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. Surprisingly, as the equilibration time of submicron-sized aerosol particles was increased from 20 min to 60 min, the experimental phase diagram converges with the results for supermicron-sized particles. Our findings indicate that nucleation kinetics are responsible for the observed lower separation relative humidities in submicron aerosol particles. Therefore, experiments and models that investigate atmospheric processes of organic aerosol particles may need to consider the temporal evolution of aerosol LLPS.

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. Here, we show that POA+SOA+SIA particles can contain three distinct liquid phases: a low-polarity organic-rich phase, a higher-polarity organic-rich phase, and an aqueous inorganic-rich phase. Based on our results, when the elemental oxygen-to-carbon (O:C) ratio of the SOA is less than 0.8, three liquid phases can coexist within the same particle over a wide relative humidity range. In contrast, when the O:C ratio of the SOA is greater than 0.8, three phases will not form. We also demonstrate, using thermodynamic and kinetic modeling, that the presence of three liquid phases in such particles impacts their equilibration timescale with the surrounding gas phase. Three phases will likely also impact their ability to act as nuclei for liquid cloud droplets, the reactivity of these particles, and the mechanism of SOA formation and growth in the atmosphere. These observations provide fundamental information necessary for improved predictions of air quality and aerosol indirect effects on climate.

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). The aerosols are studied at the single-particle level by using optical trapping and cavity-enhanced Raman spectroscopy. Optical resonances in the spectra enable precise size tracking, while vibrational bands allow real-time monitoring of pH. Results are compared to a Maxwell-type model that accounts for volatile and nonvolatile solutes in aqueous droplets that are held at a constant relative humidity. The aerosol inorganic-organic mixture functional group activity coefficients thermodynamic model and Debye-Hückel theory are both used to calculate the activities of the species present in the droplet. For DCAs, we find that the evaporation rate is highly sensitive to the particle pH. For acidity changes of approximately 1.5 pH units, we observe a shift from a volatile system to one that is completely nonvolatile. We also observe that the pH itself is not constant during evaporation; it increases as DCAs evaporate, slowing the rate of evaporation until it eventually ceases. Whether a DCA evaporates or remains a stable component of the droplet is determined by the difference between the lowest pKa of the DCA and the pH of the droplet.

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. Here we present observational and theoretical evidence illustrating that, in ambient air, surface tension lowering can prevail over the reduction in the Raoult effect, leading to substantial increases in cloud droplet concentrations. We suggest that consideration of liquid-liquid phase separation, leading to complete or partial engulfing of a hygroscopic particle core by a hydrophobic organic-rich phase, can explain the lack of concomitant reduction of the Raoult effect, while maintaining substantial lowering of surface tension, even for partial surface coverage. Apart from the importance of particle size and composition in droplet activation, we show by observation and modelling that incorporation of phase-separation effects into activation thermodynamics can lead to a CCN number concentration that is up to ten times what is predicted by climate models, changing the properties of clouds. An adequate representation of the CCN activation process is essential to the prediction of clouds in climate models, and given the effect of clouds on the Earth's energy balance, improved prediction of aerosol-cloud-climate interactions is likely to result in improved assessments of future climate change.

Comparison of Phase States of PM2.5 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 (PM2.5) in two megacities, Seoul and Beijing, we collected PM2.5 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 PM2.5 as a function of relative humidity (RH) were determined and compared to the ambient RH ranges in the two cities. PM2.5 was found to be liquid to semisolid in Seoul but mostly semisolid to solid in Beijing. The liquid state was dominant on polluted days, while a semisolid state was dominant on clean days in Seoul. These findings can be explained by the aerosol liquid water content related to the chemical compositions of the aerosols at ambient RH; the water content of PM2.5 was much higher in Seoul than in Beijing. Furthermore, the overall phase states of PM2.5 observed in Seoul and Beijing were interrelated with the particle size distribution. The results of this study aid in a better understanding of the fundamental physical properties of aerosols and in examining how these are linked to PM2.5 in polluted urban atmospheres.

