Aerosol Formation from OH Oxidation of the Volatile Cyclic Methyl Siloxane (cVMS) Decamethylcyclopentasiloxane

Abstract

Aerosol formation from OH oxidation of decamethylcyclopentasiloxane (D₅, C₁₀H₃₀O₅Si₅), a cyclic volatile methyl siloxane (cVMS) found in consumer products, was studied in a flow-through photo-oxidation chamber with and without the presence of ammonium sulfate seed aerosol. For the unseeded experiments, chemical characterization with high-performance mass spectrometry showed that the molecular composition changed substantially with aerosol mass loading in the 1-12 μg/m³ range. Monomers (5 Si atoms/molecule) and dimers (10 Si atoms/molecule) dominated the mass spectra of aerosols at higher mass loadings, while ring-opened species (neither 5 nor 10 Si atoms/molecule) dominated the mass spectra of aerosols at lower mass loadings. Molecular signal intensity dependencies upon the aerosol volume/surface area ratio suggest that non-volatile ring-opened species are formed in the gas phase and assist particle formation through condensation, while dimers are formed by accretion reactions within the particle phase as the particles grow. These conclusions are supported by experiments in the presence of seed aerosol with a similar siloxane aerosol mass loading but higher volume/surface area ratio, where ring-opened species are much less prevalent than monomers or dimers and the aerosol yield is higher. Because of the importance of accretion chemistry, the aerosol yield from D₅ oxidation is likely to be strongly dependent upon the particle size and morphology.