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.

Chemically Resolved Evaporation Dynamics of Dicarboxylic Acid Mixtures in Solid Particles.

The evaporation rate and corresponding vapor pressure of dicarboxylic acids have been the subject of numerous scientific studies over the years, with reported values spanning several orders of magnitude. Recent work has identified the importance of considering the phase state of the material during evaporation, likely accounting for some of the variability in measured vapor pressures. In the homologous series of dicarboxylic acids, the phase state under dry conditions may be crystalline or amorphous, with particles of odd-carbon-numbered acids exhibiting tendencies to remain amorphous and spherical. Although measurements of vapor pressures for pure components make up most of the available literature data, for many applications, these compounds are not present in isolation. Additionally, many systems containing a semi-volatile material exist in a solid state, especially under dry and low relative humidity conditions. In this work, we explore the evaporation of compounds present in mixed solid-state particles. Specifically, we use single particle levitation coupled with mass spectrometry to measure the evolving composition of solid particles containing mixtures of glutaric acid and succinic acid, glutaric acid and adipic acid, and malonic acid and succinic acid. Under dry conditions, these systems exhibit non-spherical geometries consistent with crystallization of one or both components into an organic crystal. Our measurements allow the evaporation of each component in the mixture to be characterized independently and effective vapor pressures of the pure components to be inferred. The resulting vapor pressures are compared against pure component vapor pressures. We demonstrate that these mixtures exhibit thermodynamic ideality but can be influenced by limited diffusion in the solid phase. These are the first results in the literature that explore the thermodynamic and kinetic factors that control the evaporative evolution of mixed solid-state particles.

Phase State and Relative Humidity Regulate the Heterogeneous Oxidation Kinetics and Pathways of Organic-Inorganic Mixed Aerosols.

Inorganic species always coexist with organic materials in atmospheric particles and may influence the heterogeneous oxidation of organic aerosols. However, very limited studies have explored the role of the inorganics in the chemical evolution of organic species in mixed aerosols. This study examines the heterogeneous oxidation of glutaric acid-ammonium sulfate and 1,2,6-hexanetriol-ammonium sulfate aerosols by hydroxyl radicals (OH) under varied organic mass fractions (forg) and relative humidity in a flow tube reactor. Coupling the oxidation kinetics and product measurements with kinetic model simulations, we found that under both low relative humidity (RH, 30-35%) and high RH conditions (85%), the decreased forg from 0.7 to 0.2 accelerates the oxidation of the organic materials by a factor of up to 11. We suggest that the faster oxidation kinetics under low-RH conditions is due to full or partial phase separation, with the organics greatly enriched at the particle outer region, while enhanced "salting-out" of the organics and OH adsorption caused by higher inorganics could explain the observations under high-RH conditions. Analysis of the oxidation products reveals that the dilution of organics by the inorganic salts and corresponding water uptake under high-RH conditions will favor alkoxy radical fragmentation by a factor of 3-4 and inhibit its secondary chain propagation chemistry. Our results suggest that atmospheric organic aerosol oxidation lifetime and composition are strongly impacted by the coexistent inorganic salts.

Connecting the Phase State and Volatility of Dicarboxylic Acids at Elevated Temperatures.

The partitioning of semivolatile organic molecules between condensed phases and the vapor phase has broad application across a range of scientific disciplines, with significant impacts in atmospheric chemistry for regulating the evolving composition of aerosol particles. Vapor partitioning depends on the molecular interactions and phase state of the condensed material and shows a well-established dependence on temperature. The phase state of solid organic material is not always well-defined, and many examples can be found for the formation of amorphous subcooled liquid states rather than crystalline solids. This can lead to significant changes to vapor equilibrium processes by modifying the thermodynamics and kinetics of evaporation. Here, we explore the influence of phase state on the evaporation dynamics of a series of straight-chain dicarboxylic acids across a range of above-ambient temperatures. These molecules show an odd/even alteration in some of their properties based on the number of carbon atoms that may be connected to their phase state under dry conditions. Using a newly developed linear-quadrupole electrodynamic balance, we levitate single particles containing the sample and expose them to dry conditions across a range of temperatures (ambient to ∼350 K). Using the rate of evaporation measured from the change in the size or relative mass, we derive the vapor pressure and enthalpy of vaporization. Light scattering data allows for unambiguous identification of the phase of the particles (crystal vs amorphous) allowing the vapor equilibrium properties to be attributed to a particular state. This work highlights a new experimental method for characterizing vapor pressures of low volatility substances and extends the temperature range of available data for the vapor pressure of terminal dicarboxylic acids. These measurements show that crystalline and subcooled liquid states persist at elevated temperatures and provide a direct comparison between subcooled and crystal phases under the same experimental conditions.

