Phase Transitions in Organic and Organic/Inorganic Aerosol Particles.

The phase state of aerosol particles can impact numerous atmospheric processes, including new particle growth, heterogeneous chemistry, cloud condensation nucleus formation, and ice nucleation. In this article, the phase transitions of inorganic, organic, and organic/inorganic aerosol particles are discussed, with particular focus on liquid-liquid phase separation (LLPS). The physical chemistry that determines whether LLPS occurs, at what relative humidity it occurs, and the resultant particle morphology is explained using both theoretical and experimental methods. The known impacts of LLPS on aerosol processes in the atmosphere are discussed. Finally, potential evidence for LLPS from field and chamber studies is presented. By understanding the physical chemistry of the phase transitions of aerosol particles, we will acquire a better understanding of aerosol processes, which in turn impact human health and climate.

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.

Liquid-Liquid Phase Separation Can Drive Aerosol Droplet Growth in Supersaturated Regimes.

It is well known that atmospheric aerosol size and composition impact air quality, climate, and health. The aerosol composition is typically a mixture and consists of a wide range of organic and inorganic particles that interact with each other. Furthermore, water vapor is ubiquitous in the atmosphere, in indoor air, and within the human body's respiratory system, and the presence of water can alter the aerosol morphology and propensity to form droplets. Specifically, aerosol mixtures can undergo liquid-liquid phase separation (LLPS) in the presence of water vapor. However, the experimental conditions for which LLPS impacts water uptake and the subsequent prediction of aerosol mixtures are poorly understood. To improve our understanding of aerosol mixtures and droplets, this study explores two ternary systems that undergo LLPS, namely, the 2MGA system (sucrose + ammonium sulfate + 2-methylglutaric acid) and the PEG1000 system (sucrose + ammonium sulfate + polyethylene glycol 1000). In this study, the ratio of species and the O:C ratios are systematically changed, and the hygroscopic properties of the resultant aerosol were investigated. Here, we show that the droplet activation above 100% RH of the 2MGA system was influenced by LLPS, while the droplet activation of the PEG1000 system was observed to be linearly additive regardless of chemical composition, O:C ratio, and LLPS. A theoretical model that accounts for LLPS with O:C ratios was developed and predicts the water uptake of internally mixed systems of different compositions and phase states. Hence, this study provides a computationally efficient algorithm to account for the LLPS and solubility parameterized by the O:C ratio for droplet activation at supersaturated relative humidity conditions and may thus be extended to mixed inorganic-organic aerosol populations with unspeciated organic composition found in the ambient environment.

Heterogeneous Ice Nucleation in Model Crystalline Porous Organic Polymers: Influence of Pore Size on Immersion Freezing.

Heterogeneous ice nucleation activity is affected by aerosol particle composition, crystallinity, pore size, and surface area. However, these surface properties are not well understood, regarding how they act to promote ice nucleation and growth to form ice clouds. Therefore, synthesized materials for which surface properties can be tuned were examined in immersion freezing mode in this study. To establish the relationship between particle surface properties and efficiency of ice nucleation, materials, here, covalent organic frameworks (COFs), with different pore diameters and degrees of crystallinity (ordering), were characterized. Results showed that out of all the highly crystalline COFs, the sample with a pore diameter between 2 and 3 nm exhibited the most efficient ice nucleation activity. We posit that the highly crystalline structures with ordered pores have an optimal pore diameter where the ice nucleation activity is maximized and that the not highly crystalline structures with nonordered pores have more sites for ice nucleation. The results were compared and discussed in the context of other synthesized porous particle systems. Such studies give insight into how material features impact ice nucleation activity.

Significance of the surface silica/alumina ratio and surface termination on the immersion freezing of ZSM-5 zeolites.

