Abstract
Abstract. Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<1% for all amines tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.
Highlights
Amines are found to be emitted into the atmosphere by a variety of anthropogenic and biogenic sources including automobile emissions, waste treatment facilities, and agricultural animal operations (Westerholm et al, 1993; Manahan, 1990; Schade and Crutzen, 1995)
Recent work has attempted to shed light on the processes that lead to the presence of amines in the aerosol-phase through mass spectrometry studies of aerosol generated in smog chambers
Particle formation was observed immediately after injection of methylamine into the clean reactors (Fig. 2). These particles result from the formation of methylaminium nitrate produced by reaction of methylamine with trace amounts of NOx present in the chamber
Summary
Removal routes for amines from the atmosphere include reactions with either nitric or sulfuric acid to form the corresponding nitrate salts or oxidation by OH, O3, and NO3 (Seinfeld and Pandis, 1998; Finlayson-Pitts and Pitts, 2000; Silva et al, 2008). Imines’ are believed to undergo reactions leading to formation of aldehyde products It is possible for these oxidation products to have a low enough vapor pressure to condense onto existing particles or form new particles by nucleating, creating secondary organic aerosol (SOA). Recent work has attempted to shed light on the processes that lead to the presence of amines in the aerosol-phase through mass spectrometry studies of aerosol generated in smog chambers. These studies have shown that most particles generated from amines are in the form of alkyl nitrate salts (Angelino et al, 2001). This paper investigates secondary particle formation from other commonly emitted primary amines
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