Hygroscopic Growth, Phase Morphology, and Optical Properties of Model Aqueous Brown Carbon Aerosol.

Brown carbon aerosol in the atmosphere contain light-absorbing chromophores that influence the optical scattering properties of the particles. These chromophores may be hydrophobic, such as PAHs, or water soluble, such as nitroaromatics, imidazoles, and other conjugated oxygen-rich molecules. Water-soluble chromophores are expected to exist in aqueous solution in the presence of sufficient water and will exhibit physical properties (e.g., size, refractive index, and phase morphology) that depend on the environmental relative humidity (RH). In this work, we characterize the RH-dependent properties of 4-nitrocatechol (4-NC) and its mixtures with ammonium sulfate, utilizing a single-particle levitation platform coupled with Mie resonance spectroscopy to probe the size, real part of the complex refractive index (RI), and phase morphology of individual micron-sized particles. We measure the hygroscopic growth properties of pure 4-NC and apply mixing rules to characterize the growth of mixtures with ammonium sulfate. We report the RI at 589 nm for these samples as a function of RH and explore the wavelength dependence of the RI at non-absorbing wavelengths. The real part of the RI at 589 nm was found to vary in the range 1.54-1.59 for pure 4-NC from 92.5 to 75% RH, with an estimated pure component RI of 1.70. The real part of the RI was also measured for mixtures of AS and 4-NC and ranged from 1.39 to 1.51 depending on the component ratio and RH. We went on to characterize phase transitions in mixed particles, identifying the onset RH of liquid-liquid phase separation (LLPS) and efflorescence transitions. Mixtures showed LLPS in the range of 85-76% RH depending on the molar ratio, while efflorescence typically fell between 22 and 42% RH. Finally, we characterized the imaginary part of the complex RI using an effective oscillator model to capture the wavelength-dependent absorption properties of the system.

An Open Port Sampling Interface for the Chemical Characterization of Levitated Microparticles.

Several studies have reported ionization methods to classify the chemical composition of levitated particles held in an electrodynamic balance using mass spectrometry (MS). These methods include electrospray-based paper spray (PS) ionization, plasma discharge ionization, and direct analysis in real-time (DART) ionization, with each showing advantages and disadvantages. Our recent work demonstrated that PS ionization could yield accurate data for the chemical evolution of mixed component particles undergoing evaporation. However, measurements were performed using an internal standard to account for and correct the inherent variability in the PS ionization source. Here, we explore a new electrospray-based method coupled to particle levitation-the Open Port Sampling Interface (OPSI), which provides many advantages over the PS method, with few disadvantages. In this application note we report experiments in which micron-sized particles, containing analytes such as citric acid, maleic acid, and tetraethylene glycol, were levitated and optically probed to determine their size and mass. Subsequent transfer of individual levitated particles into the OPSI allowed for the ionization and mass spectrometry analysis of these particles. We discuss the stability and reproducibility of MS measurements, demonstrate effective quantitation in both positive and negative mode, and determine the sensitivity of the OPSI to a range of analyte mass present in levitated particles. Importantly, we show stability of the OPSI over >6 h without the need for normalizing signal variations with an internal standard in the sample, demonstrating robust application of the OPSI to measurements over extended periods of time.

Evidence for a semisolid phase state of aerosols and droplets relevant to the airborne and surface survival of pathogens.

