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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

Squalene is a major skin oil lipid which can react with ozone forming a range of products including carbonyls, carboxylic acids, hydroxy ketones, secondary ozonides and hydroperoxides. Previous experimental studies have shown that the yield of these products depends on relative humidity. A new mechanism is developed which treats the reaction of ozone with carbon–carbon double bonds and the subsequent reactions of the Criegee intermediates forming a range of products in both condensed and gas phases. The mechanism is included in kinetic models for a variety of ozonolysis reaction systems including pure squalene particles, squalene and skin oil films, clothing, and skin covered by clothing. The models reproduce experimental measurements reasonably well using relatively consistent parameters, providing insights into the important reactions and processes controlling the concentrations of different species. In general, gas-phase secondary carbonyl product concentrations increase significantly as a function of relative humidity due to their formation from the reaction of Criegee intermediates with water, while carboxylic acids and hydroxy ketone concentrations decrease. For example, human exposure to gas-phase 6-methyl-5-hepten-2-one can increase by approximately a factor of two as the relative humidity increases from 10% to 95%. The model can also reproduce the decay of carboxylic acids in skin oil due to their reaction with Criegee intermediates. Discrepancies between some of the measurements and model outputs indicate that in addition to impacting chemistry, relative humidity may affect other processes such as partitioning to surfaces and condensed-phase diffusion.

A phase state of ambient aerosols is a key parameter to understand physicochemical properties of aerosols such as growth rate, size distribution, and mass concentration that affect climate and human health. However, only limited information of real aerosol phase states has been obtained. Herein, to explore phase states of fine particulate matter (PM2.5) in megacities, we collected daily PM2.5 filter samples during December 2020 – January 2021 in Seoul and Beijing. Optical microscopy and a poke-and-flow technique were used to observe the morphologies and phase states of the PM2.5. Results showed that the average phase states of the PM2.5 were significantly different in the two megacities. The PM2.5 existed as a liquid state to a semisolid in Seoul while it existed as a semisolid to a solid in Beijing. These differences were governed by the chemical composition of PM2.5 and aerosol liquid water content. Furthermore, the phase state of PM2.5 in two megacities was correlated with particle size distribution. Our findings can provide an understanding of the phase states of real-world aerosols and how the phase state is linked to chemical compositions, ALWC, and size distributions of PM2.5.

To explore aerosol chemistry and climate change, information of the physical state of aerosol particles is essential. Herein, we measured viscosities of binary mixtures of sucrose/H2O and ammonium sulfate (AS)/H2O, and ternary mixtures of sucrose/AS/H2O with different organic-to-inorganic dry mass ratios. For sucrose droplets, the viscosity gradually enhanced from ~4 × 10-1 to > ~1 × 108 Pa‧s as the relative humidity (RH) decreased from ~81% to ~24%. This corresponds from liquid to semisolid or solid state. For AS droplets, the viscosity dramatically enhanced at ~ 50% RH upon dehydration; to be < 102 Pa‧s for RH > ~50% (liquid state), and > ~1 × 1012 Pa‧s for RH ≤ ~50% (solid state). In case of the ternary mixtures, remarkable enhancement in viscosity was observed as the inorganic ratio increased at a given RH. All particles studied in this work were observed to exist as a liquid, semi-solid or solid depending on the organic-to-inorganic dry mass ratios and RH. Moreover, the measured viscosities of the binary and ternary mixtures were compared with the calculated viscosities using the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients Viscosity model (AIOMFAC-VISC) predictions with the Zdanovskii–Stokes–Robinson (ZSR)-style organic–inorganic mixing model. It showed excellent model–measurement agreement. The result will be discussed.

Aerosol viscosity is determined by mixture composition and temperature, with a key influence from relative humidity (RH) in modulating aerosol water content. Aerosol particles frequently contain mixtures of water, organic compounds, and inorganic ions, so we have extended the thermodynamics-based group-contribution model AIOMFAC-VISC to predict viscosity for aqueous electrolyte solutions and aqueous organic–inorganic mixtures. For aqueous electrolyte solutions, our new, semi-empirical approach uses a physical expression based on Eyring's absolute rate theory, and we define activation energy for viscous flow as a function of temperature, ion activities, and ionic strength. The AIOMFAC-VISC electrolyte model's ion-specific expressions were simultaneously fitted, which arguably makes this approach more predictive than that of other models. This also enables viscosity calculations for aqueous solutions containing an arbitrary number of cation and anion species, including mixtures that have never been studied experimentally. These predictions achieve an excellent level of accuracy while also providing physically meaningful extrapolations to extremely high electrolyte concentrations, which is essential in the context of microscopic aqueous atmospheric aerosols. For organic–inorganic mixtures, multiple mixing approaches were tested to couple the AIOMFAC-VISC electrolyte model with its existing aqueous organic model. We discuss the best-performing mixing models implemented in AIOMFAC-VISC for reproducing viscosity measurements of aerosol surrogate systems. We present advantages and drawbacks of different model design choices and associated computational costs of these methods, of importance for use of AIOMFAC-VISC in dynamic simulations. Finally, we demonstrate the capabilities of AIOMFAC-VISC predictions for phase-separated organic–inorganic particles equilibrated to observed temperature and relative humidity conditions from atmospheric balloon soundings. The predictions for the studied cases suggest liquid-like viscosities for an aqueous electrolyte-rich particle phase throughout the troposphere, yet a highly viscous or glassy organic-rich phase in the middle and upper troposphere.

