Controlling and characterizing the coagulation of liquid aerosol droplets

We demonstrate that optical tweezers can be used to control and characterize the coagulation and mixing state of aerosols. Liquid aerosol droplets of 2-14 mum in diameter are optically trapped and characterized by spontaneous and stimulated Raman scatterings, which together provide a unique signature of droplet size and composition. From the conventional bright field image, the size of the trapped droplet can be estimated and compared with that determined from stimulated Raman scattering, and the motion of the particle within the trapping plane can be recorded. A maximum of four droplets can be manipulated in tandem by forming multiple optical traps through rapid beam steering. The coagulation of two droplets can be studied directly by controlling two droplets. The limiting conditions under which optical forces and capillary forces dominate the aerosol coagulation event are explored by varying the relative optical trap strengths and characterizing the coagulation of different droplet sizes. Finally, we demonstrate that the coagulation of different aerosol components can be compared and the mixing state of the final coagulated droplet can be investigated. In particular, we compare the outcome of the coagulation of an aqueous sodium chloride aerosol droplet with a second aqueous droplet, with an ethanol droplet or with a decane droplet.     

Characterizing multiphase organic/inorganic/aqueous aerosol droplets

The partitioning of an immiscible and volatile organic component between the gas and aqueous condensed phases of an aerosol is investigated using optical tweezers. Specifically, the phase segregation of immiscible decane and aqueous components within a single liquid aerosol droplet is characterized by brightfield microscopy and by spontaneous and stimulated Raman scattering. The internally mixed phases are observed to adopt equilibrium geometries that are consistent with predictions based on surface energies and interfacial tensions and the volume fractions of the two immiscible phases. In the limit of low organic volume fraction, the stimulated Raman scattering signature is consistent with the formation of a thin film or lens of the organic component on the surface of an aqueous droplet. By comparing the nonlinear spectroscopic signature with Mie scattering predictions for a core-shell structure, the thickness of the organic layer can be estimated with nanometer accuracy. Time-dependent measurements allow the evolving partitioning of the volatile organic component between the condensed and vapor phases to be investigated.     

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.     

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.     

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.     

Comparative thermodynamic studies of aqueous glutaric acid, ammonium sulfate and sodium chloride aerosol at high humidity

Aerosol optical tweezers are used to simultaneously characterize and compare the hygroscopic properties of two aerosol droplets, one containing inorganic and organic solutes and the second, referred to as the control droplet, containing a single inorganic salt. The inorganic solute is either sodium chloride or ammonium sulfate and the organic component is glutaric acid. The time variation in the size of each droplet (3-7 microm in radius) is recorded with 1 s time resolution and with nanometre accuracy. The size of the control droplet is used to estimate the relative humidity with an accuracy of better than +/-0.09%. Thus, the Kohler curve of the multicomponent inorganic/organic droplet, which characterizes the variation in equilibrium droplet size with relative humidity, can be determined directly. The measurements presented here focus on high relative humidities, above 97%, in the limit of dilute solutes. The experimental data are compared with theoretical treatments that, while ignoring the interactions between the inorganic and organic components, are based upon accurate representations of the activity-concentration relationships of aqueous solutions of the individual salts. The organic component is treated by a parametrized fit to experimental data or by the UNIFAC model and the water activity of the equilibrium solution droplet is calculated using the approach suggested by Clegg, Seinfeld and Brimblecombe or the Zdanovskii-Stokes-Robinson approximation. It is shown that such an experimental strategy, comparing directly droplets of different composition, enables highly accurate measurements of the hygroscopic properties, allowing the theoretical treatments to be rigorously tested. Typical deviations of the experimental measurements from theoretical predictions are shown to be around 1% in equilibrium size, comparable to the variation between the theoretical frameworks considered.     

Determining the composition of aqueous microdroplets with broad-band cavity enhanced Raman scattering

We demonstrate that broad-band cavity enhanced Raman scattering (CERS) can be used to determine the composition of binary alcohol-water aerosol droplets over a wide compositional range from 10% v/v to 90% v/v. In contrast to conventional CERS using narrow-band laser excitation, the excitation is provided by a broad-band Nd:YAG pumped dye laser. A change in the spontaneous spectrum resulting from the change of the linewidth of the excitation laser permits tuning of the sensitivity range over which the droplet composition can be determined by CERS. We demonstrate that this change in sensitivity can be estimated using a simulation of the change in the sensitivity to the species in spontaneous bulk phase measurements. We further show that the compositional calibration is independent of droplet radius in the range 33-56 microm. The compositional range over which CERS is sensitive can be controlled and optimised for any particular application by exploiting the dependence of the stimulated Raman scattering on the laser linewidth and wavelength. Thus, quantitative measurements of droplet composition can be made in situ with high accuracy, providing a valuable new tool for analysing aerosol composition.     

