Phase, morphology, and hygroscopicity of mixed oleic acid/sodium chloride/water aerosol particles before and after ozonolysis

Aerosol optical tweezers are used to probe the phase, morphology, and hygroscopicity of single aerosol particles consisting of an inorganic component, sodium chloride, and a water insoluble organic component, oleic acid. Coagulation of oleic acid aerosol with an optically trapped aqueous sodium chloride droplet leads to formation of a phase-separated particle with two partially engulfed liquid phases. The dependence of the phase and morphology of the trapped particle with variation in relative humidity (RH) is investigated by cavity enhanced Raman spectroscopy over the RH range <5% to >95%. The efflorescence and deliquescence behavior of the inorganic component is shown to be unaffected by the presence of the organic phase. Whereas efflorescence occurs promptly (<1 s), the deliquescence process requires both dissolution of the inorganic component and the adoption of an equilibrium morphology for the resulting two phase particle, occurring on a time-scale of <20 s. Comparative measurements of the hygroscopicity of mixed aqueous sodium chloride/oleic acid droplets with undoped aqueous sodium chloride droplets show that the oleic acid does not impact on the equilibration partitioning of water between the inorganic component and the gas phase or the time response of evaporation/condensation. The oxidative aging of the particles through reaction with ozone is shown to increase the hygroscopicity of the organic component.     

Spectroscopy of growing and evaporating water droplets: exploring the variation in equilibrium droplet size with relative humidity

We demonstrate that the thermodynamic properties of a single liquid aerosol droplet can be explored through the combination of a single-beam gradient force optical trap with Raman spectroscopy. A single aqueous droplet, 2-6 microm in radius, can be trapped in air indefinitely and the response of the particle to variations in relative humidity investigated. The Raman spectrum provides a unique fingerprint of droplet composition, temperature, and size. Spontaneous Raman scattering is shown to be consistent with that from a bulk phase sample, with the shape of the OH stretching band dependent on the concentration of sodium chloride in the aqueous phase and on the polarization of the scattered light. Stimulated Raman scattering at wavelengths commensurate with whispering gallery modes is demonstrated to provide a method for determining the size of the trapped droplet with nanometer precision and with a time resolution of 1 s. The polarization dependence of the stimulated scatter is consistent with the dependence observed for the spontaneous scatter from the droplet. By characterizing the spontaneous and stimulated Raman scattering from the droplet, we demonstrate that it is possible to measure the equilibrium size and composition of an aqueous droplet with variation in relative humidity. For this benchmark study we investigate the variation in equilibrium size with relative humidity for a simple binary sodium chloride/aqueous aerosol, a typical representative inorganic/aqueous aerosol that has been studied extensively in the literature. The measured equilibrium sizes are shown to be in excellent agreement with the predictions of K?hler theory. We suggest that this approach could provide an important new strategy for characterizing the thermodynamic properties and kinetics of transformation of aerosol particles.     

Spectroscopic characterization of aqueous microdroplets containing inorganic salts

We have developed and studied methods to characterize the time-varying composition of liquid microdroplets, under controlled changes to environmental conditions, using Raman tweezers. This work has focussed on measurements of inorganic salts, such as nitrate and sulfate anions, which comprise a major fraction of the dissolved solutes in atmospheric aerosols. The experimental Raman intensities for the anions of inorganic salts in optically tweezed droplets were found to be in good agreement with theoretical estimates of photon scattering. The detection limit for sodium nitrate salt in a single particle was found to be ~4 pg. The mass of an inorganic salt in the droplet can be estimated from the Raman intensity of the anion bands using a calibration curve which is independent of droplet volume. The volume of the droplet, and concentration of solute, can be found directly from the spacing of morphology dependent resonances in the Raman band of water, or indirectly from the integrated-intensity of the Raman band for the solvent. The later strategy eliminates the uncertainty in the collection efficiency of Raman-scattered light related to varying particle sizes.     

Deliquescence and efflorescence behavior of ternary inorganic/organic/water aerosol particles

The deliquescence behavior of ternary inorganic (ammonium sulfate and ammonium nitrate)/organic (glutaric acid and malonic acid)/water aerosol particles has been investigated at 293 K using a novel surface aerosol microscopy (SAM) technique. The results obtained for the deliquescence relative humidities (DRH) for particles of variable inorganic/organic contents show a eutectic behavior with the mixed particles showing deliquescence at lower DRH compared to the pure inorganic and organic components, respectively. This behavior has been quantitatively modeled using the extended aerosol inorganics (E-AIM) thermodynamic model of Clegg et al. in combination with the UNIFAC group activity approach to account for organic molecular solutes. In addition, we have investigated the crystallization behavior of supersatured and formerly deliquesced ternary solution droplets using space resolved Raman spectroscopy. It is found that such droplets produce solid particles in which the inorganic and organic phases show some spatial separation with the organic component being predominantly found at the outer part of the particle. Independent measurements of the contact angles of such ternary droplets reveal that their angles are within experimental error identical to those of the purely organic/water solutions.     

