Molecular Characterization of Secondary Aerosol from Oxidation of Cyclic Methylsiloxanes.

Cyclic volatile methylsiloxanes (cVMS) have been identified as important gas-phase atmospheric contaminants, but knowledge of the molecular composition of secondary aerosol derived from cVMS oxidation is incomplete. Here, the chemical composition of secondary aerosol produced from the OH-initiated oxidation of decamethylcyclopentasiloxane (D5, C10H30O5Si5) is characterized by high performance mass spectrometry. ESI-MS reveals a large number of monomeric (300 < m/z < 470) and dimeric (700 < m/z < 870) oxidation products. With the aid of high resolution and MS/MS, it is shown that oxidation leads mainly to the substitution of a CH3 group by OH or CH2OH, and that a single molecule can undergo many CH3 group substitutions. Dimers also exhibit OH and CH2OH substitutions and can be linked by O, CH2, and CH2CH2 groups. GC-MS confirms the ESI-MS results. Oxidation of D4 (C8H24O4Si4) exhibits similar substitutions and oligomerizations to D5, though the degree of oxidation is greater under the same conditions and there is direct evidence for the formation of peroxy groups (CH2OOH) in addition to OH and CH2OH.