Secondary organic aerosol (SOA) particles in Earth's atmosphere can exist in phase states where mass transport and chemical transformations are greatly impeded.

Organic aerosols are a major component of particulate matter but have a complex and uncertain effect on climate and health.

Atmospheric aerosol particles and their interactions with clouds are among the largest sources of uncertainty in global climate modeling. Aerosol particles in the ultrafine size range with diameters less than 100 nm have very high surface-area-to-volume ratios, with a substantial fraction of molecules occupying the air–droplet interface. The partitioning of surface-active species between the interior bulk of a droplet and the interface with the surrounding air plays a large role in the physicochemical properties of a particle and in the activation of ultrafine particles, especially those of less than 50 nm diameter, into cloud droplets. In this work, a novel and thermodynamically rigorous treatment of bulk–surface equilibrium partitioning is developed through the use of a framework based on the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model in combination with a finite-depth Guggenheim interface region on spherical, finite-volume droplets. We outline our numerical implementation of the resulting modified Butler equation, including accounting for challenging extreme cases when certain compounds have very limited solubility in either the surface or the bulk phase. This model, which uses a single, physically constrained interface thickness parameter, is capable of predicting the size-dependent surface tension of complex multicomponent solutions containing organic and inorganic species. We explore the impacts of coupled surface tension changes and changes in bulk–surface partitioning coefficients for aerosol particles ranging in diameters from several micrometers to as small as 10 nm and across atmospherically relevant relative humidity ranges. The treatment of bulk–surface equilibrium leads to deviations from classical cloud droplet activation behavior as modeled by simplified treatments of the Köhler equation that do not account for bulk–surface partitioning. The treatments for bulk–surface partitioning laid out in this work, when applied to the Köhler equation, are in agreement with measured critical supersaturations of a range of different systems. However, we also find that challenges remain in accurately modeling the growth behavior of certain systems containing small dicarboxylic acids, especially in a predictive manner. Furthermore, it was determined that the thickness of the interfacial phase is a sensitive parameter in this treatment; however, constraining it to a meaningful range allows for predictive modeling of aerosol particle activation into cloud droplets, including cases with consideration of co-condensation of semivolatile organics.

International audience; 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 κGF values. 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.

Although knowledge of the physical state of aerosol particles is essential to understand atmospheric chemistry model and measurements, information on the viscosity and physical state of aerosol particles consisting of organic and inorganic salts is still rare. Herein, we quantified viscosities at 293 ± 1 K upon dehydration for the binary systems, sucrose–H2O and ammonium sulfate (AS)–H2O, and the ternary systems, sucrose–AS–H2O for organic-to-inorganic dry mass ratios (OIRs) = 4:1, 1:1, and 1:4 using bead-mobility and poke-and-flow techniques. Based on the viscosity value of the aerosol particles, we defined the physical states of the total aerosol particles studied in this work. For binary systems, the viscosity of sucrose–H2O particles gradually increased from ∼ 4 × 10−1 to > ∼ 1 × 108 Pa s when the relative humidity (RH) decreased from ∼ 81 % to ∼ 24 %, ranging from liquid to semisolid or solid state, which agrees with previous studies. The viscosity of AS–H2O particles remained in the liquid state (< 102 Pa s) for RH > ∼ 50 %, while for RH ≤∼ 50 %, the particles showed a viscosity of > ∼ 1 × 1012 Pa s, corresponding to a solid state. In case of the ternary systems, the viscosity of organic-rich particles (OIR = 4:1) gradually increased from ∼ 1 × 10−1 to ∼ 1 × 108 Pa s for a RH decrease from ∼ 81 % to ∼ 18 %, similar to the binary sucrose–H2O particles. This indicates that the sucrose–AS–H2O particles range from liquid to semisolid or solid across the RH. In the ternary particles for OIR = 1:1, the viscosities ranged from less than ∼ 1 × 102 for RH > 34 % to > ∼ 1 × 108 Pa s at ∼ 27 % RH. The viscosities correspond to liquid for RH > ∼ 34 %, semisolid for ∼ 34 % < RH < ∼ 27 %, and semisolid or solid for RH < ∼ 27 %. Compared to the organic-rich particles, in the inorganic-rich particles (OIR = 1:4), drastic enhancement in viscosity was observed as RH decreased; the viscosity increased by approximately 8 orders of magnitude during a decrease in RH from 43 % to 25 %, resulting in liquid to semisolid or solid in the RH range. Overall, all particles studied in this work were observed to exist as a liquid, semisolid, or solid depending on the RH. Furthermore, we compared the measured viscosities of ternary systems with OIRs of 4:1, 1:1, and 1:4 to the predicted viscosities using the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients Viscosity model (AIOMFAC-VISC) predictions with the Zdanovskii–Stokes–Robinson (ZSR) organic–inorganic mixing model, with excellent model–measurement agreement for all OIRs.