Direct comparison of the hygroscopic properties of ammonium sulfate and sodium chloride aerosol at relative humidities approaching saturation

Holographic optical tweezers are used to make comparative measurements of the hygroscopic properties of single component aqueous aerosol containing sodium chloride and ammonium sulfate over a range of relative humidity from 84% to 96%. The change in RH over the course of the experiment is monitored precisely using a sodium chloride probe droplet with accuracy better than ±0.09%. The measurements are used to assess the accuracy of thermodynamic treatments of the relationship between water activity and solute mass fraction with particular attention focused on the dilute solute limit approaching saturation vapor pressure. The consistency of the frequently used Clegg-Brimblecombe-Wexler (CBW) treatment for predicting the hygroscopic properties of sodium chloride and ammonium sulfate aerosol is confirmed. Measurements of the equilibrium size of ammonium sulfate aerosol are found to agree with predictions to within an uncertainty of ±0.2%. Given the accuracy of treating equilibrium composition, the inconsistencies highlighted in recent calibration measurements of critical supersaturations of sodium chloride and ammonium sulfate aerosol cannot be attributed to uncertainties associated with the thermodynamic predictions and must have an alternative origin. It is concluded that the CBW treatment can allow the critical supersaturation to be estimated for sodium chloride and ammonium sulfate aerosol with an accuracy of better than ±0.002% in RH. This corresponds to an uncertainty of ≤1% in the critical supersaturation for typical supersaturations of 0.2% and above. This supports the view that these systems can be used to accurately calibrate instruments that measure cloud condensation nuclei concentrations at selected supersaturations. These measurements represent the first study in which the equilibrium properties of two particles of chemically distinct composition have been compared simultaneously and directly alongside each other in the same environment.     

The morphology of aerosol particles consisting of hydrophobic and hydrophilic phases: hydrocarbons, alcohols and fatty acids as the hydrophobic component

The morphology of bi-phase aerosol particles containing phase separated hydrophobic and hydrophilic components is considered, comparing simulations based on surface and interfacial tensions with measurements made by aerosol optical tweezers. The competition between the liquid phases adopting core-shell and partially engulfed configurations is considered for a range of organic compounds including saturated and unsaturated hydrocarbons, aromatics, alcohols, ketones, carboxylic acids, esters and amines. When the solubility of the organic component and the salting-out of the organic component to the surface by the presence of concentrated inorganic solutes in the aqueous phase are considered, it is concluded that the adoption of a partially engulfed structure predominates, with the organic component forming a surface lens. The aqueous surface can be assumed to be stabilised by a surface enriched in the organic component. The existence of acid-base equilibria can lead to the dissociation of organic surfactants and to significant lowering of the surface tension of the aqueous phase, further supporting the predominance of partially engulfed structures. Trends in morphology from experimental measurements and simulations are compared for mixed phased droplets in which the organic component is decane, 1-octanol or oleic acid with varying relative humidity. The consequences of partially engulfed structures for aerosol properties are considered.     

Manipulation and characterization of aqueous sodium dodecyl sulfate/sodium chloride aerosol particles

Aerosol optical tweezers coupled with Raman spectroscopy can allow the detailed investigation of aerosol dynamics. We describe here measurements of the evolving size, composition, and phase of single aqueous aerosol droplets containing the surfactant sodium dodecyl sulfate and the inorganic salt sodium chloride. Not only can the evolving wet particle size be probed with nanometer accuracy, but we show that the transition to a metastable microgel particle can be followed, demonstrating that optical tweezers can be used to manipulate both spherical and non-spherical aerosol particles. Further, through the simultaneous manipulation and characterization of two aerosol droplets of different composition in two parallel optical traps, the phase behavior of a surfactant-doped particle and a surfactant-free droplet can be compared directly in situ. We also illustrate that the manipulation of two microgel particles can allow studies of the coagulation and interaction of two solid particles. Finally, we demonstrate that such parallel measurements can permit highly accurate comparative measurements of the evolving wet particle size of a surfactant-doped droplet with a surfactant-free droplet.     

