Detection of atmospheric gaseous amines and amides by a high resolution time-of-flight chemical ionization mass spectrometer with protonated ethanol reagent ions

Amines and amides are important atmospheric organic-nitrogen compounds but high time resolution, highly sensitive, and simultaneous ambient measurements of these species are rather sparse. Here, we present the development of a high resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) method utilizing protonated ethanol as reagent ions to simultaneously detect atmospheric gaseous amines (C1 to C6) and amides (C1 to C6). This method possesses sensitivities of 5.6–19.4 Hz pptv−1 for amines and 3.8–38.0 Hz pptv−1 for amides under total reagent ion signals of ~ 0.32 MHz, and detection limits of 0.10–0.50 pptv for amines and 0.29–1.95 pptv for amides at 3σ of the background signal for a 1-min integration time, respectively. Controlled characterization in the laboratory indicates that relative humidity has significant influences on detection of amines and amides, whereas the presence of organics has no obvious effects. Ambient measurements of amines and amides utilizing this method were conducted from 25 July 2015 to 25 August 2015 in urban Shanghai, China. While the concentrations of amines ranged from a few pptv to hundreds of pptv, concentrations of amides varied from tens of pptv to a few ppbv. Among the C1- to C6-amines, the C2-amines were the dominant species with concentrations up to 130 pptv. For amides, the C3-amides (up to 8.7 ppb) were the most abundant species. The diurnal profiles of amines and amides suggest that in addition to the secondary formation of amides in the atmosphere, industrial emissions could be important sources of amides in urban Shanghai. During the campaign, photo-oxidation of amines and amides might be a main loss pathway for them in day time, and wet deposition was also an important sink.