Heterogeneous ice nucleation in the atmosphere impacts climate, but the magnitude of the effect of ice clouds on radiative forcing is uncertain. Surfaces that promote ice nucleation are varied. Because O, Si, and Al are the most abundant elements in the Earth's crust, understanding how the Si : Al ratio impacts the ice nucleation activity of aluminosilicates through exploration of synthetic ZSM-5 samples provides a good model system. This paper investigates the immersion freezing of ZSM-5 samples with varying Si : Al ratios. Ice nucleation temperature increases with increasing surface Al content. Additionally, when ammonium, a common cation in aerosol particles, is adsorbed to the zeolite surface, initial freezing temperatures are reduced by up to 6 °C in comparison to proton-terminated zeolite surfaces. This large decrease in ice nucleation activity in the presence of ammonium suggests that the cation can interact with the surface to block or modify active sites. Our results on synthetic samples in which the surface composition is tunable gives insight into the role of surfaces in heterogeneous ice nucleation processes in the atmosphere. We emphasize the importance of examining surface chemical heterogeneities in ice nucleating particles that could result from a variety of aging pathways for a deeper understanding of the freezing mechanism.

Silica as a Model Ice-Nucleating Particle to Study the Effects of Crystallinity, Porosity, and Low-Density Surface Functional Groups on Immersion Freezing.

Aerosol particles can facilitate heterogeneous ice formation in the troposphere and stratosphere by acting as ice-nucleating particles, modulating cloud formation/dissipation, precipitation, and their microphysical properties. Heterogeneous ice nucleation is driven by ice embryo formation on the particle surface, which can be influenced by features of the surface such as crystallinity, surface structure, lattice structure, defects, and functional groups. To characterize the effect of crystallinity, pores, and surface functional groups toward ice nucleation, samples of comparable silica systems, specifically, quartz, ordered and nonordered porous amorphous silica samples with a range of pore sizes (2-11 nm), and nonporous functionalized silica spheres, were used as models for mineral dust aerosol particles. The ice nucleation activity of these samples was investigated by using an immersion freezing chamber. The results suggest that crystallinity has a larger effect than porosity on ice nucleation activity, as all of the porous silica samples investigated had lower onset freezing temperatures and lower ice nucleation activities than quartz. Our findings also suggest that pores alone are not sufficient to serve as effective active sites and need some additional chemical or physical property, like crystallinity, to nucleate ice in immersion mode freezing. The addition of a low density of organic functional groups to nonporous samples showed little enhancement compared to the inherent nucleation activity of silica with native surface hydroxyl groups. The density of functional groups investigated in this work suggests that a different arrangement of surface groups may be needed for enhanced immersion mode ice nucleation activity. In summary, crystallinity dictates the ice nucleation activity of silica samples rather than porosity or low-density surface functional groups. This work has broader implications regarding the climate impacts resulting from ice cloud formation.

Direct measurement of the pH of aerosol particles using carbon quantum dots.

The pH of aerosol particles remains challenging to measure because of their small size, complex composition, and high acidity. Acidity in aqueous aerosol particles, which are found abundantly in the atmosphere, impacts many chemical processes from reaction rates to cloud formation. Only one technique - pH paper - currently exists for directly determining the pH of aerosol particles, and this is restricted to measuring average acidity for entire particle populations. Other methods for evaluating aerosol pH include filter samples, particle-into-liquid sampling, Raman spectroscopy, organic dyes, and thermodynamic models, but these either operate in a higher pH range or are unable to assess certain chemical species or complexity. Here, we present a new method for determining acidity of individual particles and particle phases using carbon quantum dots as a novel in situ fluorophore. Carbon quantum dots are easily synthesized, shelf stable, and sensitive to pH in the highly acidic regime from pH 0 to pH 3 relevant to ambient aerosol particles. To establish the method, a calibration curve was formed from the ratiometric fluorescence intensity of aerosolized standard solutions with a correlation coefficient (R2) of 0.99. Additionally, the pH of aerosol particles containing a complex organic mixture (COM) representative of environmental aerosols was also determined, proving the efficacy of using carbon quantum dots as pH-sensitive fluorophores for complex systems. The ability to directly measure aerosol particle and phase acidity in the correct pH range can help parametrize atmospheric models and improve projections for other aerosol properties and their influence on health and climate.