Deliquescence phase transition measurements by quartz crystal microbalance frequency shifts

Measurements of the hygroscopic properties of aerosols are needed to better understand the role of aerosols as cloud condensation nuclei. Several techniques have been used to measure deliquescence (solid to liquid) phase transitions in particular. In this study, we have measured the deliquescence relative humidity (DRH) of organic and inorganic salts, organic acids (glutaric and succinic acid), and mixtures of organic acids with ammonium sulfate using a quartz crystal microbalance (QCM). The QCM allows for measurement of the deliquescence phase transition due to inherent measurement differences between solids and liquids in the oscillation frequency of a quartz crystal. The relative humidity dependent frequency measurements can be used to identify compounds that adsorb monolayer amounts of water or form hydrates prior to deliquescence (e.g., lithium chloride, potassium and sodium acetate). Although the amount of water uptake by a deliquescing material cannot be quantified with this technique, deliquescence measurements of mixtures of hygroscopic and nonhygroscopic components (e.g., ammonium sulfate and succinic acid (DRH > 95%)) show that the mass fraction of the deliquescing portion of the sample can be quantitatively determined from the relative change in oscillation frequency at deliquescence. The results demonstrate the use of this technique as an alternative method for phase transition measurements and as a direct measurement of the mass fraction of a sample that undergoes deliquescence. Further, deliquescence measurements by the QCM may provide improved understanding of discrepancies in atmospheric particle mass measurements between filter samples and the tapered element oscillating microbalance given the similar measurement principle employed by the QCM.     

Monodisperse w/w/w Double Emulsion Induced by Phase Separation

We develop an approach to fabricate monodisperse water-in-water-in-water (w/w/w) double emulsion in microfluidic devices. A jet of aqueous solution containing two incompatible solutes, dextran and polyethylene glycol (PEG), is periodically perturbed into water-in-water (w/w) droplets. By extracting water out of the w/w droplet, the solute concentrations in the droplet phase increase; when the concentrations exceed the miscibility limit, the droplet phase separates into two immiscible phases. Consequently, PEG-rich droplets are formed within the single emulsion templates. These PEG-rich droplets subsequently coalesce with each other, resulting in transiently stable w/w/w double emulsions with a high degree of size uniformity. These double emulsions are free of organic solvents and thus are ideal for use as droplet-vessels in protein purification, as microreactors for biochemical reactions, and as templates for fabrication of biomaterials.     

Master curves for elastic and plastic properties of highly concentrated emulsions

Critical comparison of dependences of elastic and plastic properties of highly concentrated emulsions (so-called “compressed” emulsions) on the concentration and droplet sizes is performed. The studied emulsions of water-in-oil type are so-called “liquid explosives.” They are characterized by different mean sizes and different droplet size distributions of the dispersed phase. Different average values (D _av, D ₃₂, and D ₄₃) are used as characteristics of droplet sizes. Experiments are carried out with emulsions of two concentrations. Aqueous phase (dispersed droplets) is presented by supercooled solutions of inorganic salt in water in a metastable state. The concentration limit of the existence of highly concentrated emulsions is determined by the condition of the closest packing of liquid droplets, which lies in the φ* = 0.77–0.80 range. In addition, there is a limiting value of the maximal size of droplets. This limiting value depends on the concentration and meets the requirement that droplets should be small enough for the solution to exist in a supercooled state. The elastic modulus and the yield stress of emulsions studied are proportional to the square of the reciprocal linear size of droplets, which contradicts some theoretical models, according to which these parameter should be proportional to the reciprocal size of droplets. Using the obtained experimental data, we constructed generalized dependences of the elastic modulus and the yield stress on the concentration and size of droplets. These characteristics are in good agreement with the experimental data.     

Homogeneous ice nucleation from aqueous inorganic/organic particles representative of biomass burning: water activity, freezing temperatures, nucleation rates

