Methanesulfonic Acid-driven New Particle Formation Enhanced by Monoethanolamine: A Computational Study

Abstract

Amines are recognized as significant enhancing species on methanesulfonic acid (MSA)-driven new particle formation (NPF). Monoethanolamine (MEA) has been detected in the atmosphere and its concentration could be significantly increased once MEA-based post-combustion CO2 capture technology is widely implemented. Here, we evaluated the enhancing potential of MEA on MSA-driven NPF by examining the formation of MEA-MSA clusters using a combination of quantum chemical calculations and kinetics modeling. The results indicate that-OH group of MEA can form at least one hydrogen bond with MSA or MEA in all MEA-containing clusters. The enhancing potential of MEA is higher than that of the strongest enhancing agent known so far, methylamine (MA), for MSA-driven NPF. Such high enhancing potential can be ascribed to not only the higher gas-phase basicity, but also the role of the additional-OH group of MEA in increasing the binding free energy by forming additional hydrogen bonds. This clarifies the importance of hydrogen-bonding capacity from the non-amino group of amines in enhancing MSA-driven NPF. The main growth pathway for MEA-MSA clusters proceeds via the initial formation of the (MEA)1(MSA)1 cluster, followed by alternately adding one MSA and one MEA molecule, differing from the case of MA-MSA clusters.

Characterization of aerosol number size distributions and their effect on cloud properties at Syowa Station, Antarctica

“…Because of low aerosol number concentrations in the Antarctic FT (Hara et al, 2011a), NPF can proceed preferentially in the FT if condensable vapor is present. Earlier studies presented that the following condensable vapors participate in tropospheric NPF: H 2 SO 4 , CH 3 SO 3 H, NH 3 , iodine species such as HIO 3 , and amines (Yu et al, 2012;Kulmala et al, 2013;Kyrö et al, 2013;Weller et al, 2015;Sipilä et al, 2016;Jen et al, 2016;Jokinen et al, 2018;Shen et al, 2019;Burrell et al, 2019). Actually, these vapors were identified along the Antarctic coasts and the Southern Ocean (Jefferson et al, 1998a, b;Sipilä et al, 2016;Jokinen et al, 2018;Dall'Osto et al, 2019).…”

“…Earlier studies presented that the following condensable vapors participate in tropospheric NPF: H 2 SO 4 , CH 3 SO 3 H, NH 3 , iodine species such as HIO 3 , and amines (Yu et al, 2012;Kulmala et al, 2013;Kyrö et al, 2013;Weller et al, 2015;Sipilä et al, 2016;Jen et al, 2016;Jokinen et al, 2018;Shen et al, 2019;Burrell et al, 2019). Actually, these vapors were identified along the Antarctic coasts and the Southern Ocean (Jefferson et al, 1998a, b;Sipilä et al, 2016;Jokinen et al, 2018;Dall'Osto et al, 2019). High contributions of photochemical processes in the atmosphere were required for an important relation among J 5 , aerosol size distributions, and CN concentrations.…”

“…Knowledge and discussion of condensable vapors (i.e., aerosol precursors) is fundamentally important to elucidate microphysical processes such as NPF and growth and locations at which NPF occurs. Earlier works have emphasized examination of the following condensable vapors (i.e., aerosol precursors) for NPF and particle growth: H 2 SO 4 , CH 3 SO 3 H, HIO 3 , NH 3 , amines, and other organics with low vapor pressure (Yu et al, 2012;Kulmala et al, 2013;Kyrö et al, 2013;Weller et al, 2015;Sipilä et al, 2016;Jen et al, 2016;Jokinen et al, 2018;Shen et al, 2019;Burrell et al, 2019). Gaseous H 2 SO 4 has been regarded as an important aerosol precursor (e.g., Kulmala et al, 2013;Kerminen et al, 2018).…”

“…Recently, simultaneous measurements of aerosol precursors and aerosol size distributions showed that H 2 SO 4 and NH 3 made important contributions to NPF and growth at Aboa in air masses from the marine boundary layer (Jokinen et al, 2018). Condensable vapors other than H 2 SO 4 and NH 3 , for example, iodine compounds such as HIO 3 and organics, are associated with atmospheric and snowpack chemistry (e.g., Saiz-Lopez et al, 2008;Atkinson et al, 2012;Roscoe et al, 2015;Sipilä et al, 2016;Hara et al, 2020) and oceanic bioactivity (Dall'Osto et al, 2019). Contributions of the condensable vapors to NPF and growth have been discussed, but this topic has remained unclear for the Antarctic.…”

The Role of Organic Acids in New Particle Formation from Methanesulfonic Acid and Methylamine

“…Atmospheric bases can enhance both SA-driven and MSA-driven NPF by stabilizing freshly formed molecular clusters via acid-base proton transfer reactions (Zhang et al, 2012;Almeida et al, 2013;Chen et al, 2020b;Perraud et al, 2020b;Perraud et al, 2020a;Kurten et al, 2008;Loukonen et al, 2010;Glasoe et al, 2015;Olenius et al, 2017;Ma et al, 2019b;Zuo et al, 2021;Shen et al, 2020;Shen et al, 2019;Chen et al, 2020a;Xu et al, 2020;Nishino et al, 2014). Amines have been shown to be much more efficient stabilizing species compared to ammonia for both SA-base and MSA-base cluster formation (Almeida et al, 2013;Kurten et al, 2008;Chen et al, 2020b;Perraud et al, 2020a;Shen et al, 2020;Chen et al, 2016).…”