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.     

Retrieval of the complex refractive index of aerosol droplets from optical tweezers measurements

The cavity enhanced Raman scattering spectrum recorded from an aerosol droplet provides a unique fingerprint of droplet radius and refractive index, assuming that the droplet is homogeneous in composition. Aerosol optical tweezers are used in this study to capture a single droplet and a Raman fingerprint is recorded using the trapping laser as the source for the Raman excitation. We report here the retrieval of the real part of the refractive index with an uncertainty of ± 0.0012 (better than ± 0.11%), simultaneously measuring the size of the micrometre sized liquid droplet with a precision of better than 1 nm (< ± 0.05% error). In addition, the equilibrium size of the droplet is shown to depend on the laser irradiance due to optical absorption, which elevates the droplet temperature above that of the ambient gas phase. Modulation of the illuminating laser power leads to a modulation in droplet size as the temperature elevation is altered. By measuring induced size changes of <1 nm, we show that the imaginary part of the refractive index can be retrieved even when less than 10 × 10(-9) with an accuracy of better than ± 0.5 × 10(-9). The combination of these measurements allows the complex refractive index of a droplet to be retrieved with high accuracy, with the possibility of making extremely sensitive optical absorption measurements on aerosol samples and the testing of frequently used mixing rules for treating aerosol optical properties. More generally, this method provides an extremely sensitive approach for measuring refractive indices, particularly under solute supersaturation conditions that cannot be accessed by simple bulk-phase measurements.     

An optical method for determining size distributions of water droplets

A method for determining aerosol size distributions by single laser-shot single droplet cavity enhanced Raman scattering (CERS) is presented. Droplets are illuminated with the tripled output from a Nd:YAG laser at 355 nm and the CERS fingerprint acquired with a spectrograph and CCD. Droplets with radii in the range 10–50 μm are probed. The extension of this to the determination of a distribution of droplet sizes is illustrated. We suggest that the CERS signature from water could be used to determine droplet size while the observation of Raman scattering from other constituents could be used to identify trace chemical constituents within water droplets.     

Observation of the binary coalescence and equilibration of micrometer-sized droplets of aqueous aerosol in a single-beam gradient-force optical trap

The binary coalescence of aqueous droplets has been observed in a single-beam gradient-force optical trap. By measuring the time-dependent intensity for elastic scattering of light from the trapping laser, the dynamics of binary coalescence have been examined and the time scale for equilibration of a composite droplet to ambient conditions has been determined. These data are required for modeling the agglomeration of aqueous droplets in dense sprays and atmospheric aerosol. Elastic-light scattering from optically trapped particles has not been used previously to study the time-resolved dynamics of mixing. It is shown to offer a unique opportunity to characterize the binary coalescence of aqueous droplets with radii from 1 to 6 μm. The study of this size regime, which cannot be achieved by conventional imaging methods, is critical for understanding the interactions of droplets in the environment of dense sprays.     

Evaporation of ethanol/water droplets: examining the temporal evolution of droplet size, composition and temperature

The evolving size, composition, and temperature of evaporating ethanol/water aerosol droplets 25-57 microm in radius are probed by cavity enhanced Raman scattering (CERS) and laser induced fluorescence. This represents the first study in which the evolving composition of volatile droplets has been probed with spatial selectivity on the millisecond time scale, providing a new strategy for exploring mass and heat transfer in aerosols. The Raman scattering intensity is shown to depend exponentially on species concentration due to the stimulated nature of the CERS technique, providing a sensitive measure of the concentration of the volatile ethanol component. The accuracy with which we can determine droplet size, composition, and temperature is discussed. We demonstrate that the CERS measurements of evolving size and composition of droplets falling in a train can be used to characterize, and thus avoid, droplet coagulation. By varying the surrounding gas pressure (7-77 kPa), we investigate the dependence of the rate of evaporation on the rate of gas diffusion, and behavior consistent with gas diffusion-limited evaporation is observed. We suggest that such measurements can allow the determination of the vapor pressures of components within the droplet and can allow the determination of activity coefficients of volatile species.     

