The Role of Oxalic Acid in New Particle Formation from Methanesulfonic Acid, Methylamine, and Water

Arquero, Kristine D.; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

doi:10.1021/acs.est.6b05056

Cited by 61 publications

(70 citation statements)

References 94 publications

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“…Numerous lab experiments and quantum chemical calculations reported amines play an important role in atmospheric nucleation and the growth of new particles (Zhang et al, 2012;Jen et 5 al., 2014;Chen et al, 2015aChen et al, , b, 2017Olenius et al, 2017), and oxalic acid, one of the most abundant dicarboxylic acids, was also proposed to be involved in NPF, and to be more readily bound to methylamine than to ammonia (Guo et al, 2016;Arquero et al, 2017;Hong et al, 2018). So far, it has been a challenge to accurately measure the mass concentrations of aminiums and oxalate in nucleation mode particles (Bzdek et al, 2013;Tao et al, 2016).…”

Section: The Roles Of Amines and Oxalic Acid In Growing New Particlesmentioning

confidence: 99%

“…The observation in the eastern Pacific Ocean revealed that an increase in gaseous precursors of amines and DMS affected the particulate chemical composition and cloud properties (Sorooshian et al, 2009). Lab studies showed that reactions of methanesulfonic acid (MSA) 25 and amines can generate new particles, even in the absence of sulfuric acid (Chen et al, 2015 a,b;Arquero et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

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New particle formation in marine atmosphere during seven cruise campaigns

Zhu

Shen

et al. 2018

Preprint

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Abstract. To study the particle number concentration, size distribution and new particle formation (NPF) events in marine atmosphere, we made measurements during six cruise campaigns over the marginal seas of China in 2011-2016 and one 10 campaign from the marginal seas to the Northwest Pacific Ocean (NWPO) in 2014. We observed relatively frequent NPF events in the atmosphere over the marginal seas of China, i.e., 23 out of 126 observational days with the highest occurrence frequency in fall, followed by spring and summer. 22 out of 23 NPF events were analyzed to be associated with the long-range transport of continental pollutants based on 24-hr air mass back trajectories and the pre-existing particle number concentrations largely exceeding the clean marine background, leaving one much weaker NPF event to be likely induced by oceanic precursors 15 alone and supported by multiple independent evidences. Although the long-range transport signal of continental pollutants can be clearly observed in the remote marine atmosphere over the NWPO, NPF events were observed only in 2 days out of 36 days. The nucleation mode particles (<30 nm), however, accounted for as high as 40%13% of the total particle number concentration during the NWPO cruise campaign, implying that there were many undetected NPF events in the sea-level atmosphere or above. 20To better characterize NPF events, we introduced a term, i.e., the net maximum increase in nucleation mode particles number concentration (NMINP) and correlated it with formation rate of new particles (FR). We found a moderately good linear correlation between NMINP and FR at FR 8 cm -3 s -1 , but there was no correlation at FR >8 cm -3 s -1. The possible mechanisms were argued in terms of roles of different vapor precursors. We also found a ceiling existing for the growth of new particles from 10 nm to larger size in most of NPF events. We thereby introduce a term, i.e., the maximum geometric 25 median diameter of new particles (Dpgmax) and correlate it with the growth rate of new particles (GR). A moderately good linear correlation was also obtained between Dpgmax and GR, and only GR larger than 7.9 nm h -1 can lead to new particles growing with Dpgmax beyond 50 nm. Combining simultaneous measurements of the particle number size distributions and cloud condensation nuclei (CCN) at different super saturations (SS), we indeed observed a clear increase in CCN when the Dpg of new particles exceeded 50 nm at SS=0.4%. However, it was not the case for SS=0.2%. Consistent with previous studies in 30 continental atmosphere, our results implied that 50 nm can be used as the threshold for new particles to be activated as CCN in the marine atmosphere. Moreover, the κ decreased from 0.4 to 0.1 during the growth period of new particles, implying that Atmos. Chem. Phys. Discuss., https://doi

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Section: The Roles Of Amines and Oxalic Acid In Growing New Particlesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

New particle formation in marine atmosphere during seven cruise campaigns

Zhu

Shen

et al. 2018

Preprint

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“…Similarly, Ortega et al 59,62 reported structures and evaporation rates for negatively and positively charged clusters containing up to four H 2 SO 4 and four DMA molecules and up to five H 2 SO 4 and five NH 3 molecules. A thermochemical analysis approach to the ternary ionic (HSO 4 À )(H 2 SO 4 ) m (NH 3 ) k (H 2 O) n (m = n r 3, k = 1, 2) clusters was reported by Herb et al 63 Recently, Finlayson-Pitts and coworkers [64][65][66][67][68][69] carried out a series of studies on the formation and growth of particles from the reactions of methanesulfonic acid (MSA, CH 3 SO 3 H) with ammonia and amines, all of which have been measured in the atmosphere. [70][71][72][73][74][75][76][77][78][79][80][81][82] Calculations on small clusters of MSA with ammonia or amines have been carried out, 41,42,56,64,65,69 but insight into the structures of the nanoparticles formed is still lacking.…”

Section: Introductionmentioning

confidence: 99%

“…The clusters studied are in the smallest size range that could be accessed in the experiments (41.4 nm). 67 Quantum chemical calculations are carried out to compute structures, energies and related properties of the clusters. The stabilities are further studied by molecular dynamic simulations from low (200 K) to high temperatures (500 K).…”

Section: Introductionmentioning

confidence: 99%

Nanoparticles grown from methanesulfonic acid and methylamine: microscopic structures and formation mechanism

Finlayson-Pitts

Gerber

2017

Phys. Chem. Chem. Phys.

