Functional group analysis of high-molecular weight compounds in the water-soluble fraction of organic aerosols

In this study, we present the analysis of functional groups of humic-like substances (HULIS) isolated from atmospheric aerosols (<1 μm). Aerosol samples were collected in an urban area (Dübendorf, Switzerland) both in summer and winter. Quantification of carboxylic, arylic, phenolic and aliphatic functional groups of HULIS was performed by a specially adapted and optimized H-NMR method. The concentrations of carboxylic, arylic, phenolic and aliphatic functional groups were between 9×10⁻¹¹ and 6×10⁻⁸ mol/m³ for all samples, corresponding up to 14% of the total HULIS mass. A good correlation between the H-NMR results and the potentiometric titration of carboxylic groups was observed for all winter and summer samples. The pK distributions of carboxylic groups of HULIS were calculated from potentiometric titration data. pK spectra showed that pK values of most carboxylic groups is between 3 and 5. The H-NMR data show that the content of aromatic groups is higher in winter than in summer. This may either be due to emission of aromatic compounds by wood burning or to slower degradation reaction of aromatics in winter.