Probing the evaporation of ternary ethanol-methanol-water droplets by cavity enhanced Raman scattering

Cavity enhanced Raman scattering is used to characterise the evolving composition of ternary aerosol droplets containing methanol, ethanol and water during evaporation into a dry nitrogen atmosphere. Measurements made using non-linear stimulated Raman scattering from these ternary alcohol-water droplets allow the in situ determination of the concentration of the two alcohol components with high accuracy. The overlapping spontaneous Raman bands of the two alcohol components, arising from C-H stretching vibrational modes, are spectrally-resolved in stimulated Raman scattering measurements. We also demonstrate that the evaporation measurements are consistent with a quasi-steady state evaporation model, which can be used to interpret the evaporation dynamics occurring at a range of pressures at a particular evaporation time.     

A strategy for characterizing the mixing state of immiscible aerosol components and the formation of multiphase aerosol particles through coagulation

We demonstrate that the coagulation of two aerosol droplets of different chemical composition can be studied directly through the unique combination of optical tweezers and Raman spectroscopy. Multiple optical traps can be established, allowing the manipulation of multiple aerosol droplets. Spontaneous Raman scattering allows the characterization of droplet composition and mixing state, permitting the phase segregation of immiscible components in multiphase aerosol to be investigated with spatial resolution. Stimulated Raman scattering allows the integrity of the droplet and uniformity of refractive index to be probed. The combination of these spectroscopic probes with optical tweezers is shown to yield unprecedented detail in studies of the coagulation of decane and water droplets.     

Determination of Thermodynamic Parameters from Evaporation of Binary Microdroplets of Volatile Constituents

An experimental technique based on a modified vibrating orifice aerosol generator has been employed to study unsteady evaporation of linear streams of highly monodisperse binary microdroplets of volatile constituents over short time periods (i.e., <1 ms), such that the droplet composition remains nearly constant. The droplet size and temperature (i.e., refractive index) have been determined with high temporal resolution from the resonances observed in the simultaneous elastic and Raman light scattering spectra obtained by varying the droplet size through modulation of droplet generation frequency. By using this technique we show that thermodynamic parameters of binary systems, such as activity coefficients as well as vapor pressures of the constituents as functions of temperature, can be determined. We have applied the procedure to study unsteady evaporation rates of pure ethanol and methanol droplets as well as binary droplets containing various ratios of ethanol and methanol. We have obtained vapor pressures of ethanol and methanol as functions of temperature as well as activity coefficients of ethanol and methanol as functions of composition, and the results show excellent agreements with the values reported in the literature. The technique presented in this paper is applicable to any binary system containing at least one volatile constituent. Copyright 2000 Academic Press.     

Thermodynamic Characteristics of the Micellization in Droplet and Quasi-Droplet Models of Surfactant Molecular Aggregates with Account of Experimental Data on Equilibrium Micelle Distribution

Formuals for the thermodynamic characteristics of micellization in the droplet and quasi-droplet models of surfactant molecular aggregates are derived. These formulas account for the experimental data on the mean size of micelles and average statistical scatter of their sizes in the equilibrium state. These formulas cover critical micellization concentration corresponded to the onset of surfactant accumulation in micelles and higher (than CMC) concentrations at which micelles incorporate noticeable or even the largest portion of surfactant in micellar solution. Analytical dependence of thermodynamic characteristics of micellization on the initial parameters of droplet and quasi-droplet models of molecular aggregates at critical micellization concentration is disclosed.     

Liquid-liquid phase separation and static light scattering of concentrated ternary mixtures of bovine alpha and gammaB crystallins

We have used light scattering, turbidimetry, and thermodynamic analysis to study the phase diagram of concentrated aqueous mixtures of the bovine lens proteins, gammaB crystallin, and alpha crystallin. We find that dilute alpha crystallin raises the phase separation temperature of concentrated gammaB crystallin, while more concentrated alpha crystallin suppresses phase separation. Very concentrated alpha/gammaB mixtures can reversibly cloud above 37 degrees C, even though gammaB alone phase separates only below temperatures near 0 degrees C, and alpha does not phase separate. At the scattering vector magnitude used, high-concentration alpha/gammaB mixtures scatter less light than the weighted average of their component alpha and gammaB solutions, while low-concentration alpha/gammaB mixtures scatter more than such a weighted average. We use a mean-field thermodynamic analysis of such ternary mixtures to show that the observed light scattering and phase boundaries of alpha and gammaB crystallin mixtures give evidence for prominent local fluctuations of relative protein composition. In the single phase, these fluctuations scatter comparatively little light, but are associated with enhanced thermodynamic instability. By applying this analysis to the experimental tie lines we estimate the magnitude of the saddlelike component of the free energy near the aqueous-gammaB critical point.     

