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.

Aerosols and droplets from expiratory events play an integral role in transmitting pathogens such as SARS-CoV-2 from an infected individual to a susceptible host. However, there remain significant uncertainties in our understanding of the aerosol droplet microphysics occurring during drying and sedimentation and the effect on the sedimentation outcomes. Here, we apply a new treatment for the microphysical behavior of respiratory fluid droplets to a droplet evaporation/sedimentation model and assess the impact on sedimentation distance, time scale, and particle phase. Above a 100 μm initial diameter, the sedimentation outcome for a respiratory droplet is insensitive to composition and ambient conditions. Below 100 μm, and particularly below 80 μm, the increased settling time allows the exact nature of the evaporation process to play a significant role in influencing the sedimentation outcome. For this size range, an incorrect treatment of the droplet composition, or imprecise use of RH or temperature, can lead to large discrepancies in sedimentation distance (with representative values >1 m, >2 m, and >2 m, respectively). Additionally, a respiratory droplet is likely to undergo a phase change prior to sedimenting if initially <100 μm in diameter, provided that the RH is below the measured phase change RH. Calculations of the potential exposure versus distance from the infected source show that the volume fraction of the initial respiratory droplet distribution, in this size range, which remains elevated above 1 m decreases from 1 at 1 m to 0.125 at 2 m.

Evaporation studies of single aqueous sucrose aerosol particles as a function of relative humidity (RH) are presented for coarse and fine mode particles down into the submicron size range (600 nm < r < 3.0 μm). These sucrose particles serve as a proxy for biogenic secondary organic aerosols that have been shown to exist, under ambient conditions, in an ultraviscous glassy state, which can affect the kinetics of water mass transport within the bulk phase and hinder particle response to changes in the gas phase water content. A counter-propagating Bessel beams (CPBBs) optical trapping setup is employed to monitor the real-time change in the particle radius with RH decreasing from 75% to 5%. The slow-down of the size change upon each RH step and the deviation from the theoretical equilibrium hygroscopic growth curve indicate the onset of glassy behavior in the RH range of 10-40%. Size-dependent effects were not observed within the uncertainty of the measurements. The influence of the drying time below the glass transition RH on the timescale of subsequent water condensation and re-equilibration for sucrose particles is explored by optical tweezers measurements of micron-sized particles (3 μm < r < 6 μm). The timescale for water condensation and re-equilibration is shown to increase with increasing drying time, i.e. the time over which a viscous particle is dried below 5% RH. These studies demonstrate the importance of the history of the particle conditioning on subsequent water condensation and re-equilibration dynamics of ultraviscous and glassy aerosol particles.

The phase-separation of mixed aerosol particles and the resulting morphology plays an important role in determining the interactions of liquid aerosols with their gas-phase environment. We present the application of a new aerosol optical tweezers chamber for delivering a uniformly mixed aerosol flow to the trapped droplet's position for performing experiments that determine the phaseseparation and resulting properties of complex mixed droplets. This facilitates stable trapping when adding additional phases through aerosol coagulation, and reproducible measurements of the droplet's equilibration timescale. We demonstrate the trapping of pure organic carbon droplets, which allows us to study the morphology of droplets containing pure hydrocarbon phases to which a second phase is added by coagulation. A series of experiments using simple compounds are presented to establish our ability to use the cavity enhanced Raman spectra to distinguish between homogeneous single-phase, and phase-separated core-shell or partially engulfed morphologies. The core-shell morphology is distinguished by the pattern of the whispering gallery modes (WGMs) in the Raman spectra where the WGMs are influenced by refraction through both phases. A coreshell optimization algorithm was developed to provide a more accurate and detailed analysis of the WGMs than is possible using the homogeneous Mie scattering solution. The unique analytical capabilities of the aerosol optical tweezers provide a new approach for advancing our understanding of the chemical and physical evolution of complex atmospheric particulate matter, and the important environmental impacts of aerosols on atmospheric chemistry, air quality, human health, and climate change. EDITORThomas Kirchstetter

General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. (0)117 9287672 e-mail: a.orr-ewing@bristol.ac.uk AbstractThe extinction cross sections of individual, optically confined aerosol particles with radii of a micron or less can, in principle, be measured using cavity ring-down spectroscopy (CRDS). However, when the particle radius is comparable in magnitude to the wavelength of light stored in a high-finesse cavity, the phenomenological cross-section retrieved from a CRDS experiment depends on the location of the particle in the intra-cavity standing wave and differs from the Mie scattering cross section for plane-wave irradiation. Using an evaporating 1,2,6-hexanetriol particle of initial radius ~1.75 m confined within the 4.5-m diameter core of a Bessel beam, we demonstrate that the scatter in the retrieved extinction efficiency of a single particle is determined by its lateral motion, which spans a few wavelengths of the intra-cavity standing wave used for CRDS measurements. Fits of experimental measurements to Mie calculations, modified to account for the intra-cavity standing wave, allow precise retrieval of the refractive index of 1,2,6-hexanetriol particles (with relative humidity, RH < 10%) of 1.47824  0.00072.