Aerosol viscosity is determined by mixture composition and temperature, with a key influence from relative humidity (RH) in modulating aerosol water content. Aerosol particles frequently contain mixtures of water, organic compounds and inorganic ions, so we have extended the thermodynamics-based group-contribution model AIOMFAC-VISC to predict viscosity for aqueous electrolyte solutions and aqueous organic-inorganic mixtures. For aqueous electrolyte solutions, our new, semi-empirical approach uses a physical expression based on Eyring's absolute rate theory, and we define activation energy for viscous flow as a function of temperature, ion activities, and ionic strength. The AIOMFAC-VISC electrolyte model's ion-specific expressions were simultaneously fitted, which arguably makes this approach more predictive than that of other models. This also enables viscosity calculations for aqueous solutions containing an arbitrary number of cation and anion species, including mixtures that have never been studied experimentally. These predictions achieve an excellent level of accuracy while also providing physically meaningful extrapolations to extremely high electrolyte concentrations, which is essential in the context of microscopic aqueous atmospheric aerosols. For organic-inorganic mixtures, multiple mixing approaches were tested to couple the AIOMFAC-VISC electrolyte model with its existing aqueous organic model. We discuss the best performing mixing models implemented in AIOMFAC-VISC for reproducing viscosity measurements of aerosol surrogate systems. We present advantages and drawbacks of different model design choices and associated computational costs of these methods, of importance for use of AIOMFAC-VISC in dynamic simulations. Finally, we demonstrate the capabilities of AIOMFAC-VISC predictions for phase-separated organic-inorganic particles equilibrated to observed temperature and relative humidity conditions from atmospheric balloon soundings. The predictions for the studied cases suggest liquid-like viscosities for an aqueous electrolyte-rich particle phase throughout the troposphere, yet a highly viscous or glassy organic-rich phase in the middle and upper troposphere.

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.

Unexpectedly high amounts of aminium salts have been detected in ambient aerosol particles, prompting investigations into their role in new particle formation and nanoparticle growth. Amine uptake ...

Significance Aerosol particles are ubiquitous in the atmosphere and play an important role in air quality and the climate system. These particles can contain mixtures of primary organic aerosol, secondary organic aerosol, and secondary inorganic aerosol. We show that such internally mixed particles can contain three liquid phases. We also demonstrate that the presence of three liquid phases impacts the time needed for the particles to reach equilibrium with the surrounding gas phase and likely impacts the ability of the particles to activate into cloud droplets. A framework is presented for predicting conditions needed for the formation of three liquid phases in the atmosphere. These results will lead to improved representations of aerosols in models for air quality and climate predictions., 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.

Aerosol particles are ubiquitous in the atmosphere and play an important role for air quality and Earth’s climate. Primary organic aerosol (POA), secondary organic aerosol (SOA), and secondary inorganic aerosol (SIA) constitute a significant mass fraction of these particles. POA, SOA, and SIA can become internally mixed within the same particle though different processes such as coagulation, gas–particle partitioning. To predict the role of these internally mixed particles in climate and air quality information on their phase behaviour is needed, i.e. information on the number and type of phases present within these particles. As an example, a particle with a single homogeneous liquid phase can have different radiative properties, reaction rates, uptake kinetics, and potential to change cloud microphysical properties by activating into a cloud droplet, compared to a particle with multiple liquid or solid phases.In the current study we used Nile red, a solvatochromic dye, and fluorescence microscopy in order to determine the phase behaviour of POA+SOA+SIA particles. Squalane was used as a proxy of POA, ammonium sulfate was used as SIA and 1 of 23 different oxidized organic molecules were used as proxies of SOA. We demonstrate that three liquid phases often coexist within individual particles. We find that the phase behaviour strongly depends on the oxygen-to-carbon ratio of the SOA proxies. Experiments with SOA generated by dark ozonolysis of α-pinene in an environmental chamber are consistent with these observations. We also used thermodynamic and kinetic modelling to investigate the atmospheric implications of our experimental results.

