Organosulfate produced from consumption of SO3 speeds up sulfuric acid–dimethylamine atmospheric nucleation DOI Creative Commons
Xiaomeng Zhang,

Yongjian Lian,

Shendong Tan

et al.

Atmospheric chemistry and physics, Journal Year: 2024, Volume and Issue: 24(6), P. 3593 - 3612

Published: March 22, 2024

Abstract. Although sulfuric acid (SA) and dimethylamine (DMA)-driven nucleation mainly dominates the new particle formation (NPF) process in atmosphere, seeking involvement of other gaseous species remains crucial for a better understanding NPF. Organosulfate has been detected gas phase abundantly atmospheric fine particles. However, its molecular mechanism impact on NPF are still much less understood. Here, we explored gas-phase reaction glycolic (GA) with SO3 evaluated enhancing potential products SA–DMA-driven using combination quantum chemical calculations kinetics modeling. We found that considerable concentration sulfate (GAS) is thermodynamically accessible from GA SO3, efficiently catalyzed by SA or H2O molecules. The produced GAS can form stable clusters DMA speeds up rate SA–DMA system obviously. Notably, enhancement SA–DMA-based be to ∼ 800 times region where about 104 molec. cm−3. Supported observations events at Mt. Tai China, our proposed ternary GAS–SA–DMA further indicates organosulfates consumption may play an important role unexpected high rates observed areas relatively low concentrations SA. presented mechanisms provide feasible source Based findings, multiple regions around world was estimated discussed.

Language: Английский

Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere DOI Open Access
Xu‐Cheng He, Mario Simon, Siddharth Iyer

et al.

Science, Journal Year: 2023, Volume and Issue: 382(6676), P. 1308 - 1314

Published: Dec. 14, 2023

The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H2SO4), stabilized by ammonia (NH3). However, marine and polar regions, NH3 generally low, H2SO4 frequently found together with iodine oxoacids [HIOx, i.e., iodic (HIO3) iodous (HIO2)]. In experiments performed CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated interplay of HIOx during atmospheric particle nucleation. We that greatly enhances H2SO4(-NH3) nucleation through two different interactions. First, HIO3 strongly binds charged clusters so they drive synergistically. Second, HIO2 substitutes for NH3, forming bound H2SO4-HIO2 acid-base pairs molecular clusters. Global observations imply enhancing rates 10- 10,000-fold regions.

Language: Английский

Citations

41
Significant contributions of trimethylamine to sulfuric acid nucleation in polluted environments DOI Creative Commons
Runlong Cai, Rujing Yin, Xue Li

et al.

npj Climate and Atmospheric Science, Journal Year: 2023, Volume and Issue: 6(1)

Published: June 27, 2023

Abstract As one of the least understood aerosol processes, nucleation can be a dominant source atmospheric aerosols. Sulfuric acid (SA)-amine binary with dimethylamine (DMA) has been recognized as governing mechanism in polluted continental boundary layer. Here we demonstrate importance trimethylamine (TMA) for complex atmosphere and propose molecular-level SA-DMA-TMA ternary an improvement upon conventional mechanism. Using proposed mechanism, could connect gaseous amines to SA-amine cluster signals measured urban Beijing. Results show that TMA accelerate SA-DMA-based new particle formation Beijing by 50–100%. Considering global abundance DMA, our findings imply comparable DMA layer, probably higher contributions from rural environments future controlled emissions.

Language: Английский

Citations

32
Enhancement of Atmospheric Nucleation Precursors on Iodic Acid-Induced Nucleation: Predictive Model and Mechanism DOI Creative Commons
Fangfang Ma, Hong‐Bin Xie, Rongjie Zhang

et al.

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(17), P. 6944 - 6954

Published: April 21, 2023

Iodic acid (IA) has recently been recognized as a key driver for new particle formation (NPF) in marine atmospheres. However, the knowledge of which atmospheric vapors can enhance IA-induced NPF remains limited. The unique halogen bond (XB)-forming capacity IA makes it difficult to evaluate enhancing potential (EP) target compounds on based widely studied sulfuric systems. Herein, we employed three-step procedure EP nucleation precursors NPF. First, evaluated 63 by simulating free energies (ΔG) IA-containing dimer clusters. Among all clusters, 44 contained XBs, demonstrating that XBs are frequently formed. Based calculated ΔG values, quantitative structure–activity relationship model was developed evaluating other precursors. Second, amines and O/S-atom-containing acids were found have high EP, with diethylamine (DEA) yielding highest combining both concentration considered Finally, studying larger (IA)1–3(DEA)1–3 IA-DEA system merely 0.1 ppt (2.5×106 cm–3) DEA yields comparable rates IA–iodous system.

