Atmospheric Sulfuric Acid‐Dimethylamine Nucleation Enhanced by Trifluoroacetic Acid

Abstract

Sulfuric acid (SA)‐dimethylamine (DMA)‐H2O cluster formation has been proven to be responsible for a significant part of new particle formation (NPF) in a Chinese megacity. However, the possible involvement of common atmospheric acids in the subsequent growth of SA‐DMA clusters remains elusive. We simulated formation and growth of clusters using atmospheric relevant concentrations of SA, DMA, and trifluoroacetic acid (TFA), a commonly observed atmospheric perfluorocarboxylic acid, using Density Functional Theory combined with Atmospheric Cluster Dynamics Code. The presence of TFA leads to complex cluster formation routes and an enhancement of NPF rates by up to 2.3 ([TFA] = 5.0 × 106 molecules cm−3, [SA] = 1.0 × 106 molecules cm−3, and [DMA] = 1.5 × 109 molecules cm−3). The agreement of (SA)1·(DMA)1‐2·(TFA)1 concentrations between simulations and ambient measurements during NPF events validates model predictions and implies that perfluorocarboxylic acids could potentially boost atmospheric SA‐DMA NPF rates.

Nonagricultural Emissions Dominate Urban Atmospheric Amines as Revealed by Mobile Measurements

“…Currently, there are 24 carcinogenic amines banned by global legislatures for use in industrial production (e.g., textile dyeing) (Lee & Wexler, 2013). Moreover, amines have much stronger basicity than NH 3 and are more likely to participate in acid‐base nucleation to initiate the formation of nanoclusters down to 1–3 nm (Jen et al., 2016; Kurtén et al., 2008; Yu et al., 2012), enabling the subsequent growth to climate‐ and health‐relevant sizes via various pathways including the formation of salts and aqueous phase reactions (Lu et al., 2020; Qiu & Zhang, 2013; L. Wang et al., 2010). New particle formation (NPF) usually occurs in pristine and clean atmospheres to overcome the scavenging losses of precursors and nanoparticles (Lawler et al., 2018; Mäkelä et al., 1997; Sellegri et al., 2016; Xiao et al., 2021).…”

The catalytic effects of H2O, basic and acidic catalysts on the gas‐phase hydrolysis mechanism of carbonyl fluoride (CF2O)

“…Here, the typical concentrations of catalysts X and the temperature range of 280-320 K in the atmosphere were considered. The concentration values [2,35,43,52,[54][55][56][57][58][59][60][61] of all catalysts were previously reported.…”

Investigation of the Production of Trifluoroacetic Acid from Two Halocarbons, HFC-134a and HFO-1234yf and Its Fates Using a Global Three-Dimensional Chemical Transport Model

“…15 However, recent research suggests that atmospheric TFA may contribute to the formation of aerosols, which would have a significant impact on climate change. 16 As a result, it is important to account for all atmospheric consequences from legislated changes to the global emission inventory, even when the consequences are not immediately seen or felt.…”

“…Despite this, TFA does not bioaccumulate and exhibits low to moderate toxicity in a range of organisms even in instances of very high exposure. , Furthermore, anthropogenically generated TFA is not expected to contribute significantly to acid rain or further terrestrial acidification . However, recent research suggests that atmospheric TFA may contribute to the formation of aerosols, which would have a significant impact on climate change . As a result, it is important to account for all atmospheric consequences from legislated changes to the global emission inventory, even when the consequences are not immediately seen or felt.…”