Organic compounds residing near the surface of atmospheric aerosol particles are exposed to chemical reactions initiated by gas-phase oxidants, such as hydroxyl (OH) radicals. Aqueous droplets composed of inorganic salts and organic compounds can undergo phase separation into two liquid phases, depending on aerosol composition and relative humidity (RH). Such phase behavior can govern the surface characteristics and morphology of the aerosols, which in turn affect the heterogeneous reactivity of organic compounds toward gas-phase oxidants. In this work, we used an aerosol flow tube reactor coupled with an atmospheric pressure ionization source (Direct Analysis in Real Time) and a high-resolution mass spectrometer to investigate how phase separation in model aqueous droplets containing an inorganic salt (ammonium sulfate, AS) and an organic acid (3-methyglutaric acid, 3-MGA) with an organic-to-inorganic dry mass ratio (OIR) of 1 alters the heterogeneous OH reactivity. At high RH, 3-MGA/AS aerosols were aqueous droplets with a single liquid phase. When the RH decreased, aqueous 3-MGA/AS droplets underwent phase separation at ~75 % RH. Once the droplets were phase-separated, they exhibited either a core–shell, partially engulfed, or a transition from core–shell to partially engulfed structure, with an organic-rich outer phase and an inorganic-rich inner phase. The kinetics, quantified by an effective heterogenous OH rate constant, was found to increase gradually from 1.01 ± 0.02 × 10e−12 to 1.73 ± 0.02 × 10e−12 cm3 molecule−1 s−1 when the RH decreased from 88 % to 55 %. The heterogeneous reactivity of phase-separated droplets is slightly higher than that of aqueous droplets with a single liquid phase. This could be explained by the finding that when the RH decreases, higher concentrations of organic molecules (i.e. 3-MGA) are present at or near the droplet surface, which are more readily exposed to OH oxidation, as demonstrated by phase separation measurements and model simulations. This could increase the reactive collision probability between 3-MGA molecules and OH radicals dissolved near the droplet surface and secondary chain reactions. Even for phase-separated droplets with a fully established core–shell structure, the diffusion rate of organic molecules across the organic-rich outer shell is predicted to be fast in this system. Thus, the overall rate of reactions is likely governed by the surface concentration of 3-MGA rather than a diffusion limitation. Overall, understanding the aerosol phase state (single liquid phase versus two separate liquid phases) is essential to better probe the heterogenous reactivity under different aerosol chemical composition and environmental conditions (e.g. RH).

Sulfate aerosols are typically the dominant source of cloud condensation nuclei (CCN) over remote oceans and their abundance is thought to be the dominating factor in determining oceanic cloud brightness. Their activation into cloud droplets depends on dynamics (i.e. vertical updrafts) and competition with other potential CCN sources for the condensing water. We present new experimental results from the remote Southern Ocean illustrating that, for a given updraft, the peak supersaturation reached in cloud, and consequently the number of droplets activated on sulfate nuclei, is strongly but inversely proportional to the concentration of sea-salt activated despite a 10-fold lower abundance. Greater sea-spray nuclei availability mostly suppresses sulfate aerosol activation leading to an overall decrease in cloud droplet concentrations; however, for high vertical updrafts and low sulfate aerosol availability, increased sea-spray can augment cloud droplet concentrations. This newly identified effect where sea-salt nuclei indirectly controls sulfate nuclei activation into cloud droplets could potentially lead to changes in the albedo of marine boundary layer clouds by as much as 30%. The research leading to these results has received funding from SFI under MaREI; the European Union’s Seventh Framework Programme (FP7/2007–2013) project BACCHUS under grant agreement n_603445; Spanish Ministry of Economy and Competitiveness (MINECO) as part of the PEGASO (Ref.: CTM2012-37615) and BIONUC (Ref: CGL2013-49020-R) projects. The Antarctic cruise that led to this study was organised by R. Simo and M. Dall’Osto from the Institut de Ciéncies del Mar (CSIC), Barcelona, Catalonia, Spain. peer-reviewed