Efficacy of oil and gas produced water as a dust suppressant.

The effectiveness of oil and gas produced water (OGPW) applied to unpaved roads to reduce particulate matter (PM10) generation has not been well-characterized. Here we quantify the efficacy of OGPW compared to commercial and alternative byproducts as dust suppressants applied to unpaved roads and estimate efficacy of a dust suppressant extrapolated from both lab experiments and published data for OGPW across U.S. states. Both treated and untreated OGPW, simulated brines, and commercial dust suppressants were characterized by major and trace element composition and then applied to road aggregate in the laboratory. PM10 generation after treatment was quantified, both before and after simulated rain events to assess the need for multiple applications. We found the dust suppression efficacy of all OGPW to be less than commercial products and alternative byproducts such as waste soybean oil. In addition, OGPW lost efficacy following simulated rain events, which would require repeated applications of OGPW to maintain dust suppression. The dust suppression efficacy of OGPW can be estimated based on two chemical measurements, the sodium absorption ratio (SAR) and the total dissolved solids (TDS). OGPW with the lowest SAR and highest TDS performed best as dust suppressants while high SAR and lower TDS led to greater dust generation.

Use of Transmission Electron Microscopy for Analysis of Aerosol Particles and Strategies for Imaging Fragile Particles.

For over 25 years, transmission electron microscopy (TEM) has provided a method for the study of aerosol particles with sizes from below the optical diffraction limit to several microns, resolving the particles as well as smaller features. The wide use of this technique to study aerosol particles has contributed important insights about environmental aerosol particle samples and model atmospheric systems. TEM produces an image that is a 2D projection of aerosol particles that have been impacted onto grids and, through associated techniques and spectroscopies, can contribute additional information such as the determination of elemental composition, crystal structure, and 3D particle structures. Soot, mineral dust, and organic/inorganic particles have all been analyzed using TEM and spectroscopic techniques. TEM, however, has limitations that are important to understand when interpreting data including the ability of the electron beam to damage and thereby change the structure and shape of particles, especially in the case of particles composed of organic compounds and salts. In this paper, we concentrate on the breadth of studies that have used TEM as the primary analysis technique. Another focus is on common issues with TEM and cryogenic-TEM. Insights for new users on best practices for fragile particles, that is, particles that are easily susceptible to damage from the electron beam, with this technique are discussed. Tips for readers on interpreting and evaluating the quality and accuracy of TEM data in the literature are also provided and explained.

Ultrafine Particles Emitted through Routine Operation of a Hairdryer.

Particulate matter is a large concern for human health. Fine and ultrafine particulate matter has been shown to negatively impact human health; for example, it causes cardiopulmonary diseases. Current regulation targets the size of the particles, but composition also impacts toxicity. Indoor sources of air pollution pose unique challenges for human health due to the potential for human exposure to high concentrations in confined spaces. In this work, six hairdryers were each operated within a plexiglass chamber, and their emissions were analyzed with transmission electron microscopy and energy-dispersive spectroscopy. All hairdryers were found to emit ultrafine iron, carbon, and copper. In addition, emissions from two hairdryers primarily contained silver nanoparticles in the ultrafine range (<100 nm). The ultrafine particle emission rates for the hairdryers that did not contain silver were measured and found to be lower than ultrafine particle emissions by gas stoves and electric burners. Based on their size, these particles can either remain in the lung or enter the bloodstream after inhalation and potentially cause long-term health effects.

Dynamics of Liquid-Liquid Phase Separation in Submicrometer Aerosol.