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-1 (PEG400) and ammonium sulfate (AS), i.e., PEG400-AS particles/droplets, were investigated at different organic-to-inorganic dry mass ratios (OIRs) under typical tropospheric temperatures and water activities (aw). The investigated droplets (60-100 µm) with or without LLPS in the closed system froze through homogeneous ice nucleation. At temperatures lower than 200 K, multiple ice nucleation events were observed within the same individual droplets at low aw. Droplets with and without LLPS shared similar lambda values at the same OIR according to the lambda approach indicating they form ice through the same mechanism. A parameterization of lambda values was provided which can be used to predict freezing temperature of aqueous PEG400-AS droplets. We found that adding AS reduces the temperature dependence of aw in aqueous PEG400 droplets. Assuming incorrectly that aw is temperature-independent for a constant droplet composition leads to a deviation between the experimental determined ice nucleation rate coefficients for droplets at OIR > 1 and the predicted values by the water-activity-based ice nucleation theory. We proposed a parameterization of temperature dependence of aw to minimize the deviations of the measured melting temperatures and nucleation rate coefficients from the corresponding predictions for aqueous PEG400-AS system.

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. The same radiation pressure that results in stable trapping will also exert a deforming optical stress on the surface of the particle. For micron-sized aqueous droplets held in the air, the deformation will be on the order of a few nanometers or less, clearly not observable through optical microscopy. In this study, we utilize cavity-enhanced Raman scattering and a phenomenon known as thermal locking to measure small deformations in optically trapped droplets. With the aid of light-scattering calculations and a model that balances the hydrostatic pressure, surface tension, and optical pressure across the air-droplet interface, we can accurately determine surface tension from our measurements. Our approach is applied to 2 systems of atmospheric interest: aqueous organic and inorganic aerosol.

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. Kinetic multilayer modeling demonstrates that the slow decay of BaP over long times can be simulated if there is slow diffusion of BaP from the film interior to the surface, resolving long-standing unresolved observations of incomplete PAH decay upon prolonged ozone exposure. Phase separation drives the slow diffusion time scales in multicomponent systems. Specifically, thermodynamic modeling predicts that BaP phase separates from secondary organic aerosol material so that the BaP-rich layer at the surface shields the inner BaP from ozone. Also, BaP is miscible with organic oils such as squalane, linoleic acid, and cooking oil, but its oxidation products are virtually immiscible, resulting in the formation of a viscous surface crust that hinders diffusion of BaP from the film interior to the surface. These findings imply that phase separation and slow diffusion significantly prolong the chemical lifetime of PAHs, affecting long-range transport of PAHs in the atmosphere and their fates in indoor environments.

Assessing Human Exposure to SVOCs in Materials, Products, and Articles: A Modular Mechanistic Framework.

A critical review of the current state of knowledge of chemical emissions from indoor sources, partitioning among indoor compartments, and the ensuing indoor exposure leads to a proposal for a modular mechanistic framework for predicting human exposure to semivolatile organic compounds (SVOCs). Mechanistically consistent source emission categories include solid, soft, frequent contact, applied, sprayed, and high temperature sources. Environmental compartments are the gas phase, airborne particles, settled dust, indoor surfaces, and clothing. Identified research needs are the development of dynamic emission models for several of the source emission categories and of estimation strategies for critical model parameters. The modular structure of the framework facilitates subsequent inclusion of new knowledge, other chemical classes of indoor pollutants, and additional mechanistic processes relevant to human exposure indoors. The framework may serve as the foundation for developing an open-source community model to better support collaborative research and improve access for application by stakeholders. Combining exposure estimates derived using this framework with toxicity data for different end points and toxicokinetic mechanisms will accelerate chemical risk prioritization, advance effective chemical management decisions, and protect public health.

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). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

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. 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.