Hygroscopic growth factors of organic surrogate compounds representing biomass burning and mixed organic–inorganic aerosol particles exhibit variability during dehydration experiments depending on their chemical composition, which we observed using a hygroscopicity tandem differential mobility analyzer (HTDMA). We observed that levoglucosan and humic acid aerosol particles release water upon dehumidification in the range from 90 to 5 % relative humidity (RH). However, 4-Hydroxybenzoic acid aerosol particles remain in the solid state upon dehumidification and exhibit a small shrinking in size at higher RH compared to the dry size. For example, the measured growth factor of 4-hyroxybenzoic acid aerosol particles is ∼ 0.96 at 90 % RH. The measurements were accompanied by RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model and Extended Aerosol Inorganics Model (E-AIM), the Zdanovskii–Stokes–Robinson (ZSR) relation, and a fitted hygroscopicity expression. We observed several effects of organic components on the hygroscopicity behavior of mixtures containing ammonium sulfate (AS) in relation to the different mass fractions of organic compounds: (1) a shift of efflorescence relative humidity (ERH) of ammonium sulfate to higher RH due to the presence of 25 wt % levoglucosan in the mixture. (2) There is a distinct efflorescence transition at 25 % RH for mixtures consisting of 25 wt % of 4-hydroxybenzoic acid compared to the ERH at 35 % for organic-free AS particles. (3) There is indication for a liquid-to-solid phase transition of 4-hydroxybenzoic acid in the mixed particles during dehydration. (4) A humic acid component shows no significant effect on the efflorescence of AS in mixed aerosol particles. In addition, consideration of a composition-dependent degree of dissolution of crystallization AS (solid–liquid equilibrium) in the AIOMFAC and E-AIM models leads to a relatively good agreement between models and observed growth factors, as well as ERH of AS in the mixed system. The use of the ZSR relation leads to good agreement with measured diameter growth factors of aerosol particles containing humic acid and ammonium sulfate. Lastly, two distinct mixtures of organic surrogate compounds, including levoglucosan, 4-hydroxybenzoic acid, and humic acid, were used to represent the average water-soluble organic carbon (WSOC) fractions observed during the wet and dry seasons in the central Amazon Basin. A comparison of the organic fraction's hygroscopicity parameter for the simple mixtures, e.g., κ ≈ 0.12 to 0.15 for the wet-season mixture in the 90 to 40 % RH range, shows good agreement with field data for the wet season in the Amazon Basin (WSOC κ ≈ 0.14±0.06 at 90 % RH). This suggests that laboratory-generated mixtures containing organic surrogate compounds and ammonium sulfate can be used to mimic, in a simplified manner, the chemical composition of ambient aerosols from the Amazon Basin for the purpose of RH-dependent hygroscopicity studies.

The spontaneous growth of cloud condensation nuclei (CCN) into cloud droplets under supersaturated water vapour conditions is described by classic Kohler theory(1,2). 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(1). 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(3,4). 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.

The interactions among low and semi-volatile organic compounds, water and other inorganic components within fine-mode aerosols are complex. We show that understanding several features of this complexity can be important in the context of phase separation, a particle surface composition enriched by organics and for related cloud droplet activation modeling. Context: oxidized organic compounds contribute to the particle hygroscopicity, yet typically to a lesser extent than dissolved inorganic ions. The overall hygroscopicity of aerosols in turn greatly affects their water uptake in an air parcel experiencing increasing relative humidity. The mechanism acts directly in terms of adding water mass, as well as indirectly via a hygroscopicity-induced feedback leading to enhanced gas–to–particle partitioning of semi-volatile organic components alongside a re-equilibration of the aerosol with inorganic acids, ammonia and further water uptake. Furthermore, non-ideal mixing may induce liquid–liquid phase separation, often leading to an organic-rich phase of relatively low surface tension surrounding an inorganic-rich particle core. This phase separation effect and related surface enhancements of organic component concentrations affect not only the morphology but also the potential for near-surface chemical reactions, as well as the thermodynamics controlling an aerosol particle’s activation into a cloud droplet at realistic water vapour supersaturations. New experimental techniques and field observations over the past few years have encouraged model development for an improved representation of these processes on a detailed level (see, e.g., discussion in Davies et al., 2019). This has led to a better understanding of the potential role of organic aerosol compounds spanning a range of polarities and an associated evolution of surface tension prior to the cloud condensation nucleus (CCN) activation point. While detailed process models still lack finer details to fully capture these composition and phase effects reliably and predictively, important challenges exist in translating these mechanisms into computationally efficient and feasible reduced-complexity models of use for air quality and chemistry-climate modelling.In this presentation, we will outline the current state of a relatively complete process-level aerosol thermodynamics model based on AIOMFAC and introduce key features of a recently developed reduced-complexity organic aerosol model that accounts for water content and hygroscopicity-induced feedbacks on composition (Gorkowski et al., 2019). A key advantage of the reduced-complexity model is its ability to use only input typically known from field measurements or data available in large-scale air quality models. Our approach is compatible with a volatility basis set approach and allows for extending it by adding a realistic humidity dependence. In addition, we account for phase separation and related effects on surface tension in a simplified, computationally efficient manner. This approach and its results for aerosol hygroscopicity and cloud droplet activation will be discussed.References:Davies, J. F., Zuend, A., and Wilson, K. R.: Technical note: The role of evolving surface tension in the formation of cloud droplets, Atmos. Chem. Phys., 19, 2933–2946, doi:10.5194/acp-19-2933-2019, 2019.Gorkowski, K., Preston, T. C., and Zuend, A.: Relative-humidity-dependent organic aerosol thermodynamics via an efficient reduced-complexity model, Atmos. Chem. Phys., 19, 13383–13407, 10.5194/acp-19-13383-2019, 2019.