Nanoscale materials, when compared to their bulk components, possess unique properties. In particular, shifts in phase transitions can occur for submicrometer particles. For instance, small particles do not undergo the process of liquid-liquid phase separation (LLPS). LLPS has applications in emulsions such as Janus particles, controllable morphology to create drug-rich phases during drug delivery, and is often observed in atmospheric aqueous aerosol particles. In atmospheric particles, LLPS is tracked as a function of particle water activity, which is equivalent to the relative humidity (RH) at equilibrium. We probed three organic/inorganic aerosol systems in the range of RH over which phase separation occurs (SRH). Our findings indicate that SRH for submicrometer aerosol particles is lower than for micrometer-sized droplets. These findings show that it may be necessary to update the representation of phase transitions in aerosol particles in climate models. The vast majority of organic/inorganic aerosol particles have submicrometer diameters, and a decrease in SRH for submicrometer particles indicates that the current estimation of phase-separated aerosols may be overestimated. Furthermore, understanding the properties of LLPS at the nanoscale can provide key parameters to describe these systems and may lead to better control of phase separation in submicrometer particles.

Ice nucleation activity of iron oxides via immersion freezing and an examination of the high ice nucleation activity of FeO.

Heterogeneous ice nucleation is a common process in the atmosphere, but relatively little is known about the role of different surface characteristics on the promotion of ice nucleation. We have used a series of iron oxides as a model system to study the role of lattice mismatch and defects induced by milling on ice nucleation activity. The iron oxides include wüstite (FeO), hematite (Fe2O3), magnetite (Fe3O4), and goethite (FeOOH). The iron oxides were characterized by X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) surface area measurements. The immersion freezing experiments were performed using an environmental chamber. Wüstite (FeO) had the highest ice nucleation activity, which we attribute to its low lattice mismatch with hexagonal ice and the exposure of Fe-OH after milling. A comparison study of MnO and wüstite (FeO) with milled and sieved samples for each suggests that physical defects alone result in only a slight increase in ice nucleation activity. Despite differences in the molecular formula and surface groups, hematite (Fe2O3), magnetite (Fe3O4), and goethite (FeOOH) had similar ice nucleation activities, which may be attributed to their high lattice mismatch to hexagonal ice. This study provides further insight into the characteristics of a good heterogeneous ice nucleus and, more generally, helps to elucidate the interactions between aerosol particles and ice particles in clouds.

Inhibition of Phase Separation in Aerosolized Water-Soluble Polymer-Polymer Nanoparticles at Small Sizes and the Effects of Molecular Weight.

The effects of confinement on the phase separation behavior of polymer-polymer mixtures have been frequently studied in morphologies such as thin films and rods, but little research exists with respect to the nanoscale droplet size regime. This paper addresses the phase separation of water-soluble polymers in submicron aerosol droplets. Atomized aerosol particles were prepared from aqueous solutions and dried using diffusion dryers. For poly(ethylene) glycol/dextran and poly(vinyl alcohol)/poly(4-styrene sulfonic acid) systems, small particles remain homogeneous, while larger particles undergo phase separation within a single particle. As the molecular weight of the polymers increases while a constant ratio between monomers of polymers A and B is maintained, phase separation occurs in smaller diameter particles. These trends are modeled using a combination of equations describing the nucleation of a new phase and the Flory-Huggins theory and provide qualitative agreement. These results provide insight into the phase separation of aqueous nanoscale polymer-polymer systems. Potential exists to make new polymer materials with unique properties due to the mixing of polymer combinations that normally undergo phase separation.

Liquid-Liquid Phase Separation in Supermicrometer and Submicrometer Aerosol Particles.

