Quantifying surface tension of metastable aerosols via electrodeformation.

Accurate surface tension measurements are key to understanding and predicting the behavior of atmospheric aerosols, particularly their formation, growth, and phase transitions. In Earth's atmosphere, aerosols often exist in metastable states, such as being supercooled or supersaturated. Standard tensiometry instruments face challenges in accessing these states due to the large sample volumes they require and rapid phase changes near surfaces.

Estimation of the Volatility and Apparent Activity Coefficient of Levoglucosan in Wood-Burning Organic Aerosols.

Biomass burning (BB) is a major source of aerosols and black carbon, thereby exerting an important impact on climate and air quality. Levoglucosan is the most well-recognized organic marker compound of BB and has been used to quantitatively assess BB's contribution to ambient aerosols. However, little is known about levoglucosan's evaporation under atmospheric conditions, primarily due to the uncertainty of its effective saturation vapor concentration (*) and its unknown activity coefficient (γ), in the complex BB emission matrix.

Probing the evaporation dynamics of semi-volatile organic compounds to reveal the thermodynamics of liquid-liquid phase separated aerosol.

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.

Experimental phase diagram and its temporal evolution for submicron 2-methylglutaric acid and ammonium sulfate aerosol particles.

Liquid-liquid phase separation (LLPS) in aerosol particles is important for the climate system due to its potential to impact heterogeneous chemistry, cloud condensation nuclei, and new particle growth. Our group and others have shown a lower separation relative humidity for submicron particles, but whether the suppression is due to thermodynamics or kinetics is unclear. Herein, we characterize the experimental LLPS phase diagram of submicron 2-methylglutaric acid and ammonium sulfate aerosol particles and compare it to that of supermicron-sized particles.

Impact of pH on Gas-Particle Partitioning of Semi-Volatile Organics in Multicomponent Aerosol.

The partitioning of semivolatile organic compounds (SVOCs) between the condensed and gas phases can have significant implications for the properties of aerosol particles. In addition to affecting size and composition, this partitioning can alter radiative properties and impact cloud activation processes. We present measurements and model predictions on how activity and pH influence the evaporation of SVOCs from particles to the gas phase, specifically investigating aqueous inorganic particles containing dicarboxylic acids (DCAs).

Comparison of Phase States of PM over Megacities, Seoul and Beijing, and Their Implications on Particle Size Distribution.

Although the particle phase state is an important property, there is scant information on it, especially, for real-world aerosols. To explore the phase state of fine mode aerosols (PM) in two megacities, Seoul and Beijing, we collected PM filter samples daily from Dec 2020 to Jan 2021. Using optical microscopy combined with the poke-and-flow technique, the phase states of the bulk of PM as a function of relative humidity (RH) were determined and compared to the ambient RH ranges in the two cities.

Does liquid-liquid phase separation impact ice nucleation in mixed polyethylene glycol and ammonium sulfate droplets?

Particles can undergo different phase transitions in the atmosphere including deliquescence, liquid-liquid phase separation (LLPS), melting, and freezing. In this study, phase transitions of particles/droplets containing polyethylene glycol with a molar mass of 400 g mol (PEG400) and ammonium sulfate (AS), , PEG400-AS particles/droplets, were investigated at different organic-to-inorganic dry mass ratios (OIRs) under typical tropospheric temperatures and water activities (). The investigated droplets (60-100 μm) with or without LLPS in the closed system froze through homogeneous ice nucleation.

Hygroscopic growth and CCN activity of secondary organic aerosol produced from dark ozonolysis of γ-terpinene.

The hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) particles produced during dark ozonolysis of γ-terpinene under different reaction conditions were investigated. The SOA particles were produced in the presence or absence of cyclohexane, an OH scavenger; 1,3,5-trimethylbenzene, an anthropogenic volatile organic compound; and (NH)SO seed particles. A hygroscopicity tandem differential mobility analyzer was used to determine the GFs of the SOA particles at RHs ≤ 93%.

Coexistence of three liquid phases in individual atmospheric aerosol particles.

Individual atmospheric particles can contain mixtures of primary organic aerosol (POA), secondary organic aerosol (SOA), and secondary inorganic aerosol (SIA). To predict the role of such complex multicomponent particles in air quality and climate, information on the number and types of phases present in the particles is needed. However, the phase behavior of such particles has not been studied in the laboratory, and as a result, remains poorly constrained.

The Acidity of Atmospheric Particles and Clouds.

Acidity, defined as pH, is a central component of aqueous chemistry. In the atmosphere, the acidity of condensed phases (aerosol particles, cloud water, and fog droplets) governs the phase partitioning of semi-volatile gases such as HNO, NH, HCl, and organic acids and bases as well as chemical reaction rates. It has implications for the atmospheric lifetime of pollutants, deposition, and human health.