The viscosity of primary and secondary organic aerosol (SOA) has important implications for the processing of aqueous organic aerosol phases in the atmosphere, their involvement in climate forcing, and transboundary pollution. Here we introduce a new thermodynamics-based group-contribution model, which is capable of accurately predicting the dynamic viscosity of a mixture over several orders of magnitude (∼10-3 to >1012 Pa s) as a function of temperature and mixture composition, accounting for the effect of relative humidity on aerosol water content. The mixture viscosity modelling framework builds on the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients) for predictions of liquid mixture non-ideality, including liquid–liquid phase separation, and the calorimetric glass transition temperature model by DeRieux et al. (2018) for pure-component viscosity values of organic components. Comparing this new model with simplified modelling approaches reveals that the group-contribution method is the most accurate in predicting mixture viscosity, although accurate pure-component viscosity predictions (and associated experimental data) are key and one of the main sources of uncertainties in current models, including the model presented here. Nonetheless, we find excellent agreement between the viscosity predictions and measurements for systems in which mixture constituents have a molar mass below 350 g mol−1. As such, we demonstrate the validity of the model in quantifying mixture viscosity for aqueous binary mixtures (glycerol, citric acid, sucrose, and trehalose), aqueous multicomponent mixtures (citric acid plus sucrose and a mixture of nine dicarboxylic acids), and aqueous SOA surrogate mixtures derived from the oxidation of α-pinene, toluene, or isoprene. We also use the model to assess the expected change in SOA particle viscosity during idealized adiabatic air parcel transport from the surface to higher altitudes within the troposphere. This work demonstrates the capability and flexibility of our model in predicting the viscosity for organic mixtures of varying degrees of complexity and its applicability for modelling SOA viscosity over a wide range of temperatures and relative humidities.

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

Water plays an essential role in aerosol chemistry, gas-particle partitioning, and particle viscosity, but it is typically omitted in thermodynamic models describing the mixing within organic aerosol phases and the partitioning of semivolatile organics. In this study, we introduce the Binary Activity Thermodynamics (BAT) model, a water-sensitive, reduced-complexity model treating the non-ideal mixing of water and organics. The BAT model can process different levels of physicochemical mixture information enabling its application in the thermodynamic aerosol treatment within chemical transport models, the evaluation of humidity effects in environmental chamber studies, and the analysis of field observations. It is capable of using organic structure information including O:C, H:C, molar mass, and vapor pressure, which can be derived from identified compounds or estimated from bulk aerosol properties. A key feature of the BAT model is predicting the extent of liquid-liquid phase separation occurring within aqueous mixtures containing hydrophobic organics. This is crucial to simulating the abrupt change in water uptake behavior of moderately hygroscopic organics at high relative humidity, which is essential for capturing the correct behavior of organic aerosols serving as cloud condensation nuclei. For gas-particle partitioning predictions, we complement a Volatility Basis Set (VBS) approach with the BAT model to account for non-ideality and liquid-liquid equilibrium effects. To improve the computational efficiency of this approach, we trained two neural networks; the first for the prediction of aerosol water content at given relative humidity, and the second for the partitioning of semivolatile components. The integrated VBS + BAT model is benchmarked against high-fidelity molecular-level gas-particle equilibrium calculations based on the AIOMFAC model. Organic aerosol systems derived from alpha-pinene or isoprene oxidation are used for comparison. Predicted organic mass concentrations agree within less than a 5 % error in the isoprene case, which is a significant improvement over a traditional VBS implementation. In the case of the alpha-pinene system, the error is less than 2 % up to a relative humidity of 94 %, with larger errors past that point. The goal of the BAT model is to represent the bulk O:C and molar mass dependencies of a wide range of water-organic mixtures to a reasonable degree of accuracy. In this context, we discuss that the reduced-complexity effort may be poor at representing a specific binary water-organic mixture perfectly. However, the averaging effects of our reduced-complexity model become more representative when the mixture diversity increases in terms of organic functionality and number of components.