ConspectusThe interactions of aerosol particles with light and clouds are among the most uncertain aspects of anthropogenic climate forcings. The effects of aerosol particles on climate depend on their optical properties, heterogeneous chemistry, water uptake behavior, and ice nucleation activity. These properties in turn depend on aerosol physics and chemistry including composition, size, shape, internal structure (morphology), and phase state. The greatest numbers of particles are found at small, submicrometer sizes, and the properties of aerosol particles can differ on the nanoscale compared with measurements of bulk materials. As a result, our focus has been on characterizing the phase transitions of aerosol particles in both supermicrometer and submicrometer particles. The phase transition of particular interest for us has been liquid-liquid phase separation (LLPS), which occurs when components of a solution phase separate due to a difference in solubilities. For example, organic compounds can have limited solubility in salt solutions especially as the water content decreases, increasing the concentration of the salt solution, and causing phase separation between organic-rich and inorganic-rich phases. To characterize the systems of interest, we primarily use optical microscopy for supermicrometer particles and cryogenic-transmission microscopy for submicrometer particles.This Account details our main results to date for the phase transitions of supermicrometer particles and the morphology of submicrometer aerosol. We have found that the relative humidity (RH) at which LLPS occurs (separation RH; SRH) is highly sensitive to the composition of the particles. For supermicrometer particles, SRH decreases as the pH is lowered to atmospherically relevant values. SRH also decreases when non-phase-separating organic compounds are added to the particles. For submicrometer particles, a size dependence of morphology is observed in systems that undergo LLPS in supermicrometer particles. In the limit of slow drying rates, particles <30 nm are homogeneous and larger particles are phase-separated. This size dependence of aerosol morphology arises because small particles cannot overcome the activation barrier needed to form a new phase when phase separation occurs by a nucleation and growth mechanism. The inhibition of LLPS in small particles is observed for mixtures of ammonium sulfate with single organic compounds as well as complex organics like α-pinene secondary organic matter. The morphology of particles affects activation diameters for the formation of cloud condensation nuclei. These results more generally have implications for aerosol properties that affect the climate system. In addition, LLPS is also widely studied in materials and biological chemistry, and our results could potentially translate to implications for these fields.

Flash Freeze Flow Tube to Vitrify Aerosol Particles at Fixed Relative Humidity Values.

Development of methods to measure the phase transitions and physical properties of submicron atmospheric aerosol particles is needed to better model these systems. In this paper, we present a method to flash freeze submicron particles to measure phase transitions as a function of relative humidity (RH). Particles are equilibrated at a fixed RH, vitrified in a temperature-controlled flow tube, and imaged with cryogenic transmission electron microscopy (cryo-TEM). We demonstrate the use of the technique for measuring the efflorescence relative humidity (ERH) of potassium sulfate and potassium chloride aerosol as well as the separation RH (SRH) for a multicomponent organic/inorganic system that undergoes liquid-liquid phase separation (LLPS). The location of phase transitions can shift between the micrometer and nanometer size regimes, and particles in a given population may have a range of RH over which a phase transition occurs. This technique addresses these requirements by allowing for characterization of the phase transitions for individual particles in a population on the submicron scale.

Size-Dependent Liquid-Liquid Phase Separation in Atmospherically Relevant Complex Systems.

Physical properties of aerosol particles, such as liquid-liquid phase separation (LLPS), have the potential to impact the climate system. Model systems have been shown to have size-dependent LLPS in the submicron regime; however, these systems are an extreme simplification of ambient aerosol, which can include myriad organic compounds. We expand the studies of LLPS in particles consisting of ammonium sulfate and more complex organic mixtures from multiple organic compounds to α-pinene secondary organic matter (SOM). All systems display a size-dependent morphology, with small particles remaining homogeneous while large particles phase-separate. Surprisingly, three-phase particles were also observed in some of the systems in addition to a new phase state that we have termed channel morphology, which can arise upon efflorescence. The existence of size-dependent LLPS in complex organic mixtures and SOM provides evidence that this is a relevant phenomenon for ambient aerosol and should be considered when modeling atmospheric aerosol.

The Effect of Crystallinity and Crystal Structure on the Immersion Freezing of Alumina.