The phase state of respiratory aerosols and droplets has been linked to the humidity-dependent survival of pathogens such as SARS-CoV-2. To inform strategies to mitigate the spread of infectious disease, it is thus necessary to understand the humidity-dependent phase changes associated with the particles in which pathogens are suspended. Here, we study phase changes of levitated aerosols and droplets composed of model respiratory compounds (salt and protein) and growth media (organic-inorganic mixtures commonly used in studies of pathogen survival) with decreasing relative humidity (RH). Efflorescence was suppressed in many particle compositions and thus unlikely to fully account for the humidity-dependent survival of viruses. Rather, we identify organic-based, semisolid phase states that form under equilibrium conditions at intermediate RH (45 to 80%). A higher-protein content causes particles to exist in a semisolid state under a wider range of RH conditions. Diffusion and, thus, disinfection kinetics are expected to be inhibited in these semisolid states. These observations suggest that organic-based, semisolid states are an important consideration to account for the recovery of virus viability at low RH observed in previous studies. We propose a mechanism in which the semisolid phase shields pathogens from inactivation by hindering the diffusion of solutes. This suggests that the exogenous lifetime of pathogens will depend, in part, on the organic composition of the carrier respiratory particle and thus its origin in the respiratory tract. Furthermore, this work highlights the importance of accounting for spatial heterogeneities and time-dependent changes in the properties of aerosols and droplets undergoing evaporation in studies of pathogen viability.

Measuring the Chemical Evolution of Levitated Particles: A Study on the Evaporation of Multicomponent Organic Aerosol.

Single-particle levitation methods provide an effective platform for probing the physical properties of atmospheric aerosol via micrometer-sized particles. Until recently, chemical composition measurements on levitated particles were limited to spectroscopy, yielding only basic chemical information. Here, we describe, benchmark, and discuss the applications of an approach for probing the physical properties and chemical composition of single levitated particles using high-resolution mass spectrometry (MS). Using a linear quadrupole electrodynamic balance (LQ-EDB) coupled to paper spray mass spectrometry, we report accurate measurements of the evolving size within 5 nm (using broadband light scattering) and relative composition (using MS) of evaporating multicomponent levitated particles in real time. Measurements of the evaporation dynamics of semivolatile organic particles containing a range of n-ethylene glycols (n = 3, 4, and 6) in various binary and ternary mixtures were made under dry conditions and compared with predictions from a gas-phase diffusion evaporation model. Under assumptions of ideal mixing, excellent agreement for both size and composition evolution between measurements and models were obtained for these mixtures. At increased relative humidity, the presence of water in particles causes the assumption of ideality to break down, and the evaporative mass flux becomes a function of the mole fraction and activity coefficient. Through compositionally resolved evaporation measurements and thermodynamic models, we characterize the activity of organic components in multicomponent particles. Our results demonstrate that the LQ-EDB-MS platform can identify time-dependent size and compositional changes with high precision and reproducibility, yielding an effective methodology for future studies on chemical aging and gas-particle partitioning in suspended particles.

Hygroscopic growth of simulated lung fluid aerosol particles under ambient environmental conditions.

The hygroscopicity of respiratory aerosol determines their particle size distribution and regulates solute concentrations to which entrained microorganisms are exposed. Here, we report the hygroscopicity of simulated lung fluid (SLF) particles. While the response of aqueous particles follow simple mixing rules based on composition, we observe phase hysteresis with increasing and decreasing relative humidity (RH) and clear uptake of water prior to deliquescence. These results indicate that RH history may control the state of respiratory aerosol in the environment and influence the viability of microorganisms.

Ion-molecule interactions enable unexpected phase transitions in organic-inorganic aerosol.

Atmospheric aerosol particles are commonly complex, aqueous organic-inorganic mixtures, and accurately predicting the properties of these particles is essential for air quality and climate projections. The prevailing assumption is that aqueous organic-inorganic aerosols exist predominately with liquid properties and that the hygroscopic inorganic fraction lowers aerosol viscosity relative to the organic fraction alone. Here, in contrast to those assumptions, we demonstrate that increasing inorganic fraction can increase aerosol viscosity (relative to predictions) and enable a humidity-dependent gel phase transition through cooperative ion-molecule interactions that give rise to long-range networks of atmospherically relevant low-mass oxygenated organic molecules (180 to 310 Da) and divalent inorganic ions. This supramolecular, ion-molecule effect can drastically influence the phase and physical properties of organic-inorganic aerosol and suggests that aerosol may be (semi)solid under more conditions than currently predicted. These observations, thus, have implications for air quality and climate that are not fully represented in atmospheric models.

Paper spray mass spectrometry for the analysis of picoliter droplets.

