Dataset Information

Probing Liquid-Liquid Phase Separation in Secondary Organic Aerosol Mimicking Solutions Using Articulated Straws.

ABSTRACT: The presence or absence of liquid-liquid phase separation (LLPS) in aerosol particles containing oxidized organic species and inorganic salts affects particle morphology and influences uptake into, diffusion through, and reactivity within those particles. We report here an accessible method, similar to ice core analyses, using solutions that are relevant for both aerosol chemical systems and aqueous two-phase extraction systems and contain ammonium sulfate and one of eight alcohols (methanol, ethanol, 1-propanol, 2-propanol, 2-butaonol, 3-methyl-2-butanol, 1,2-propanediol, or 1,3-propanediol) frozen in articulated (bendable) straws to probe LLPS. For alcohols with negative octanol-water partitioning coefficient (K _OW) values and O/C ratios ≥0.5, no LLPS occurs, while for alcohols with positive K _OW values and O/C ratios ≤0.33, phase separation always occurs, both findings consistent with observations using different experimental techniques. When a third species, glyoxal, is added, the glyoxal stays in the aqueous phase, regardless of whether LLPS occurs. When phase separation occurs, the glyoxal forms a strong intermolecular interaction with the sulfate ion, red-shifting the ν₃(SO₄ ^2-) peak by 15 cm^-1. These results provide evidence of chemical interactions within phase-separated systems that have implications for understanding chemical reactivity within those, and related, systems.

SUBMITTER: Longnecker ER

PROVIDER: S-EPMC8674910 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Probing Liquid-Liquid Phase Separation in Secondary Organic Aerosol Mimicking Solutions Using Articulated Straws.

Longnecker Emmaline R ER Metz Lucy L Miller Rebecca S RS Berke Andrew E AE

ACS omega 20211130 49

The presence or absence of liquid-liquid phase separation (LLPS) in aerosol particles containing oxidized organic species and inorganic salts affects particle morphology and influences uptake into, diffusion through, and reactivity within those particles. We report here an accessible method, similar to ice core analyses, using solutions that are relevant for both aerosol chemical systems and aqueous two-phase extraction systems and contain ammonium sulfate and one of eight alcohols (methanol, et ...[more]

PMID: 34926893

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Project description:Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM/OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM/OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH > SRH led to increased SOA concentrations,· particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties· such as the OM/OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were highly water soluble and expected to contribute to water-soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night, but additional improvements in daytime organic aerosol are needed to close the model-measurement gap. When taking into account deviations from ideality, including both inorganic (when RH > SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from this work will be released in CMAQ v5.2.

Project description:Liquid-liquid phase separation (LLPS) is a thermodynamically driven process that occurs in mixtures of low miscibility material. LLPS is an important process in chemical, biological, and environmental systems. In atmospheric chemistry, LLPS in aerosol containing internally-mixed organic and inorganic particles has been an area of significant interest, with particles separating to form organic-rich and aqueous phases on dehydration. This alters the optical properties of the particles, has been connected to changes in the cloud nucleation ability of the aerosol, and potentially changes the reactivity of particles towards gas-phase oxidants. Although the chemical systems that undergo LLPS have become quite well-characterized, the properties and processes of LLPS particles are quite poorly understood. In this work, we characterize LLPS in aerosol particles containing ammonium sulfate and triethylene glycol (3EG), a semi-volatile organic molecule. We explore the relative humidity (RH) conditions under which LLPS occurs and characterize the rate of evaporation of 3EG from well-mixed and LLPS particles as a function of RH. We show that the evaporation rates vary with RH due to changes in chemical activity, however no clear change in the dynamics following LLPS are observed. We interpret our observations using a thermodynamic model (AIOMFAC) coupled with an evaporation model and show that a significant increase in the activity coefficient of 3EG as the RH decreases, required for LLPS to occur, obscures a clear step-change in the evaporation rates following LLPS. By characterizing the evaporation rates, we estimate the composition of the organic-rich phase and compare our results to thermodynamic predictions. This study is the first to explore the connection between LLPS and the chemical evolution of aerosol particles via the evaporation of semi-volatile organic material. Ultimately, we reveal that the thermodynamics of non-ideal mixing are primarily responsible for the controlling both the rate of evaporation and the onset of LLPS, with LLPS itself having limited impact on the rate of evaporation in a fluid system. These results have significant implications for understanding and predicting the lifetime of aerosol particles, their effect on cloud formation, and the chemical evolution of multiphase systems by particle-gas partitioning and heterogeneous reactions.

Dataset Information

Probing Liquid-Liquid Phase Separation in Secondary Organic Aerosol Mimicking Solutions Using Articulated Straws.

Publications

Probing Liquid-Liquid Phase Separation in Secondary Organic Aerosol Mimicking Solutions Using Articulated Straws.

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