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. SOA evaporation is induced by heating the chamber aerosol from room temperature (25 °C) to 42 °C over 7 h and detected by a shift in the peak diameter of the SOA size distribution. With this protocol, α-pinene SOA is found to be more volatile than toluene SOA. When SOA is formed from the two precursors sequentially, the evaporation behavior of the SOA most closely resembles that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA resembles a core of SOA from the initial precursor coated by a layer of SOA from the second precursor. Such a core-and-shell configuration of the organic aerosol phases implies limited mixing of the SOA from the two precursors on the time scale of the experiments, consistent with a high viscosity of at least one of the phases.

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. Using the canonical system of ammonium sulfate mixed with organics from the ozone oxidation of α-pinene, we illustrate theoretically the interplay of physical state, non-ideality, and particle morphology affecting aerosol mass concentration and the characteristic timescale of gas-particle mass transfer. Phase separation can significantly affect overall particle mass and chemical composition. Semi-solid or glassy phases can kinetically inhibit the partitioning of semivolatile components and hygroscopic growth, in contrast to the traditional assumption that organic compounds exist in quasi-instantaneous gas-particle equilibrium. These effects have significant implications for the interpretation of laboratory data and the development of improved atmospheric air quality and climate models.

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. In addition, the density and refractive index of binary aqueous citric acid and raffinose solutions and the glass transition temperatures of binary aqueous L(+)-tartaric acid and levoglucosan solutions have been measured. The data presented here are derived from experiments on single levitated microdroplets and bulk solutions and should find application in thermodynamic and atmospheric aerosol models as well as in food science applications.

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. 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.

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 (NH4)2SO4 seed particles. A hygroscopicity tandem differential mobility analyzer was used to determine the GFs of the SOA particles at RHs ≤ 93%. For some experiments, a CCN counter was used for size-resolved measurement of CCN activation at supersaturation (S) in the range of 0.1 to 1%. The single hygroscopicity parameter κ was derived from both the GF and CCN measurements. Under subsaturated conditions, all the SOA (except those in the presence of the (NH4)2SO4 seeds) showed small GF values. These GFs demonstrated that SOA mass loading affected the GF. A decrease in the SOA mass loading led to increased GF and corresponding κGFvalues. However, in a supersaturation regime, the SOA mass loading and the size of the particles did not significantly alter the CCN activity of the SOA. Our CCN measurements showed higher κCCN values (κCCN = 0.20-0.24) than those observed in most monoterpene ozonolysis studies (κCCN = 0.1-0.14). This difference may have been due to the presence of the two endocyclic double bonds in the γ-terpinene structure, which may have affected the SOA chemical composition, in contrast to monoterpenes that contain an exocyclic double bond. Our comparisons of sub- and supersaturated conditions showed a larger range of κ values than other experiments. Average κCCN/κGF ratios of ~7 and 14 were obtained in the unseeded SOA experiments at low and high SOA mass loadings, respectively. The average κCCN of 0.23 indicated that the SOA produced during ozonolysis of γ-terpinene exhibited fairly high CCN activity.

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 36.3% 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 mum 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 mum 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.

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 HNO3, NH3, 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. Despite its fundamental role in atmospheric processes, only recently has this field seen a growth in the number of studies on particle acidity. Even with this growth, many fine particle pH estimates must be based on thermodynamic model calculations since no operational techniques exist for direct measurements. Current information indicates acidic fine particles are ubiquitous, but observationally-constrained pH estimates are limited in spatial and temporal coverage. Clouds and fogs are also generally acidic, but to a lesser degree than particles, and have a range of pH that is quite sensitive to anthropogenic emissions of sulfur and nitrogen oxides, as well as ambient ammonia. Historical measurements indicate that cloud and fog droplet pH has changed in recent decades in response to controls on anthropogenic emissions, while the limited trend data for aerosol particles indicates acidity may be relatively constant due to the semi-volatile nature of the key acids and bases and buffering in particles. This paper reviews and synthesizes the current state of knowledge on the acidity of atmospheric condensed phases, specifically particles and cloud droplets. It includes recommendations for estimating acidity and pH, standard nomenclature, a synthesis of current pH estimates based on observations, and new model calculations on the local and global scale.

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.