Recent experimental efforts have shown that single particle levitation methods may be effectively coupled with mass spectrometry (MS) using paper spray (PS) ionization for compositional analysis of picoliter droplets. In this work, we characterize the response of PS-MS to analytes delivered in the form of picoliter droplets and explore its potential for identification and quantification of these samples. Using a microdroplet dispenser to generate droplets, we demonstrate sensitivity to a range of oxygenated organic molecules typical of compounds found in atmospheric secondary organic aerosol. We assess experimental factors that influence the reproducibility and sensitivity of the method and explore the linearity of the system response to increasing analyte mass in droplets containing single or multicomponent analytes. We show that the ratio of analyte signal from multicomponent samples may be used to characterize the relative composition of the system. These measurements demonstrate that the droplet PS-MS method is an effective tool for qualitative and quantitative analysis of single picoliter droplets containing picogram levels of analyte. The potential applications of this technique for characterizing the composition of levitated particles will be discussed.

Simultaneous Retrieval of the Size and Refractive Index of Suspended Droplets in a Linear Quadrupole Electrodynamic Balance.

Single-particle trapping is an effective strategy to explore the physical and optical properties of aerosol with high precision. Laser-based methods are commonly used to probe the size, optical properties, and composition of nonlight-absorbing droplets in optical and electrodynamic traps. However, these methods cannot be applied to droplets containing photoactive chromophores, and thus, single-particle methods have been restricted to only a subset of atmospherically relevant particle compositions. In this work, we explore the application of a broadband light scattering approach, Mie resonance spectroscopy, to simultaneously probe the size and the refractive index (RI) of droplets in a linear quadrupole electrodynamic balance. We examine the evaporation of poly(ethylene glycol)s and compare the calculated vapor pressures with literature values to benchmark the size accuracy without prior constraint on the RI. We then explore the hygroscopic growth and deliquescence of sodium chloride droplets, measuring RI at the deliquescence relative humidity and demonstrating agreement to literature values. These data allow the wavelength dependence of the RI of aqueous NaCl to be determined using a first-order Cauchy equation, and we effectively reproduce literature data from multiple techniques. We finally discuss measurements from a light-absorbing aqueous droplet containing humic acid and interpret the spectra via the imaginary component of the RI. The approach described here allows the radius of nonabsorbing droplets to be determined within 0.1%, the refractive index within 0.2%, and the first-order term in the Cauchy dispersion equation within ∼5%.

Exploring Chemistry in Microcompartments Using Guided Droplet Collisions in a Branched Quadrupole Trap Coupled to a Single Droplet, Paper Spray Mass Spectrometer.

Recent studies suggest that reactions in aqueous microcompartments can occur at significantly different rates than those in the bulk. Most studies have used electrospray to generate a polydisperse source of highly charged microdroplets, leading to multiple confounding factors potentially influencing reaction rates (e.g., evaporation, charge, and size). Thus, the underlying mechanism for the observed enhancement remains unclear. We present a new type of electrodynamic balance-the branched quadrupole trap (BQT)-which can be used to study reactions in microdroplets in a controlled environment. The BQT allows for condensed phase chemical reactions to be initiated by colliding droplets with different reactants and levitating the merged droplet indefinitely. The performance of the BQT is characterized in several ways. Sub-millisecond mixing times as fast as ∼400 µs are measured for low velocity (∼0.1 m/s) collisions of droplets with <40 µm diameters. The reaction of o-phthalaldehyde (OPA) with alanine in the presence of dithiolthreitol is measured using both fluorescence spectroscopy and single droplet paper spray mass spectrometry. The bimolecular rate constant for reaction of alanine with OPA is found to be 84 ± 10 and 67 ± 6 M-1 s-1 in a 30 µm radius droplet and bulk solution, respectively, which demonstrates that bimolecular reaction rate coefficients can be quantified using merged microdroplets and that merged droplets can be used to study rate enhancements due to compartmentalization. Products of the reaction of OPA with alanine are detected in single droplets using paper spray mass spectrometry. We demonstrate that single droplets with <100 pg of analyte can easily be studied using single droplet mass spectrometry.

Effects of Relative Humidity and Particle Phase Water on the Heterogeneous OH Oxidation of 2-Methylglutaric Acid Aqueous Droplets.

