Optical extinction efficiency measurements on fine and accumulation mode aerosol using single particle cavity ring-down spectroscopy

A new experiment is presented for the measurement of single aerosol particle extinction efficiencies, Q<inf>ext</inf>, combining cavity ring-down spectroscopy (CRDS, λ = 405 nm) with a Bessel beam trap (λ = 532 nm) in tandem with phase function (PF) measurements. This approach allows direct measurements of the changing optical cross sections of individual aerosol particles over indefinite time-frames facilitating some of the most comprehensive measurements of the optical properties of aerosol particles so far made. Using volatile 1,2,6-hexanetriol droplets, Q<inf>ext</inf> is measured over a continuous radius range with the measured Q<inf>ext</inf> envelope well described by fitted cavity standing wave (CSW) Mie simulations. These fits allow the refractive index at 405 nm to be determined. Measurements are also presented of Q<inf>ext</inf> variation with RH for two hygroscopic aqueous inorganic systems ((NH<inf>4</inf>)<inf>2</inf>SO<inf>4</inf> and NaNO<inf>3</inf>). For the PF and the CSW Mie simulations, the refractive index, n<inf>λ</inf>, is parameterised in terms of the particle radius. The radius and refractive index at 532 nm are determined from PFs, while the refractive index at 405 nm is determined by comparison of the measured Q<inf>ext</inf> to CSW Mie simulations. The refractive indices determined at the shorter wavelength are larger than at the longer wavelength consistent with the expected dispersion behaviour. The measured values at 405 nm are compared to estimates from volume mixing and molar refraction mixing rules, with the latter giving superior agreement. In addition, the first single-particle Q<inf>ext</inf> measurements for accumulation mode aerosol are presented for droplets with radii as small as ∼300 nm.