Homogeneous ice nucleation plays an important role in the formation of cirrus clouds with subsequent effects on the global radiative budget. Here we report on homogeneous ice nucleation temperatures and corresponding nucleation rate coefficients of aqueous droplets serving as surrogates of biomass burning aerosol. Micrometer-sized (NH(4))(2)SO(4)/levoglucosan droplets with mass ratios of 10:1, 1:1, 1:5, and 1:10 and aqueous multicomponent organic droplets with and without (NH(4))(2)SO(4) under typical tropospheric temperatures and relative humidities are investigated experimentally using a droplet conditioning and ice nucleation apparatus coupled to an optical microscope with image analysis. Homogeneous freezing was determined as a function of temperature and water activity, a(w), which was set at droplet preparation conditions. The ice nucleation data indicate that minor addition of (NH(4))(2)SO(4) to the aqueous organic droplets renders the temperature dependency of water activity negligible in contrast to the case of aqueous organic solution droplets. The mean homogeneous ice nucleation rate coefficient derived from 8 different aqueous droplet compositions with average diameters of ～60 μm for temperatures as low as 195 K and a(w) of 0.82-1 is 2.18 × 10(6) cm(-3) s(-1). The experimentally derived freezing temperatures and homogeneous ice nucleation rate coefficients are in agreement with predictions of the water activity-based homogeneous ice nucleation theory when taking predictive uncertainties into account. However, the presented ice nucleation data indicate that the water activity-based homogeneous ice nucleation theory overpredicts the freezing temperatures by up to 3 K and corresponding ice nucleation rate coefficients by up to ～2 orders of magnitude. A shift of 0.01 in a(w), which is well within the uncertainty of typical field and laboratory relative humidity measurements, brings experimental and predicted freezing temperatures and homogeneous ice nucleation rate coefficients into agreement. The experimentally derived ice nucleation data are applied to constrain the water activity-based homogeneous ice nucleation theory to smaller than ±1 order of magnitude compared to the predictive uncertainty of larger than ±6 orders of magnitude. The atmospheric implications of these findings are discussed.     

Capacitive sensing of droplets for microfluidic devices based on thermocapillary actuation

The design and performance of a miniaturized coplanar capacitive sensor is presented whose electrode arrays can also function as resistive microheaters for thermocapillary actuation of liquid films and droplets. Optimal compromise between large capacitive signal and high spatial resolution is obtained for electrode widths comparable to the liquid film thickness measured, in agreement with supporting numerical simulations which include mutual capacitance effects. An interdigitated, variable width design, allowing for wider central electrodes, increases the capacitive signal for liquid structures with non-uniform height profiles. The capacitive resolution and time response of the current design is approximately 0.03 pF and 10 ms, respectively, which makes possible a number of sensing functions for nanoliter droplets. These include detection of droplet position, size, composition or percentage water uptake for hygroscopic liquids. Its rapid response time allows measurements of the rate of mass loss in evaporating droplets.     

Characterizing the formation of organic layers on the surface of inorganic/aqueous aerosols by Raman spectroscopy

We demonstrate that nonlinear Raman spectroscopy coupled with aerosol optical tweezers can be used to probe the evolving phase partitioning in mixed organic/inorganic/aqueous aerosol droplets that adopt a core-shell structure in which the aqueous phase is coated in an organic layer. Specifically, we demonstrate that the characteristic fingerprint of wavelengths at which stimulated Raman scattering is observed can be used to assess the phase behavior of multiphase decane/aqueous sodium chloride droplets. Decane is observed to form a layer on the surface of the core aqueous droplet, and from the spectroscopic signature the aqueous core size can be determined with nanometer accuracy and the thickness of the decane layer with an accuracy of +/-8 nm. Further, the presence of the organic layer is observed to reduce the rate at which water evaporates from the core of the droplet with an increasing rate of evaporation observed with diminishing layer thickness.     

The electrochemical detection of droplets in microfluidic devices

This paper presents a new electrochemical method for the detection and characterisation of aqueous droplets in an organic carrier fluid (1,2-dichloroethane) formed in flow-focusing microfluidic devices. The devices consist of a conventional flow-focusing channel 250 microm wide and 250 microm deep cast out of poly(dimethylsiloxane) (PDMS) which is sealed onto a glass substrate containing a set of microelectrodes 100 microm long. Chronoamperometric analysis of a suitable electrolyte contained in the organic phase is presented for characterising the droplet frequency and size. This chronoamperometric method is then extended to a dual working electrode approach in order to determine the velocity of the droplet. Good agreement between experimental measurements and theory was observed.     

Surface tension of different sized single-component droplets,according to macroscopic data obtained using the lattice gas model and the critical droplet size during phase formation

Size dependences of the surface tension of spherical single-component droplets are calculated using equations of the lattice gas model for 19 compounds. Parameters of the model are found from experimental data on the surface tension of these compounds for a macroscopic planar surface. The chosen low-molecular compounds satisfy the law of corresponding states. To improve agreement with the experimental data, Lennard-Jones potential parameters are varied within 10% deviations. The surface tensions of different sized equilibrium droplets are calculated at elevated and lowered temperatures. It is found that the surface tension of droplets grows monotonically as the droplet size increases from zero to its bulk value. The droplet size R ₀ corresponding to zero surface tension corresponds to the critical size of the emergence of a new phase. The critical droplet sizes in the new phase of the considered compounds are estimated for the first time.     

