Abstract
Abstract. 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. Meanwhile, the detection limits were 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. Controlled characterization in the laboratory indicates that relative humidity has significant influences on the 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 to 25 August 2015 in urban Shanghai, China. While the concentrations of amines ranged from a few parts per trillion by volume to hundreds of parts per trillion by volume, concentrations of amides varied from tens of parts per trillion by volume to a few parts per billion by volume. 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 and backward trajectory analysis profiles of 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 daytime, and wet deposition was also an important sink.
Highlights
Amines and amides are nitrogen-containing organic compounds widely observed in the atmosphere (Cape et al, 2011; Cheng et al, 2006; Ge et al, 2011; Laskin et al, 2009; Rogge et al, 1991;)
Measurements by an ambient pressure proton transfer mass spectrometer (AmPMS) in urban Atlanta showed that TMA was the most abundant amine species and that the concentration of DMA was ∼ 3 pptv (Hanson et al, 2011)
Since a large number of ambient organics can be detected by this protonated ethanol reagent ion methodology as shown later, laboratory measurements of amines and amides in presence of and in absence of organics formed from photooxidation of α-pinene and p-xylene, respectively, were carried out to examine the influence of organics on detection of amines and amides
Summary
Amines and amides are nitrogen-containing organic compounds widely observed in the atmosphere (Cape et al, 2011; Cheng et al, 2006; Ge et al, 2011; Laskin et al, 2009; Rogge et al, 1991;). Detection of gaseous alkyl amines were conducted in Toronto, Canada, using an ambient ion monitor ion chromatography system, and the concentrations of DMA, and TMA+DEA were both less than 2.7 pptv (parts per trillion by volume; VandenBoer et al 2011). Measurements by an ambient pressure proton transfer mass spectrometer (AmPMS) in urban Atlanta showed that TMA (or isomers or amide) was the most abundant amine species and that the concentration of DMA was ∼ 3 pptv (Hanson et al, 2011). A HR-ToF-CIMS method utilizing protonated ethanol as reagent ions has been developed to simultaneously detect atmospheric gaseous amines (C1 to C6) and amides (C1 to C6). The potential sources and sinks of amines and amides are discussed
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