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Mechanisms of particle formation and growth in the atmosphere are of great interest due to their impacts on climate, health and visibility. However, the microscopic structures and related properties of the smallest nanoparticles are not known. In this paper we pursue computationally a microscopic description for the formation and growth of methanesulfonic acid (MSA) and methylamine (MA) particles under dry conditions. Energetic and dynamics simulations were used to assess the stabilities of proposed model structures for these particles. Density functional theory (DFT) and semi-empirical (PM3) calculations suggest that (MSA-MA) is a major intermediate in the growth process, with the dissociation energies, enthalpies and free energies indicating considerable stability for this cluster. Dynamics simulations show that this species is stable for at least 100 ps at temperatures up to 500 K, well above atmospheric temperatures. In order to reach experimentally detectable sizes (>1.4 nm), continuing growth is suggested to occur via clustering of (MSA-MA). The dimer (MSA-MA)(MSA-MA) may be one of the smaller experimentally measured particles. Step by step addition of MSA to (MSA-MA), is also a likely potential growth mechanism when MSA is excess. In addition, an MSA-MA crystal is predicted to exist. These studies demonstrate that computations of particle structure and dynamics in the nano-size range can be useful for molecular level understanding of processes that grow clusters into detectable particles.

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“…In the clear marine atmosphere, oxidation products of dimethyl sulfide (DMS) and iodine compounds, together with reactive amines, are generally considered to be the important biogenic precursors of the nucleation and growth of newly formed particles (e.g., Charlson et al, 1987;O'Dowd and de Leeuw, 2007;Quinn and Bates, 2011;Sellegri et al, 2016). Over the past 3 decades, many observational and modeling studies have been conducted to investigate the roles of DMS in NPF events in various marine atmospheres and the related effects on the climate (e.g., Charlson et al, 1987;Ayers and Gras, 1991;Hegg et al, 1991;Yu and Luo, 2010;Chang et al, 2011;Lana et al, 2012). The responses of grown new particles and clouds to marine biogenic products are much more complex than those derived from DMS (Quinn and Bates, 2011).…”

Section: Introductionmentioning

confidence: 99%

New particle formation in the marine atmosphere during seven cruise campaigns

Zhu

Shen

et al. 2019

Atmos. Chem. Phys.

View full text Add to dashboard Cite

We measured the particle number concentration, size distribution, and new particle formation (NPF) events in the marine atmosphere during six cruise campaigns over the marginal seas of China in 2011-2016 and one campaign from the marginal seas to the Northwest Pacific Ocean (NWPO) in 2014. We observed relatively frequent NPF events in the atmosphere over the marginal seas of China, i.e., on 23 out of 126 observational days, with the highest frequency of occurrence in fall, followed by spring and summer. In total, 22 out of 23 NPF events were found to be associated with the long-range transport of continental pollutants based on 24 h air mass back trajectories and pre-existing particle number concentrations, which largely exceeded the clean marine background, leaving one much weaker NPF event that was likely induced by oceanic precursors alone, as supported by multiple independent pieces of evidence. Although the longrange transport signal of continental pollutants can be clearly observed in the remote marine atmosphere over the NWPO, NPF events were observed on only 2 out of 36 days. The nucleation-mode particles (<30 nm), however, accounted for as high as 35 % ± 13 % of the total particle number concentration during the NWPO cruise campaign, implying the existence of many undetected NPF events in the near-sea-level atmosphere or above.To better characterize NPF events, we introduce a term called the net maximum increase in the nucleation-mode particle number concentration (NMINP) and correlate it with the formation rate of new particles (FR). We find a moderately good linear correlation between NMINP and FR at FR ≤ 8 cm −3 s −1 , but no correlation exists at FR>8 cm −3 s −1 . The possible mechanisms are argued in terms of the roles of different vapor precursors. We also find that a ceiling exists for the growth of new particles from 10 nm to larger sizes in most NPF events. We thereby introduce a term called the maximum geometric median diameter of new particles (D pgmax ) and correlate it with the growth rate of new particles (GR). A moderately good linear correlation is also obtained between the D pgmax and GR, and only GR values larger than 7.9 nm h −1 can lead to new particles growing with a D pgmax beyond 50 nm based on the equation. By combining simultaneous measurements of the particle number size distributions and cloud condensation nuclei (CCN) at different super saturations (SS), we observed a clear increase in CCN when the D pg of new particles exceeded 50 nm at SS = 0.4 %. However, this case did not occur for SS = 0.2 %. Consistent with the results of previous studies in the continental atmosphere, our results imply that particles smaller than 50 nm are unlikely activated as CCN at SS = 0.4 % in the marine atmosphere. Moreover, κ decrease from 0.4 to 0.

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The Role of Oxalic Acid in New Particle Formation from Methanesulfonic Acid, Methylamine, and Water

Cited by 61 publications

References 94 publications

New particle formation in marine atmosphere during seven cruise campaigns

New particle formation in marine atmosphere during seven cruise campaigns

Nanoparticles grown from methanesulfonic acid and methylamine: microscopic structures and formation mechanism

New particle formation in the marine atmosphere during seven cruise campaigns

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