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Thursday, July 17, 2014

Volatility and Oxidative Ageing of Aqueous Maleic Acid Aerosol Droplets and the Dependence on Relative Humidity

Benjamin J. Dennis-Smither , Frances H. Marshall , Rachael E.H. Miles , Thomas C Preston, and Jonathan Philip Reid

The microphysical structure and heterogeneous oxidation by ozone of single aerosol particles containing maleic acid (MA) has been studied using aerosol optical tweezers and cavity enhanced Raman spectroscopy. The evaporation rate of MA from aqueous droplets has been measured over a range of relative humidities and the pure component vapour pressure determined to be (1.7± 0.2)×10^-3 Pa. Variation in the refractive index (RI) of an aqueous MA droplet with relative humidity (RH) allowed the sub-cooled liquid RI of MA to be estimated as 1.481 ± 0.001. Measurements of the hygroscopic growth are shown to be consistent with equilibrium model predictions from previous studies. Simultaneous measurements of the droplet composition, size and refractive index have been made during ozonolysis at RHs in the range 50 to 80 %, providing insight into the volatility of organic products, changes in the droplet hygroscopicity and optical properties. Exposure of the aqueous droplets to ozone leads to the formation of products with a wide range of volatilities spanning from involatile to volatile. Reactive uptake coefficients show a weak dependence on ozone concentration, but no dependence on RH or salt concentration. The time evolving RI depends significantly on the RH at which the oxidation proceeds and can even show opposing trends; while the RI increases with ozone exposure at low relative humidity, the RI decreases when the oxidation proceeds at high relative humidity. The variations in RI are broadly consistent with a framework for predicting RIs for organic components published by Cappa et al.1 Once oxidised, particles are shown to form amorphous phases on drying rather than crystallisation, with slow evaporation kinetics of residual water.

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