Characterization of Imidazole Compounds in Aqueous Secondary Organic Aerosol Generated from Evaporation of Droplets Containing Pyruvaldehyde and Inorganic Ammonium

Abstract

Imidazole compounds are important constituents of atmospheric brown carbon. The imidazole components of aqueous secondary organic aerosol (aqSOA) that are generated from the evaporation of droplets containing pyruvaldehyde and inorganic ammonium are on-line characterized by an aerosol laser time-of-flight mass spectrometer (ALTOFMS) and off-line detected by optical spectrometry in this study. The results demonstrated that the laser desorption/ionization mass spectra of aqSOA particles that were detected by ALTOFMS contained the characteristic mass peaks of imidazoles at m/z = 28 (CH2N+), m/z = 41 (C2H3N+) and m/z = 67 (C3H4N2+). Meanwhile, the extraction solution of the aqSOA particles that were measured by off-line techniques showed that the characteristic absorption peaks at 217 nm and 282 nm appeared in the UV-Vis spectrum, and the stretching vibration peaks of C-N bond and C=N bond emerged in the infrared spectrum. Based on these spectral information, 4-methyl-imidazole and 4-methyl-imidazole-2-carboxaldehyde are identified as the main products of the reaction between pyruvaldehyde and ammonium ions. The water evaporation accelerates the formation of imidazoles inside the droplets, possibly owing to the highly concentrated environment. Anions, such as F−, CO32−, NO3−, SO42− and Cl− in the aqueous phase promote the reaction of pyruvaldehyde and ammonium ions to produce imidazole products, resulting in the averaged mass absorption coefficient (<MAC>) in the range of 200–600 nm of aqSOA increases, and the order of promotion is: F− > CO32− > SO42− ≈ NO3− ≈ Cl−. These results will help to analyze the constituents and optics of imidazoles and provide a useful basis for evaluating the formation process and radiative forcing of aqSOA particles.