A single horizontally-propagating zeroth order Bessel laser beam with a counter-propagating gas flow 9 was used to confine single fine-mode aerosol particles over extended periods of time, during which 10 process measurements were performed. Particle sizes were measured by the analysis of the angular 11 variation of light scattered at 532 nm by a particle in the Bessel beam, using either a probe beam at 12 405 nm or 633 nm. The vapour pressures of glycerol and 1,2,6-hexanetriol particles were determined 13 to be 7.5 2.6 mPa and 0.20 0.02 mPa respectively. The lower volatility of hexanetriol allowed better 14 definition of the trapping environment relative humidity profile over the measurement time period, 15 thus higher precision measurements were obtained compared to those for glycerol. The size evolution 16 of a hexanetriol particle, as well as its refractive index at wavelengths 532 nm and 405 nm, were 17 determined by modelling its position along the Bessel beam propagation length while collecting phase 18 functions with the 405 nm probe beam. Measurements of the hygroscopic growth of sodium chloride 19 and ammonium sulfate have been performed on particles as small as 350 nm in radius, with growth 20 curves well described by widely used equilibrium state models. These are the smallest particles for 21 which single-particle hygroscopicity has been measured and represent the first measurements of 22 hygroscopicity on fine mode and near-accumulation mode aerosols, the size regimes bearing the most 23 atmospheric relevance in terms of loading, light extinction and scattering. Finally, the technique is 24 contrasted with other single particle and ensemble methods, and limitations are assessed. 25 26 2

Bessel beams were used to create a counter-propagating optical trap for capturing and manipulating aerosol particles. Aerosol droplets were characterized through measurement of the elastic scattered light at three wavelengths; the trapping wavelength of 532 nm was used in conjunction with two probe beams at 405 nm and 633 nm to reduce the uncertainty in estimating droplet radii of 1 μm or less. Control of the aerosol size distribution sampled by the counter-propagating trap was demonstrated by varying the trapping beam core diameters and intensities. Smaller droplet sizes were preferentially selected with a 1.7 μm core diameter compared to cores of 2.7 μm and 4.5 μm. Further, an increase in core intensity was shown to broaden the range in droplet sizes that were optically trapped. The possibility of using such an approach to isolate and analyze the properties of single accumulation mode aerosol particles is discussed.

Industrial processes such as spray drying of pharmaceutical and food products often involve the drying of aerosol droplets containing colloidal suspensions into powdered microparticles of desired properties. The morphology and surface properties of the final dry products/microparticles obtained after the drying process are strongly influenced by the parameters of the initial aerosol droplet composition and the drying conditions. In particular, the final dry microparticle morphology can be dependent on the dimensionless Péclet number (Pe), which expresses the relative competition between the diffusion of the dispersed particles within the droplet and the rate of solvent loss via evaporation. In this work, we examine how control over the gas phase drying conditions and initial aerosol droplet composition can be used to influence the aerosol droplet drying kinetics in the gas phase for a range of Péclet numbers. We used a single-particle levitation instrument, the electrodynamic balance, to measure the drying kinetics of colloidal silica droplets (0.10 -0.60 % v/v) under controlled gas phase drying conditions of temperature (263 -326 K) and relative humidity (0 -90 %) and obtained Péclet numbers ranging from 4.05 -184.5. We demonstrate that, for aerosol droplets with initially dilute feed colloid concentrations and within the constant evaporation regime, the starting composition does not strongly influence the solvent evaporation rate with the included nanoparticles (NPs) acting as spectators. However, the gas phase drying conditions, temperature, and relative humidity, directly influences the droplet temperature via evaporative cooling as well as the droplet drying kinetics and the final dry microparticle properties. With a priori knowledge of the droplet drying kinetics from the single droplet measurements, we further demonstrate the possibility of tailoring the morphology of the dried microparticles. Dried silica microparticles collected at Pe = 23.8 had dense spherical morphologies whiles those at the highest Pe = 180.0 had crumpled surface morphologies with a transition in morphology between these limiting Pe values. Our results extend the fundamental understanding of the mechanisms controlling the drying of aerosol droplets in colloidal suspensions across a wide range of application areas extending from spray drying, to the drying of respiratory fluid droplets containing bacteria and viruses, and the drying of atmospheric aerosol droplets.