Measuring rates of reaction in supercooled organic particles with implications for atmospheric aerosol

Abstract

The kinetics of heterogeneous reactions involving supercooled organic droplets is reported for the first time. Reactions between ozone and internally-mixed sub-micrometre particles containing an unsaturated alkenoic acid, oleic acid, and an n-alkanoic acid, myristic acid, were studied as a simple model for the oxidation of meat-cooking aerosol. The reactions were followed by monitoring the rate of oleic acid loss using an Aerosol CIMS (chemical ionization mass spectrometry) instrument for real-time particle analysis. Evidence of as much as 32 °C supercooling at room temperature was observed depending on particle composition. FTIR spectra of the aerosol also demonstrate features indicative of supercooling. Particles in which crystallization was induced by cooling below room temperature demonstrated decreased reactivity by a factor of 12 compared to supercooled particles of the same composition. This drastic difference in reactivity could have significant implications for the lifetimes of reactive species in ambient aerosol as well as for the accurate source apportionment of particulate matter.