Organic aerosols can exist as aqueous droplets, with variable water content depending on their composition and environmental conditions (e.g., relative humidity (RH)). Recent laboratory studies have revealed that oxidation kinetics in highly concentrated droplets can be much slower than those in dilute solutions. However, it remains unclear whether aerosol phase water affects the formation of reaction products physically and/or chemically. In this work, we investigate the role of aerosol phase water on the heterogeneous chemistry of aqueous organic droplets consisting of 2-methylglutaric acid (2-MGA), measuring the reaction kinetics and the reaction products upon heterogeneous OH oxidation over a range of RH. An atmospheric pressure soft ionization source (direct analysis in real time, DART) coupled with a high-resolution mass spectrometer is used to obtain real-time molecular information on the reaction products. Aerosol mass spectra show that the same reaction products are formed at all measured RH. At a given reaction extent of the parent 2-MGA, the aerosol composition is independent of RH. These results suggest the aerosol phase water does not alter reaction mechanisms significantly. Kinetic measurements find that the effective OH uptake coefficient, γeff, decreases with decreasing RH below 72%. Isotopic exchange measurements performed using aerosol optical tweezers reveal water diffusion coefficients in the 2-MGA droplets to be 3.0 × 10-13 to 8.0 × 10-13 m2 s-1 over the RH range of 47-58%. These values are comparable to those of other viscous organic aerosols (e.g., citric acid), indicating that 2-MGA droplets are likely to be viscous at low humidity. Smaller γeff at low RH is likely attributed to the slower diffusion of reactants within the droplets. Taken together, the observed relationship between the γeff and RH is likely attributed to changes in aerosol viscosity rather than changes in reaction mechanisms.

The frequency-dependent response of single aerosol particles to vapour phase oscillations and its application in measuring diffusion coefficients.

A new method for measuring diffusion in the condensed phase of single aerosol particles is proposed and demonstrated. The technique is based on the frequency-dependent response of a binary particle to oscillations in the vapour phase of one of its chemical components. We discuss how this physical situation allows for what would typically be a non-linear boundary value problem to be approximately reduced to a linear boundary value problem. For the case of aqueous aerosol particles, we investigate the accuracy of the closed-form analytical solution to this linear problem through a comparison with the numerical solution of the full problem. Then, using experimentally measured whispering gallery modes to track the frequency-dependent response of aqueous particles to relative humidity oscillations, we determine diffusion coefficients as a function of water activity. The measured diffusion coefficients are compared to previously reported values found using the two common experiments: (i) the analysis of the sorption/desorption of water from a particle after a step-wise change to the surrounding relative humidity and (ii) the isotopic exchange of water between a particle and the vapour phase. The technique presented here has two main strengths: first, when compared to the sorption/desorption experiment, it does not require the numerical evaluation of a boundary value problem during the fitting process as a closed-form expression is available. Second, when compared to the isotope exchange experiment, it does not require the use of labeled molecules. Therefore, the frequency-dependent experiment retains the advantages of these two commonly used methods but does not suffer from their drawbacks.

The influence of the surface composition of mixed monolayer films on the evaporation coefficient of water.

We explore the dependence of the evaporation coefficient of water from aqueous droplets on the composition of a surface film, considering in particular the influence of monolayer mixed component films on the evaporative mass flux. Measurements with binary component films formed from long chain alcohols, specifically tridecanol (C13H27OH) and pentadecanol (C15H31OH), and tetradecanol (C14H29OH) and hexadecanol (C16H33OH), show that the evaporation coefficient is dependent on the mole fractions of the two components forming the monolayer film. Immediately at the point of film formation and commensurate reduction in droplet evaporation rate, the evaporation coefficient is equal to a mole fraction weighted average of the evaporation coefficients through the equivalent single component films. As a droplet continues to diminish in surface area with continued loss of water, the more-soluble, shorter alkyl chain component preferentially partitions into the droplet bulk with the evaporation coefficient tending towards that through a single component film formed simply from the less-soluble, longer chain alcohol. We also show that the addition of a long chain alcohol to an aqueous-sucrose droplet can facilitate control over the degree of dehydration achieved during evaporation. After undergoing rapid gas-phase diffusion limited water evaporation, binary aqueous-sucrose droplets show a continued slow evaporative flux that is limited by slow diffusional mass transport within the particle bulk due to the rapidly increasing particle viscosity and strong concentration gradients that are established. The addition of a long chain alcohol to the droplet is shown to slow the initial rate of water loss, leading to a droplet composition that remains more homogeneous for a longer period of time. When the sucrose concentration has achieved a sufficiently high value, and the diffusion constant of water has decreased accordingly so that bulk phase diffusion arrest occurs in the monolayer coated particle, the droplet is found to have lost a greater proportion of its initial water content. A greater degree of slowing in the evaporative flux can be achieved by increasing the chain length of the surface active alcohol, leading to a greater degree of dehydration.