Significance Polycyclic aromatic hydrocarbons (PAHs) are among the most prominent toxic compounds in the air. Heterogeneous reactions involving O3 can change the toxicity of PAHs, but the reaction mechanism and kinetics remain to be elucidated. Based on new experiments combined with state-of-the-art kinetic and thermodynamic models, we show that phase separation plays a critical role in the ozonolysis of PAHs mixed with secondary organic aerosols and organic oils. Ozonolysis products of PAHs phase separate to form viscous surface crusts, which protect underlying PAHs from ozonolysis to prolong their chemical lifetime. These results have significant implications for outdoor and indoor air quality by affecting PAH long-range transport and fate in indoor environments., 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.

The role of surface tension (σ) in cloud droplet activation has long been ambiguous. Recent studies have reported observations attributed to the effects of an evolving surface tension in the activation process. However, the adoption of a surface-mediated activation mechanism has been slow and many studies continue to neglect the composition dependence of aerosol–droplet surface tension, using instead a value equal to the surface tension of pure water (σw). In this technical note, we clearly describe the fundamental role of surface tension in the activation of multicomponent aerosol particles into cloud droplets. It is demonstrated that the effects of surface tension in the activation process depend primarily on the evolution of surface tension with droplet size, typically varying in the range 0.5σw≲σ≤σw due to the partitioning of organic species with a high surface affinity. We go on to report some recent laboratory observations that exhibit behavior that may be associated with surface tension effects and propose a measurement coordinate that will allow surface tension effects to be better identified using standard atmospheric measurement techniques. Unfortunately, interpreting observations using theory based on surface film and liquid–liquid phase separation models remains a challenge. Our findings highlight the need for experimental measurements that better reveal the role of composition-dependent surface tensions, critical for advancing predictive theories and parameterizations of cloud droplet activation.

The hygroscopic behavior of complex mixed organic–organic and organic–inorganic particles consisting of various dry mass ratios of ammonium sulfate (AS), oxalic acid (OA), malonic acid (MA) and polyethylene glycol-300 (PEG) has been studied using a Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) setup. The measured growth factors (GFs) are compared to values predicted by the AIOMFAC-based thermodynamic equilibrium model and the Zdanovskii–Stokes–Robinson (ZSR) mixing rule. The measured GFs for PEG–OA and PEG–MA systems are found to be significantly lower than those predicted by the two models, which assume the complete dissolution of the organic compounds. The observed behavior suggests that the presence of PEG substantially affects the solubility of organic acids and associated water uptake. For quinary systems containing PEG, organic acids, and AS, a complete deliquescence of the mixed particles is observed during hydration conditions at RH ~78–80% close to the deliquescence point of pure AS particles. A clear disagreement was observed between measurements and predictions from AIOMFAC and ZSR for hydration conditions prior to the full particle deliquescence. We provide indirect evidence for the presence of an organic solid alongside solid AS. Hypothetically, the observed disagreement could also be due to a preferential interaction between –COOH and –CH2OCH2- groups, which may prevent a fraction of the organic acid amount to interact with water. For fully deliquesced particles, good agreement between model predictions and measurements are found for the mixed PEG–organic acids–AS systems. Upon dehydration, when the mass fraction of PEG

Recent work has demonstrated that organic and mixed organic–inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle-phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic–inorganic aerosol systems with physical states ranging from well-mixed liquids to phase-separated particles to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40 to 90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids; (2) forcing a single phase but accounting for non-ideal interactions through activity coefficient calculations; and (3) a Zdanovskii–Stokes–Robinson-like calculation in which complete separation of the inorganic and organic components is assumed at all RH values, with water uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid–liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF measurements. The performances of the simplified modeling approaches, however, differ for particles with differing phase states. This suggests that no single simplified modeling approach can be used to capture the water-uptake behavior for the diversity of particle-phase behavior expected in the atmosphere. Errors in HGFs calculated with the simplified models are of sufficient magnitude to produce substantial errors in estimates of particle optical and radiative properties, particularly for the assumption that water uptake is driven by absorptive equilibrium partitioning with ideal particle-phase mixing.

