Michael I. Cotterell

Measurements of the evaporation and hygroscopic response of single fine-mode aerosol particles using a Bessel beam optical trap.

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

Comparison of Methods for Predicting the Compositional Dependence of the Density and Refractive Index of Organic–Aqueous Aerosols

Representing the physicochemical properties of aerosol particles of complex composition is of crucial importance for understanding and predicting aerosol thermodynamic, kinetic, and optical properties and processes and for interpreting and comparing analysis methods. Here, we consider the representations of the density and refractive index of aqueous-organic aerosol with a particular focus on the dependence of these properties on relative humidity and water content, including an examination of the properties of solution aerosol droplets existing at supersaturated solute concentrations. Using bulk phase measurements of density and refractive index for typical organic aerosol components, we provide robust approaches for the estimation of these properties for aerosol at any intermediate composition between pure water and pure solute. Approximately 70 compounds are considered, including mono-, di- and tricarboxylic acids, alcohols, diols, nitriles, sulfoxides, amides, ethers, sugars, amino acids, aminium sulfates, and polyols. We conclude that the molar refraction mixing rule should be used to predict the refractive index of the solution using a density treatment that assumes ideal mixing or, preferably, a polynomial dependence on the square root of the mass fraction of solute, depending on the solubility limit of the organic component. Although the uncertainties in the density and refractive index predictions depend on the range of subsaturated compositional data available for each compound, typical errors for estimating the solution density and refractive index are less than ±0.1% and ±0.05%, respectively. Owing to the direct connection between molar refraction and the molecular polarizability, along with the availability of group contribution models for predicting molecular polarizability for organic species, our rigorous testing of the molar refraction mixing rule provides a route to predicting refractive indices for aqueous solutions containing organic molecules of arbitrary structure.

Direct measurements of the optical cross sections and refractive indices of individual volatile and hygroscopic aerosol particles.

We present measurements of the evolving extinction cross sections of individual aerosol particles (spanning 700-2500 nm in radius) during the evaporation of volatile components or hygroscopic growth using a combination of a single particle trap formed from a Bessel light beam and cavity ring-down spectroscopy. For single component organic aerosol droplets of 1,2,6-hexanetriol, polyethylene glycol 400, and glycerol, the slow evaporation of the organic component (over time scales of 1000 to 10,000 s) leads to a time-varying size and extinction cross section that can be used to estimate the refractive index of the droplet. Measurements on binary aqueous-inorganic aerosol droplets containing one of the inorganic solutes ammonium bisulfate, ammonium sulfate, sodium nitrate, or sodium chloride (over time scales of 1000 to 15,000 s) under conditions of changing relative humidity show that extinction cross-section measurements are consistent with expectations from accepted models for the variation in droplet refractive index with hygroscopic growth. In addition, we use these systems to establish an experimental protocol for future single particle extinction measurements. The advantages of mapping out the evolving light extinction cross-section of an individual particle over extended time frames accompanied by hygroscopic cycling or component evaporation are discussed.

Assessing the accuracy of complex refractive index retrievals from single aerosol particle cavity ring-down spectroscopy

ABSTRACT Cavity ring-down spectroscopy (CRDS) of single, optically manipulated aerosol particles affords quantitative retrieval of refractive indices for particles of fixed or evolving composition with high precision. Here, we quantify the accuracy with which refractive index determinations can be made by CRDS for single particles confined within the core of a Bessel laser beam and how that accuracy is degraded as the particle size is progressively reduced from the coarse mode (>1 μm radius) to the accumulation mode (<500 nm radius) regime. We apply generalized Lorenz–Mie theory to the intra-cavity standing wave to explore the effect of particle absorption on the distribution of extinction cross section determinations resulting from stochastic particle motion in the Bessel beam trap. The analysis provides an assessment of the accuracy with which the real, n, and imaginary, κ, components of the refractive index can be determined for a single aerosol particle. Published with license by American Association for Aerosol Research Video abstract Read the transcript Watch the video on Vimeo

Extinction cross section measurements for a single optically trapped particle

Bessel beam (BB) optical traps have become widely used to confine single and multiple aerosol particles across a broad range of sizes, from a few microns to < 200 nm in radius. The radiation pressure force exerted by the core of a single, zeroth-order BB incident on a particle can be balanced by a counter-propagating gas flow, allowing a single particle to be trapped indefinitely. The pseudo non-diffracting nature of BBs enables particles to be confined over macroscopic distances along the BB core propagation length; the position of the particle along this length can be finely controlled by variation of the BB laser power. This latter property is exploited to optimize the particle position at the center of the TEM00 mode of a high finesse optical cavity, allowing cavity ring-down spectroscopy (CRDS) to be performed on single aerosol particles and their optical extinction cross section, σext, measured. Further, the variation in the light from the illuminating BB elastically scattered by the particle is recorded as a function of scattering angle. Such intensity distributions are fitted to Lorenz-Mie theory to determine the particle radius. The trends in σext with particle radius are modelled using cavity standing wave Mie simulations and a particle’s varying refractive index with changing relative humidity is determined. We demonstrate σext measurements on individual sub-micrometer aerosol particles and determine the lowest limit in particle size that can be probed by this technique. The BB-CRDS method will play a key role in reducing the uncertainty associated with atmospheric aerosol radiative forcing, which remains among the largest uncertainties in climate modelling.

Measurements of the imaginary component of the refractive index of weakly absorbing single aerosol particles

The interaction of atmospheric aerosols with radiation remains a significant source of uncertainty in modeling radiative forcing. Laboratory measurements of the microphysical properties of atmospherically relevant particles is one approach to reduce this uncertainty. We report a new method to investigate light absorption by a single aerosol particle, inferring changes in the imaginary part of the refractive index with a change in environmental conditions (e.g., relative humidity) and inferring the size dependence of the optical extinction cross section. More specifically, we present measurements of the response of single aerosol particles to near-infrared (NIR) laser-induced heating at a wavelength of 1520 nm. Particles were composed of aqueous NaCl or (NH4)2SO4 and were studied over ranges in relative humidity (40-85%), particle radius (1-2.2 μm), and NIR laser power. The ensuing size change and real component of the refractive index were extracted from measurements of the angular variation in elastically scattered light. From the heating-induced size change at varying NIR beam intensities, we retrieved the change in the imaginary component of the refractive index. In addition, cavity ring-down spectroscopy measurements monitored the change in extinction cross section with modulation of the heating laser power.

Aerosol optical chromatography and measurements of light extinction by single particles

To resolve some of the significant uncertainties in the impact of aerosols on global climate, new tools are required to probe light scattering and absorption by aerosol particles. Ideally, such tools should allow direct measurements on individual particles over extended periods of time, providing data to better constrain the optical properties of aerosol, how they depend on the environmental conditions (relative humidity and temperature) and how they change with time. Here, we present a new technique using a combination of a Bessel beam to manipulate individual particles and cavity ringdown spectroscopy for ultrasensitive measurements of the optical extinction. We show that particles can be spatially separated along the propagation direction of a Bessel beam according to their size and refractive index when confined by a Bessel beam core and a counter-propagating gas flow, referred to as optical chromatography. The time-dependent position of a particle is shown to be a consequence of the differing size dependencies of the forces arising from Stokes drag and radiation pressure. We also show that particles captured in a Bessel beam can be moved in and out of an optical cavity formed by two highly reflective mirrors. The time constant for the ringdown in light coupled within the cavity can then be used to measure the optical cross-section of the individual particle with high accuracy. An individual particle can be captured indefinitely and its change in optical cross-section measured with change in environmental conditions.