Laura Mitchem

Control and characterisation of a single aerosol droplet in a single-beam gradient-force optical trap

Optical tweezers are used to control aerosol droplets, 4–14 μm in diameter, over time frames of hours at trapping powers of less than 10 mW. When coupled with cavity enhanced Raman scattering (CERS), the evolution of the size of a single droplet can be examined with nanometre accuracy. Trapping efficiencies for water and decane droplets are reported and the possible impact of droplet heating is discussed. We demonstrate that the unique combination of optical tweezing and CERS can enable the fundamental factors governing the coagulation of two liquid droplets to be studied.

Spectroscopic studies of the size and composition of single aerosol droplets

The characterization of aerosol properties and processes, non-intrusively and directly, poses a severe analytical challenge. In order to understand the role of aerosols in often complex environments, it is necessary to probe the particles in situ and without perturbation. Sampling followed by end-of-line analysis can lead to perturbations in particle composition, morphology and size, particularly when analysing liquid aerosol droplets containing volatile components. Optical spectroscopy can provide a strategy for the direct assessment of particle size, composition and phase. We review here the application of linear and non-linear Raman spectroscopies in the characterization of liquid aerosol droplets. Spontaneous Raman scattering can allow the unambiguous identification of chemical components and the determination of droplet composition. Stimulated Raman spectroscopy can allow the determination of droplet size with nanometre accuracy and can allow the characterization of near-surface composition. When combined, the mixing state and homogeneity in droplet composition can be investigated. We highlight some applications of these spectroscopic techniques in studies of the kinetics of particle transformation, the equilibrium composition of aqueous aerosol droplets, and the coagulation and mixing state of organic and aqueous aerosol components. Specifically, we examine the heat and mass transfer accompanying the evaporation of volatile components from liquid droplets, the equilibrium size of aqueous/sodium chloride droplets with varying relative humidity, and the mixing of the immiscible decane and water components during droplet coagulation. We conclude by considering the potential of these techniques for improving our understanding of aerosol properties and processes.

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.

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.

Direct measurements of the axial displacement and evolving size of optically trapped aerosol droplets

The axial displacement of optically tweezed liquid aerosol droplets has been studied directly through the application of side imaging at 90° to the trapping laser beam. In conjunction with imaging in the plane of the optical trap and cavity-enhanced Raman spectroscopy (CERS), the optical forces experienced by a trapped aerosol have been interrogated. By varying the power of the trapping laser and observing changes in the axial position of a trapped particle it has been possible to examine the fine balance between the gradient and scattering forces, a key parameter in optical manipulation. Clear differences observed in sizing trapped particles from bright field microscopy and CERS have been reconciled. As a consequence, a novel technique for probing the evolving size of a single aerosol particle is proposed.

In situ comparative measurements of the properties of aerosol droplets of different chemical composition

Aerosol optical tweezers can be used to manipulate multiple aerosol particles simultaneously. When coupled with spontaneous and stimulated Raman scattering, the composition, size and phase partitioning of different chemical components within a liquid droplet can be investigated. In combination, these two techniques suggest the possibility of a new strategy for characterising the thermodynamic behaviour of aerosols and the kinetics of mass transfer between the gas and condensed phases. We demonstrate here that two droplets can be characterised simultaneously, examining specifically the variation in wet particle size with relative humidity, recording the changes in size with nanometre accuracy. In a further demonstration, we use the size of a sodium chloride droplet to determine the relative humidity of the gas phase, allowing the variation in hygroscopicity of a second aqueous glutaric acid/sodium chloride droplet to be studied. We suggest that such a comparative approach can provide new insights into aerosol dynamics.

The influence of resonant absorption and heating on the equilibrium size of aqueous-solute aerosol droplets

The time-dependent evolution in the equilibrium size of an optically trapped aqueous sodium chloride droplet (>2 microm radius) within an environment of varying relative humidity (RH) is shown to depend on both the depression in vapour pressure due to the presence of the solute and the elevation in temperature due to optical absorption. In particular, the level of optical absorption is highly dependent on the size of the droplet relative to the wavelength of the absorbed light. Thus, as the droplet size tunes into a Mie resonance at the trapping laser wavelength, the increased level of optical absorption leads to an elevation in droplet temperature. This increase in resonant heating can balance a continual increase in RH, leading to only marginal growth in droplet size and change in solute concentration. Once the RH is sufficiently high that the resonance condition can be surpassed, the droplet cools instantaneously and the solute concentration again dominates in determining the vapour pressure, with a rapid increase in size and a decrease in solute concentration returning the droplet to equilibrium with the gas phase RH. Thus, a growing droplet is observed to pass through periods of apparent size stability followed by instantaneous growth, consistent with the variation in absorption efficiency with droplet size. This provides a clear example of the coupling between the optical and physical properties of an aerosol and their influence on the equilibrium state.

Towards airborne optofluidics

This paper details progress towards the possibility of creating integrated optical devices capable of manipulating and analyzing airborne particles in the form of aerosols. We also describe work designed to look at the possibility of controlling optical cavities created using liquid aerosols using light.

Optical manipulation and characterisation of aerosol droplets

Aerosol droplets are trapped and manipulated with a single-beam gradient-force optical trap for timescales of hours. By coupling the optical trap with cavity enhanced Raman scattering, the size of the trapped droplet can be determined with nanometre accuracy and high time resolution. This allows the evolution in droplet size and composition to be monitored during the growth or evaporation of a single trapped droplet, providing a method for characterising the factors that govern aerosol droplet size. The simultaneous trapping of two or more aerosol droplets in parallel optical traps can permit studies of aerosol coagulation.