ToF-SIMS characterization of glyoxal surface oxidation products by hydrogen peroxide: A comparison between dry and liquid samples

As one of the simplest volatile organic compounds, glyoxal and its oxidation products were considered to be important precursors to aqueous secondary organic aerosol formation. Herein, we analyzed products from glyoxal oxidation by hydrogen peroxide in dry and liquid samples using time-of-flight secondary ion mass spectrometry (ToF-SIMS). ToF-SIMS spectra and spectral principal component analysis (PCA) were used to investigate surface oxidation products. Dry samples were prepared on clean silicon wafers. Liquid samples consisting of glyoxal and hydrogen peroxide (H₂O₂) were introduced to a vacuum compatible microfluidic reactor prior to UV illumination or dark aging followed by in situ liquid SIMS analysis. A number of reaction products were observed in both dry and liquid samples; different oligomers and carboxylic acids could be formed depending on reaction conditions. In addition, hydrolyzed products were observed in the liquid samples, but not in the dry samples. Although dry samples reveal some products of the aqueous process, they are not fully representative as results from those of the aqueous samples. Our findings suggest that the ability to characterize the liquid surface reaction products provides more realistic information of the reaction products associated with aqueous secondary organic aerosol formation in the atmosphere. Meanwhile, the high mass resolution spectra from the dry sample SIMS measurement are helpful to identify oxidation products in the liquid samples.