An interfacial mechanism for cloud droplet formation on organic aerosols.

Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depression by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation.

Raman Spectroscopy of Isotopic Water Diffusion in Ultraviscous, Glassy, and Gel States in Aerosol by Use of Optical Tweezers.

The formation of ultraviscous, glassy, and amorphous gel states in aqueous aerosol following the loss of water results in nonequilibrium dynamics due to the extended time scales for diffusive mixing. Existing techniques for measuring water diffusion by isotopic exchange are limited by contact of samples with the substrate, and methods applied to infer diffusion coefficients from mass transport in levitated droplets requires analysis by complex coupled differential equations to derive diffusion coefficients. We present a new technique that combines contactless levitation with aerosol optical tweezers with isotopic exchange (D2O/H2O) to measure the water diffusion coefficient over a broad range (Dw ≈ 10(-12)-10(-17) m(2)·s(-1)) in viscous organic liquids (citric acid, sucrose, and shikimic acid) and inorganic gels (magnesium sulfate, MgSO4). For the organic liquids in binary and ternary mixtures, Dw depends on relative humidity and follows a simple compositional Vignes relationship. In MgSO4 droplets, water diffusivity decreases sharply with water activity and is consistent with predictions from percolation theory. These measurements show that, by combining micrometer-sized particle levitation (a contactless measurement with rapid mixing times) with an established probe of water diffusion, Dw can be simply and directly quantified for amorphous and glassy states that are inaccessible to existing methods.

Dynamics of Particle Size on Inhalation of Environmental Aerosol and Impact on Deposition Fraction.

Inhalation of elevated levels of particulate air pollution has been shown to elicit the onset of adverse health effects in humans, where the magnitude of the response is a product of where in the lung the particulate dose is delivered. At any point in time during inhalation the depositional flux of the aerosol is a function of the radius of the droplet, thus a detailed understanding of the rate and magnitude of the mass flux of water to the droplet during inhalation is crucial. In this study, we assess the impact of aerosol hygroscopicity on deposited dose through the inclusion of a detailed treatment of the mass flux of water to account for the dynamics of particle size in a modified version of the standard International Commission on Radiological Protection (ICRP) whole lung deposition model. The ability to account for the role of the relative humidity (RH) of the aerosol prior to, and during, inhalation on the deposition pattern is explored, and found to have a significant effect on the deposition pattern. The model is verified by comparison to previously published measurements, and used to demonstrate that ambient RH affects where in the lung indoor particulate air pollution is delivered.

Water diffusion in atmospherically relevant α-pinene secondary organic material.

Secondary organic material (SOM) constitutes a large mass fraction of atmospheric aerosol particles. Understanding its impact on climate and air quality relies on accurate models of interactions with water vapour. Recent research shows that SOM can be highly viscous and can even behave mechanically like a solid, leading to suggestions that particles exist out of equilibrium with water vapour in the atmosphere. In order to quantify any kinetic limitation we need to know water diffusion coefficients for SOM, but this quantity has, until now, only been estimated and has not yet been measured. We have directly measured water diffusion coefficients in the water soluble fraction of α-pinene SOM between 240 and 280 K. Here we show that, although this material can behave mechanically like a solid, at 280 K water diffusion is not kinetically limited on timescales of 1 s for atmospheric-sized particles. However, diffusion slows as temperature decreases. We use our measured data to constrain a Vignes-type parameterisation, which we extend to lower temperatures to show that SOM can take hours to equilibrate with water vapour under very cold conditions. Our modelling for 100 nm particles predicts that under mid- to upper-tropospheric conditions radial inhomogeneities in water content produce a low viscosity surface region and more solid interior, with implications for heterogeneous chemistry and ice nucleation.