Optical deformation of single aerosol particles.

Advancements in designing complex models for atmospheric aerosol science and aerosol-cloud interactions rely vitally on accurately measuring the physicochemical properties of microscopic particles. Optical tweezers are a laboratory-based platform that can provide access to such measurements as they are able to isolate individual particles from an ensemble. The surprising ability of a focused beam of light to trap and hold a single particle can be conceptually understood in the ray optics regime using momentum transfer and Newton's second law.

Author Correction: Summertime Primary and Secondary Contributions to Southern Ocean Cloud Condensation Nuclei.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has been fixed in the paper.

Multiphase reactivity of polycyclic aromatic hydrocarbons is driven by phase separation and diffusion limitations.

Benzo[a]pyrene (BaP), a key polycyclic aromatic hydrocarbon (PAH) often associated with soot particles coated by organic compounds, is a known carcinogen and mutagen. When mixed with organics, the kinetics and mechanisms of chemical transformations of BaP by ozone in indoor and outdoor environments are still not fully elucidated. Using direct analysis in real-time mass spectrometry (DART-MS), kinetics studies of the ozonolysis of BaP in thin films exhibited fast initial loss of BaP followed by a slower decay at long exposure times.

Summertime Primary and Secondary Contributions to Southern Ocean Cloud Condensation Nuclei.

Atmospheric aerosols in clean remote oceanic regions contribute significantly to the global albedo through the formation of haze and cloud layers; however, the relative importance of 'primary' wind-produced sea-spray over secondary (gas-to-particle conversion) sulphate in forming marine clouds remains unclear. Here we report on marine aerosols (PM) over the Southern Ocean around Antarctica, in terms of their physical, chemical, and cloud droplet activation properties. Two predominant pristine air masses and aerosol populations were encountered: modified continental Antarctic (cAA) comprising predominantly sulphate with minimal sea-salt contribution and maritime Polar (mP) comprising sulphate plus sea-salt.

Coupling of organic and inorganic aerosol systems and the effect on gas-particle partitioning in the southeastern US.

Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.

Surface tension prevails over solute effect in organic-influenced cloud droplet activation.

The spontaneous growth of cloud condensation nuclei (CCN) into cloud droplets under supersaturated water vapour conditions is described by classic Köhler theory. This spontaneous activation of CCN depends on the interplay between the Raoult effect, whereby activation potential increases with decreasing water activity or increasing solute concentration, and the Kelvin effect, whereby activation potential decreases with decreasing droplet size or increases with decreasing surface tension, which is sensitive to surfactants. Surface tension lowering caused by organic surfactants, which diminishes the Kelvin effect, is expected to be negated by a concomitant reduction in the Raoult effect, driven by the displacement of surfactant molecules from the droplet bulk to the droplet-vapour interface.

Role of nucleation mechanism on the size dependent morphology of organic aerosol.

The origins of the size dependent morphology of organic aerosol are explored by probing the morphology of poly(ethylene glycol)-400/ammonium sulfate mixtures using cryogenic-transmission electron microscopy. Surprisingly, we observe a size dependence at some compositions, but not at others. Our results suggest that size dependence occurs due to an activated process.

Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs).

Gas-particle partitioning of atmospheric aerosols: interplay of physical state, non-ideal mixing and morphology.

Atmospheric aerosols, comprising organic compounds and inorganic salts, play a key role in air quality and climate. Mounting evidence exists that these particles frequently exhibit phase separation into predominantly organic and aqueous electrolyte-rich phases. As well, the presence of amorphous semi-solid or glassy particle phases has been established.

On the mixing and evaporation of secondary organic aerosol components.

The physical state and chemical composition of an organic aerosol affect its degree of mixing and its interactions with condensing species. We present here a laboratory chamber procedure for studying the effect of the mixing of organic aerosol components on particle evaporation. The procedure is applied to the formation of secondary organic aerosol (SOA) from α-pinene and toluene photooxidation.

Measurements of thermodynamic and optical properties of selected aqueous organic and organic-inorganic mixtures of atmospheric relevance.

Atmospheric aerosol particles can exhibit liquid solution concentrations supersaturated with respect to the dissolved organic and inorganic species and supercooled with respect to ice. In this study, thermodynamic and optical properties of sub- and supersaturated aqueous solutions of atmospheric interest are presented. The density, refractive index, water activity, ice melting temperatures, and homogeneous ice freezing temperatures of binary aqueous solutions containing L(+)-tartaric acid, tannic acid, and levoglucosan and ternary aqueous solutions containing levoglucosan and one of the salts NH(4)HSO(4), (NH(4))(2)SO(4), and NH(4)NO(3) have been measured in the supersaturated concentration range for the first time.

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(4)HSO(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.

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 approximately 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.