Estimating the Lower Limit of the Impact of Amines on Nucleation in the Earth’s Atmosphere

Abstract

Amines, organic derivatives of NH3, are important common trace atmospheric species that can enhance new particle formation in the Earth's atmosphere under favorable conditions. While methylamine (MA), dimethylamine (DMA) and trimethylamine (TMA) all efficiently enhance binary nucleation, MA may represent the lower limit of the enhancing effect of amines on atmospheric nucleation. In the present paper, we report new thermochemical data concerning MA-enhanced nucleation, which were obtained using the DFT PW91PW91/6-311++G (3df, 3pd) method, and investigate the enhancement in production of stable pre-nucleation clusters due to the MA. We found that the MA ternary nucleation begins to dominate over ternary nucleation of sulfuric acid, water and ammonia. This means that under real atmospheric conditions ([MA] ~ 1 ppt, [NH3] ~ 1 ppb) the lower limit of the enhancement due to methylamines is either close to or higher than the typical effect of NH3. A very strong impact of the MA is observed at low RH; however it decreases quickly as the RH grows. Low RH and low ambient temperatures were found to be particularly favorable for the enhancement in production of stable sulfuric acid-water clusters due to the MA.

Quantitation of 11 alkylamines in atmospheric samples: separating structural isomers by ion chromatography

“…Theoretical calculations and studies have also found that amines have a high disposition to form atmospheric nanoparticles (Barsanti et al, 2009;Kurtén et al, 2008;Loukonen et al, 2014Loukonen et al, , 2010Nadykto et al, 2015;Ortega et al, 2012). From these works, alkylamines have been shown to form clusters via neutralization reactions at rates up to 3 orders of magnitude greater than ammonia (Almeida et al, 2013;Berndt et al, 2010;Bzdek et al, 2011;Kurtén et al, 2008;Loukonen et al, 2010;Nadykto et al, 2015) and readily exchange with ammonium in ammonium-bisulfate molecular clusters (Bzdek et al, 2010;Lloyd et al, 2009;Qiu et al, 2011). These studies suggest that alkylamines can compete with ammonia to form particles even though they have been quantified at mixing ratios that are 3 or more orders of magnitude lower in the atmosphere (Chang et al, 2003;Ge et al, 2011;Schade and Crutzen, 1995).…”

“…Multiple laboratory investigations have shown the nucleation potential of methyl-and ethyl-substituted amines through gaseous acid-base chemistry reactions (Almeida et al, 2013;Angelino et al, 2001;Berndt et al, 2010Berndt et al, , 2014Bzdek et al, 2010Bzdek et al, , 2011Erupe et al, 2011;Jen et al, 2016a, b;Lloyd et al, 2009;Murphy et al, 2007;Qiu et al, 2011;Silva et al, 2008;Smith et al, 2010;Wang et al, 2010a, b;Yu et al, 2012;Zhao et al, 2011;Zollner et al, 2012). Theoretical calculations and studies have also found that amines have a high disposition to form atmospheric nanoparticles (Barsanti et al, 2009;Kurtén et al, 2008;Loukonen et al, 2014Loukonen et al, , 2010Nadykto et al, 2015;Ortega et al, 2012). From these works, alkylamines have been shown to form clusters via neutralization reactions at rates up to 3 orders of magnitude greater than ammonia (Almeida et al, 2013;Berndt et al, 2010;Bzdek et al, 2011;Kurtén et al, 2008;Loukonen et al, 2010;Nadykto et al, 2015) and readily exchange with ammonium in ammonium-bisulfate molecular clusters (Bzdek et al, 2010;Lloyd et al, 2009;Qiu et al, 2011).…”

Phosphoric acid – a potentially elusive participant in atmospheric new particle formation

“…It is certain that sulfuric acid is a key component [2], but another stabilizing compound is required to explain observed new particle formation rates [3,4]. The predominantly investigated stabilizers are bases such as ammonia [5][6][7][8][9][10][11][12] and monoamines [13][14][15][16][17][18][19][20][21][22][23]. Amines have been shown to have an especially strong interaction with sulfuric acid, with a few ppt of dimethylamine yielding new particle formation rates of up to three orders of magnitude higher than ammonia [24].…”

Identification of the Relation and System aticresearch of The Nature of Intermolecular Interactions and Acquired Physical Properties of Objects formed.

“…The stability of the positively charged clusters containing sulphuric acid, water and ammonia were studied using the density functional theory (DFT) in the work 4 . It is shown that under normal conditions of the boundary layer of the atmosphere a considerable part of the positive ions may include ammonia, while the majority of neutral and negative ions contain no ammonia.…”