Secondary aerosol formation from atmospheric reactions of aliphatic amines

Abstract

Abstract. Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NO x with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R 3 NH + ) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant nonsalt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

Single particle analysis of amines in ambient aerosol in Shanghai

“…They can also undergo photooxidation and oxidation reactions with OH radicals, NO 3 radicals and O 3 in the ambient atmosphere to form non-volatile aerosol components. [13,[18][19][20] De Haan et al [21,22] observed that reactions between glyoxal and amines or amino acids can produce light-absorbing, nitrogen-containing imidazoles and oligomers. Particle phase amines have been extensively observed in many areas [9,17,[23][24][25] especially in ultrafine particles during nucleation [26][27][28] and particle growth [29] events.…”

“…Because of the high vapour pressures of low-molecular-weight amines, over 150 gaseous amines [5,6] have been identified in the atmosphere from both natural and anthropogenic sources including animal husbandry, waste incineration and sewage treatment, marine sources and vehicle exhaust. [7][8][9][10][11][12] Gaseous amine concentrations are usually at least an order of magnitude lower than that of ammonia in the atmosphere, [13] but they can reach as high as 23 % of that of ammonia in animal husbandry environments. [14] The mass concentration of gaseous amines varies from 0.3-4.2 ng m À3 in the marine atmosphere [15] to 70.4-561.4 mg m À3 near a commercial dairy.…”

“…[14] The mass concentration of gaseous amines varies from 0.3-4.2 ng m À3 in the marine atmosphere [15] to 70.4-561.4 mg m À3 near a commercial dairy. [16] Being strong gaseous bases and soluble in water, amines undergo acid-base reactions with nitric and sulfuric acid [13,17] to form low-volatility aminium salts. They can also undergo photooxidation and oxidation reactions with OH radicals, NO 3 radicals and O 3 in the ambient atmosphere to form non-volatile aerosol components.…”

Measurement of neutral sulfuric acid-dimethylamine clusters using CI-APi-TOF-MS

“…Such compounds could be amines of which a huge variety has been identified in the atmosphere 7 . Amines have already been predicted as likely candidates enhancing the nucleation rates based on quantum-chemical studies 8,9 and it has been observed that they contribute in the formation of secondary aerosol 10,11 . Laboratory studies as well as atmospheric measurements have also revealed that amines enhance ternary nucleation [12][13][14] .…”

Ideas and perspectives: on the emission of amines from terrestrial vegetation in the context of new atmospheric particle formation

“…The importance of amines for NPF has recently been established by field (Angelino et al, 2001;Makela et al, 2001;Smith et al, 2010;Zhao et al, 2011) and laboratory experiments (Murphy et al, 2007;Berndt et al, 2010;Erupe et al, 2011;Bzdek et al, 2010;Zhao et al, 2011;Yu et al, 2012;Zollner et al, 2012;Almeida et al, 2013;Jen et al, 2014;Kurten et al, 2014), as well as from modelling studies (Kurten et al, 2008;Barsanti et al, 2009;Bzdek et al, 2010;Ortega et al, 2012;Loukonen et al, 2010;Nadykto et al, 2011;Paasonen et al, 2012;Almeida et al, 2013;DePalma et al, 2014). On a molecular level, Kurten et al (2014) observed how DMA stabilises SA, increasing the stable cluster concentration by up to 6 orders of magnitude.…”