Determining the factors that constitute an efficient ice nucleus is an ongoing area of research in the atmospheric community. In particular, surface characteristics such as functional groups and surface defects impact the ice nucleation efficiency. Crystal structure has been proposed to be a possible factor that can dictate ice nucleation activity through the templating of water molecules on the surface of the aerosol particle. If the crystal structure of the surface matches that of the crystal structure of ice, it has been shown to increase ice nucleation activity. In this study, alumina was chosen as a model system because crystal structure and crystallinity can be tuned, and the effect on immersion freezing was explored. The nine alumina samples include polymorphs of AlOOH, Al(OH)3, and Al2O3, which have a range of crystal structures and crystallinities. The samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and Brunauer-Emmett-Teller (BET) analysis. From the immersion freezing experiments, corundum [α-Al2O3] was shown to have the highest ice nucleation activity likely because of its high lattice match and high degree of crystallinity. Crystal structure alone did not show a strong correlation with ice nucleation activity, but a combination of a hexagonal crystal structure and a highly crystalline surface was seen to nucleate ice at warmer temperatures than the other alumina samples. This study provides experimental results in the study of ice nucleation of a range of alumina samples, which have possible implications for alumina-based mineral dust particles. Our findings suggest that crystallinity and crystal structure are important to consider when evaluating the ice nucleation efficiency of aerosol particles in laboratory and modeling studies.

Role of pH in Aerosol Processes and Measurement Challenges.

pH is one of the most basic chemical properties of aqueous solution, but its measurement in nanoscale aerosol particles presents many challenges. The pH of aerosol particles is of growing interest in the atmospheric chemistry community because of its demonstrated effects on heterogeneous chemistry and human health, as well as potential effects on climate. The authors have shown that phase transitions of aerosol particles are sensitive to pH, focusing on systems that undergo liquid-liquid phase separation. Currently, aerosol pH is calculated indirectly from knowledge of species present in the gas and aerosol phases through the use of thermodynamic models. From these models, ambient aerosol is expected to be highly acidic (pH ∼ 0-3). Direct measurements have focused on model systems due to the difficulty of this measurement. This area is one in which physical chemists should be encouraged to contribute because of the potential consequences for aerosol processes in the environment.

Acidic processing of fly ash: chemical characterization, morphology, and immersion freezing.

Fly ash can undergo aging in the atmosphere through interactions with sulfuric acid and water. These reactions could result in chemical and physical changes that could affect the cloud condensation or ice nucleation activity of fly ash particles. To explore this process, different water and acid treated fly ash types were characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), electron dispersive spectroscopy (EDS), selected area diffraction (SAED), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). Then, their immersion freezing activity was assessed. With water and acid treatment, a wide variety of metals were leached, depending on the starting composition of the fly ash. Acid treatment resulted in the formation of gypsum, Ca(SO4)·2H2O, for fly ash containing Ca as well as morphological changes. The immersion freezing activity was also assessed for each fly ash system to compare the effects of water and acid processing. Our results support the assertion that fly ash can serve as a cloud condensation or ice nucleus to affect climate.

Effects of High Acidity on Phase Transitions of an Organic Aerosol.

Aerosol particle morphology influences the effect of particles on climate. Recent studies have documented the high acidity found in many ambient aerosol particles. The effect of this acidity on the phase transitions of mixed organic/inorganic aerosol particles has not been addressed. To investigate this effect, six organic compounds and ammonium sulfate were investigated individually with varying amounts of sulfuric acid to determine the role of low pH in the separation, efflorescence, and deliquescence transitions. All phase transitions were affected by the addition of sulfuric acid. This effect was attributed primarily to the change in the identity of the inorganic component as the ammonium/sulfate ratio (ASR) was changed from 2 to 1.5 to 1. The separation relative humidity (SRH) decreased with increasing amounts of sulfuric acid for each system studied, with the largest effect seen in compounds that have a lower SRH when mixed with ammonium sulfate. Control studies without an inorganic salt revealed that for some systems, phase separation occurs for mixtures of sulfuric acid and an organic acid. Overall, it was found that for aerosol particles at low pH (≤0.35) composed of organic acids and inorganic salts, phase separation can be impeded in some cases.