This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic–water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~ 275 to ~ 400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures. To this end we introduce a new parameterisation for the temperature dependence. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multi-component system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~ 190 to ~ 440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 28% in comparison to the previous model version, when both versions are compared to our database of experimentally determined activity coefficients and related thermodynamic data. When comparing the previous and new AIOMFAC model parameterisations to the subsets of experimental data with all temperatures below 274 K or all temperatures above 322 K (i.e. outside a 25 K margin of the reference temperature of 298 K), applying the new parameterisation leads to 37% improvement in each of the two temperature ranges considered. The new parameterisation of AIOMFAC agrees well with a large number of experimental data sets. Larger model–measurement discrepancies were found particularly for some of the systems containing multi-functional organic compounds. The affected systems were typically also poorly represented at room temperature and further improvements will be necessary to achieve better performance of AIOMFAC in these cases (assuming the experimental data are reliable). The performance of the AIOMFAC parameterisation is typically better for systems containing relatively small organic compounds and larger deviations may occur in mixtures where molecules of high structural complexity such as highly oxygenated compounds or molecules of high molecular mass (e.g. oligomers) prevail. Nevertheless, the new parameterisation enables the calculation of activity coefficients for a wide variety of different aqueous/water-free organic solutions down to the low temperatures present in the upper troposphere.

Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phase for conditions in the southeastern United States 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 1.6 to 1.8 (Ratio of ammonium to 2 × sulfate, RN/2S ≈ 0.8 to 0.9) with approximately 70 % of total ammonia and ammonium (NHx) in the particle. Southeastern Aerosol Research and Characterization (SEARCH) network gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for Aerosols and Gases in Air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to biases in the nonvolatile cations that resulted from either overestimated emissions and/or underestimated mixing. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and Aerosol Mass Spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H+]air (H+ in μg m−3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid-liquid phase separation. In addition, accounting for non-ideal mixing modified the pH such that a fully interactive inorganic-organic system had a pH roughly 0.7 units higher than predicted by traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O : C ≥ 0.6) compounds including several isoprene-derived tracers as well as levoglucosan, but decrease particle-phase partitioning for low O : C, monoterpene-derived species.

Hygroscopic growth factors of organic surrogate compounds representing biomass burning and mixed organic-inorganic aerosol particles exhibit variability during dehydration experiments depending on their chemical composition, which we observed using a hygroscopicity tandem differential mobility analyzer (HTDMA). We observed that levoglucosan and humic acid aerosol particles release water slightly in the range of 90–5 % relative humidity (RH). 4-Hydroxybenzoic acid aerosol particles, however, remain in the solid state without diameter growth and even slightly shrinking at higher RH compared to the dry size. The measurements were accompanied by RH-dependent thermodynamic equilibrium calculations using the AIOMFAC and the E-AIM models, the ZSR relation, and a fitted hygroscopicity expression. We observed several effects of organic components on the hygroscopicity behavior of mixtures containing ammonium sulfate (AS) in relation to the different mass fractions of organic compounds: (1) a shift of efflorescence relative humidity (ERH) of ammonium sulfate to higher RH due to the presence of 25 wt % levoglucosan in the mixture. (2) There is a distinct efflorescence transition at 25 % RH for mixtures consisting of 25 wt % of 4-hydroxybenzoic acid compared to the ERH at 35 % for organic-free AS particles. (3) There is indication for a liquid-to-solid phase transition of 4-hydroxybenzoic acid in the mixed particles during dehydration. (4) A humic acid component shows no significant effect on the efflorescence of AS in mixed aerosol particles. In addition, relatively good measurement-model agreement in the case of the AIOMFAC and E-AIM models is mainly due to composition-dependent consideration of crystallization of AS in the model prediction. The use of the ZSR relation leads to good agreement with measured diameter growth factors of aerosol particles containing humic acid and ammonium sulfate. A similarity of the hygroscopicity parameter ĸ for organic surrogate compounds mixed with ammonium sulfate for different mass fractions during the different seasonal periods in the Amazon is observed. The RH-dependent hygroscopicity parameter ĸ measured at sub-saturated is consistent with kappa values for observations in the central Amazon Basin at the same environment, which suggests the similar O : C ratios and ammonium sulfate mass fraction in the laboratory and field observation conditions.

Organic compounds present at/near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH radical initiated oxidation of aqueous methylsuccinic acid (C5H8O4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modelling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5) hydroxyl functionalization product (C5H8O5) and a C4 fragmentation product (C4H6O3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH-abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high oxidation stages.