutaric acid + 2,2-dimethylsuccinic acid)/AS/H2O. Measured Mie spectra of PEG-400/AS/H2O at 93.5% and at 80.9% RH agreed with computed Mie spectra for a homogeneous and a core-shell configuration, respectively, confirming the results obtained from droplets deposited on a hydrophobic substrate. Based on the presented evidence, we therefore consider the core-shell morphology to be the prevalent configuration of liquid-liquid-phase-separated tropospheric organic/AS/H2O particles.

Microphysical explanation of the RH‐dependent water affinity of biogenic organic aerosol and its importance for climate

Abstract A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH‐dependent SOA water‐uptake with solubility and phase separation; (2) show that laboratory data on IP‐ and MT‐SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single‐parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.

Estimating the viscosity of a highly viscous liquid droplet through the relaxation time of a dry spot

We discuss in this paper a technique which enables the estimation of the viscosity of microscopic droplets, with application to particles suspended in the atmosphere. The principle of this technique is to deposit a droplet of material approximately 30–100 μm in diameter on a substrate and poke it with a sharp needle hence generating a hole. The amount of sample needed to perform such measurement allows the viscosity of small sample volumes (less than a microliter), such as those generated from atmospheric sampling, to be determined. We show here that the time required for the droplet to relax to its equilibrium shape can be related to the viscosity. We hereby present two mathematical models based on the lubrication approximation which are able to capture the droplet relaxation dynamics. One model is fully transient and resolves the dynamics of the wetting front using a disjoining pressure approach. The other is quasistatic and requires a relationship between the contact line velocity and the contact angle...

Resolving the mechanisms of hygroscopic growth and cloud condensation nuclei activity for organic particulate matter

Hygroscopic growth and cloud condensation nuclei activation are key processes for accurately modeling the climate impacts of organic particulate matter. Nevertheless, the microphysical mechanisms of these processes remain unresolved. Here we report complex thermodynamic behaviors, including humidity-dependent hygroscopicity, diameter-dependent cloud condensation nuclei activity, and liquid–liquid phase separation in the laboratory for biogenically derived secondary organic material representative of similar atmospheric organic particulate matter. These behaviors can be explained by the non-ideal mixing of water with hydrophobic and hydrophilic organic components. The non-ideality-driven liquid–liquid phase separation further enhances water uptake and induces lowered surface tension at high relative humidity, which result in a lower barrier to cloud condensation nuclei activation. By comparison, secondary organic material representing anthropogenic sources does not exhibit complex thermodynamic behavior. The combined results highlight the importance of detailed thermodynamic representations of the hygroscopicity and cloud condensation nuclei activity in models of the Earth’s climate system.The interactions between organic particulate matter and water vapour affect climate predictions, yet the mechanisms of these interactions remain unresolved. Here, the authors propose a phase separation mechanism that reconciles the observed hygroscopicity and cloud condensation nuclei activity.