Heterogeneous Reactions of Glyoxal on Particulate Matter: Identification of Acetals and Sulfate Esters

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Abstract
Reactive uptake of glyoxal onto particulate matter has been studied in laboratory experiments in a 2 m3 Teflon reaction chamber. Inorganic seed particles of different composition were utilized, including (NH4)2SO4, (NH4)2SO4/H2SO4, NaNO3, and simulated sea salt, while the relative humidity and acid concentration were varied. The organic composition of the growing particles was measured in situ with an aerosol mass spectrometer, providing particle mass spectra as a means of product identification. Aerosol physical characteristics were also measured with a differential mobility analyzer and condensation nucleus counter. Regardless of seed composition, particle growth was rapid and continuous over the course of several hours. Identification of several mass fragments greater than the glyoxal monomer suggested that heterogeneous reactions to form glyoxal adducts of low volatility had occurred. Temporal analysis of the mass fragments was consistent with a proposed acid-catalyzed mechanism whereby glyoxal is first hydrated, followed by self-reaction to form cyclic acetal structures. Increased relative humidity slowed the formation of higher order oligomers, also consistent with the proposed mechanism. The relative contribution of various oligomers to the overall organic composition was strongly dependent on the relative humidity and hence the particulate water concentration. A mild acid catalysis was also observed upon increasing the acidity of the seed particles. Specific mass fragments were found that could only arise from sulfate esters and were not present on the non-sulfur-containing seed particles. This first evidence of the formation of organic sulfates in particles is presented together with a proposed mechanism and molecular structure. These results suggest that the formation of these products of glyoxal uptake can contribute significantly to secondary organic aerosol.