Infrared spectroscopic properties of sodium bromide aerosols

The infrared extinction spectra of aqueous NaBr aerosols at ambient temperature have been measured as a function of relative humidity. Submicron-sized aerosol particles atomized from aqueous NaBr solutions at various concentrations are dried and/or mixed with nitrogen at different humidities and spectroscopically monitored as they flow through an infrared absorption cell. Estimated dry particle median diameters range from 0.24 to 0.15 microm, as calculated from Mie extinction theory. Measured deliquescence and efflorescence relative humidities (35-40% and 25-30%, respectively) are in accordance with previously reported ones. Our results show that NaBr particles take up water only moderately over the deliquescence point, with a significant increase at relative humidities above 70%. The effect of particle size onto water uptake properties has been studied, indicating that smaller particles take up lower amounts of water, and only increase their size significantly at relative humidities near saturation. Particle composition and diameter growth factors have been calculated from spectral data and are shown to be consistent with those predicted from thermodynamic data and Kohler theory. Band centers of liquid water in NaBr aerosols relative to pure water are blue-shifted up to 50 cm-1 at low humidities. Particle structure and phase, together with atmospheric implications, are also discussed.     

Enhanced and normal Raman scattering from pyridine adsorbed on rough and smooth silver electrodes

A multiplex spectrograph has been used to record potential difference and modulation Raman spectra of pyridine adsorbed on silver electrodes in an electrochemical cell. Spectra have been obtained from rough silver surfaces which give SERS and from surfaces where SERS has been diminished by prolonged cathodic polarisation (DSERS). Raman scattering from pyridine at smooth silver surfaces in potassium perchlorate and fluoride solutions has been distinguished from solution scatter by a potential modulation technique. The results show that the enhanced scattering caused by silver atom or cluster sites is respresentative of the surface as a whole as similar Raman spectra are obtained on smooth surfaces at a count rate as low as ?1.4 photons s^?1 (incident laser power 500 mW).Correlation of simultaneous differential capacitance data and “snapshot” SER spectra indicate that pyridine molecules in aqueous chloride ion solutions adsorb on silver in a flat π-bonded configuration at potentials markedly positive to the point of zero charge and exhibit specific reorientation at ?0.3 V and ?0.45 V (vs. SCE) to become N-bonded, perpendicular to the surface. Results also show that the adsorption behaviour of pyridine in chloride and fluoride ion solutions is largely similar.     

Ultra-slow water diffusion in aqueous sucrose glasses

We present measurements of water uptake and release by single micrometre-sized aqueous sucrose particles. The experiments were performed in an electrodynamic balance where the particles can be stored contact-free in a temperature and humidity controlled chamber for several days. Aqueous sucrose particles react to a change in ambient humidity by absorbing/desorbing water from the gas phase. This water absorption (desorption) results in an increasing (decreasing) droplet size and a decreasing (increasing) solute concentration. Optical techniques were employed to follow minute changes of the droplet's size, with a sensitivity of 0.2 nm, as a result of changes in temperature or humidity. We exposed several particles either to humidity cycles (between ～2% and 90%) at 291 K or to constant relative humidity and temperature conditions over long periods of time (up to several days) at temperatures ranging from 203 to 291 K. In doing so, a retarded water uptake and release at low relative humidities and/or low temperatures was observed. Under the conditions studied here, the kinetics of this water absorption/desorption process is controlled entirely by liquid-phase diffusion of water molecules. Hence, it is possible to derive the translational diffusion coefficient of water molecules, D(H(2)O,) from these data by simulating the growth or shrinkage of a particle with a liquid-phase diffusion model. Values for D(H(2)O)-values as low as 10(-24) m(2) s(-1) are determined using data at temperatures down to 203 K deep in the glassy state. From the experiment and modelling we can infer strong concentration gradients within a single particle including a glassy skin in the outer shells of the particle. Such glassy skins practically isolate the liquid core of a particle from the surrounding gas phase, resulting in extremely long equilibration times for such particles, caused by the strongly non-linear relationship between concentration and D(H(2)O). We present a new parameterization of D(H(2)O) that facilitates describing the stability of aqueous food and pharmaceutical formulations in the glassy state, the processing of amorphous aerosol particles in spray-drying technology, and the suppression of heterogeneous chemical reactions in glassy atmospheric aerosol particles.