Shrinking droplets in electrospray ionization and their influence on chemical equilibria

We investigated how chemical equilibria are affected by the electrospray process, using simultaneous in situ measurements by laser-induced fluorescence (LIF) and phase Doppler anemometry (PDA). The motivation for this study was the increasing number of publications in which electrospray ionization mass spectrometry is used for binding constant determination. The PDA was used to monitor droplet size and velocity, whereas LIF was used to monitor fluorescent analytes within the electrospray droplets. Using acetonitrile as solvent, we found an average initial droplet diameter of 10 microm in the electrospray. The PDA allowed us to follow the evolution of these droplets down to a size of 1 microm. Rhodamine B-sulfonylchloride was used as a fluorescent analyte within the electrospray. By spatially resolved LIF it was possible to probe the dimerization equilibrium of this dye. Measurements at different spray positions showed no influence of the decreasing droplet size on the monomer-dimer equilibrium. However, with the fluorescent dye pair DCM and oxazine 1 it was shown that a concentration increase does occur within electrosprayed droplets, using fluorescence resonance energy transfer as a probe for the average pair distance.     

Sessile nanofluid droplet drying

Nanofluid droplet evaporation has gained much audience nowadays due to its wide applications in painting, coating, surface patterning, particle deposition, etc. This paper reviews the drying progress and deposition formation from the evaporative sessile droplets with the suspended insoluble solutes, especially nanoparticles. The main content covers the evaporation fundamental, the particle self-assembly, and deposition patterns in sessile nanofluid droplet. Both experimental and theoretical studies are presented. The effects of the type, concentration and size of nanoparticles on the spreading and evaporative dynamics are elucidated at first, serving the basis for the understanding of particle motion and deposition process which are introduced afterward. Stressing on particle assembly and production of desirable residue patterns, we express abundant experimental interventions, various types of deposits, and the effects on nanoparticle deposition. The review ends with the introduction of theoretical investigations, including the Navier–Stokes equations in terms of solutions, the Diffusion Limited Aggregation approach, the Kinetic Monte Carlo method, and the Dynamical Density Functional Theory. Nanoparticles have shown great influences in spreading, evaporation rate, evaporation regime, fluid flow and pattern formation of sessile droplets. Under different experimental conditions, various deposition patterns can be formed. The existing theoretical approaches are able to predict fluid dynamics, particle motion and deposition patterns in the particular cases. On the basis of further understanding of the effects of fluid dynamics and particle motion, the desirable patterns can be obtained with appropriate experimental regulations.     

Ultrasonic attenuation spectroscopy of emulsions with droplet sizes greater than 10 microm

Ultrasonic attenuation measurement is a frequently used tool for non-destructive determination of dispersion characteristics. Useful information like particle or droplet size and their concentration can be obtained, if the relation between size and attenuation of the dispersion is known. In this work, the theoretical model by Faran for the intermediate sound wave regime (IWR) is presented in combination with experimental data. In the IWR, the acoustic behavior is governed by elastic scattering rather than by dissipative effects. Experiments with emulsion of droplet sizes greater than 10 mum were carried out. Silicone oil, sunflower oil and olive oil were selected for the disperse phase of the oil-in-water emulsions. First, emulsions having droplets in the micrometer range were created. Afterwords, attenuation measurements of different concentrated emulsion were carried out. Some adjustments reflecting concentration influence were performed to outline the agreement between calculations and measurements. The validity of the model can be confirmed, if the volume fraction of the disperse phase is considered as a variable. Finally, droplet size distributions from theoretical attenuation spectra could be calculated based on a log-normal distribution.     

Investigations of the hygroscopic properties of ammonium sulfate and mixed ammonium sulfate and glutaric acid micro droplets by means of optical levitation and Raman spectroscopy

In the presented work an optical levitation technique performed by means of a focused laser beam, Mie and Raman spectroscopy have been utilized for measuring hygroscopic growth curves and composition of laboratory generated single ammonium sulfate (AS) and internally mixed ammonium sulfate-glutaric acid (GA) droplets in the micrometer range. The generated particles have been found to immediately supersaturate (above 45wt% for AS) at 297 K after capturing in the laser beam. Further increase of the relative humidity (RH) up to 85% does not dilute the droplets under the saturation point. A spontaneous hygroscopic growth takes place at 73.5-78% RH for pure AS. The particle grows with an average factor of 1.62 at the deliquescence relative humidity (DRH). Efflorescence of AS occurs at 43% RH with a corresponding concentration of more than 85wt%. Independent of the mixing ratios in ranges 25/75, 50/50, 75/25% AS/GA mixed particles don't exist as a metastable supersaturated solution droplets in the 35-85% RH range. Instead of growing with increasing relative humidity internally mixed particles build up a solid crystalline layer on the surface. This crystalline phase is not further influenced by ambient relative humidities.