Language: Английский

Citations

30
Quantum chemical modeling of organic enhanced atmospheric nucleation: A critical review DOI Creative Commons
Jonas Elm, Daniel Ayoubi, Morten Engsvang

et al.

Wiley Interdisciplinary Reviews Computational Molecular Science, Journal Year: 2023, Volume and Issue: 13(5)

Published: May 9, 2023

Abstract Aerosol particles are important for our global climate, but the mechanisms and especially relative importance of various vapors new formation (NPF) remain uncertain. Quantum chemical (QC) studies on organic enhanced nucleation has past couple decades attracted immense attention, very little remains known about exact compounds that potentially NPF. Here we comprehensively review QC literature atmospheric cluster involving compounds. We outline potential systems should be further investigated. Cluster complex multi‐functional accretion products warrant investigations, such out reach with currently applied methodologies. suggest a “cluster functional groups” approach to address this issue, which will allow identification structure involved in This article is categorized under: Theoretical Physical Chemistry > Reaction Dynamics Kinetics Software Thermochemistry Molecular Statistical Mechanics Interactions

Language: Английский

Citations

27
Characteristics, Origins, and Atmospheric Processes of Amines in Fine Aerosol Particles in Winter in China DOI
Tang Liu, Yu Xu, Qibin Sun

et al.

Journal of Geophysical Research Atmospheres, Journal Year: 2023, Volume and Issue: 128(14)

Published: July 9, 2023

Abstract Amines affect particle formation, aerosol acidity, nitrogen cycle, and climate change. However, little is known about the temporal spatial differences in composition, source, formation process of amines fine particulate matter (PM 2.5 ) different regions China. Seven (amine salts) were investigated PM collected Yangtze River Delta (YRD, Shanghai Nanjing), Pearl (PRD, Guangzhou), northern China (Xi'an Haerbin), background (Puding) areas winter 2017–2018. Methylamine was dominant amine species at YRD, China, sites, while diethylamine dominated PRD site; moreover, mass concentration fraction lowest site. These results could be attributed to changes sources atmospheric processes. Further, coal combustion biomass burning found important contributors cities winter. The contribution weakened other urban sites. In contrast, abundance site largely controlled by biogenic sources. Acid‐base chemistry displacement mechanism tightly associated with salts all particular, degradation hydroxyl radical (•OH) significant Nanjing, Guangzhou, Xi'an, Haerbin insignificant photochemical sites can explained differentiated sources, meteorological conditions, •OH levels. Overall, our findings deepen understanding origins processes amines.

Language: Английский

Citations

26
Clusteromics V: Organic Enhanced Atmospheric Cluster Formation DOI Creative Commons
Daniel Ayoubi, Yosef Knattrup, Jonas Elm

et al.

ACS Omega, Journal Year: 2023, Volume and Issue: 8(10), P. 9621 - 9629

Published: Feb. 28, 2023

Formic acid (FA) is a prominent candidate for organic enhanced nucleation due to its high abundance and stabilizing effect on smaller clusters. Its role in new particle formation studied through the use of state-of-the-art quantum chemical methods cluster systems (acid)1–2(FA)1(base)1–2 with acids being sulfuric (SA)/methanesulfonic (MSA) bases consisting ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylenediamine (EDA). A funneling approach used determine structures initial configurations generated ABCluster program, followed by semiempirical PM7 ωB97X-D/6-31++G(d,p) calculations. The final binding free energy calculated at DLPNO-CCSD(T0)/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level theory using quasi-harmonic approximation. Cluster dynamics simulations show that FA has minuscule or negligible MSA–FA–base as well most SA–FA–base systems. SA–FA–DMA system shows highest influence from an enhancement 21%, compared non-FA counterpart.

Language: Английский

Citations

24
Clusteromics III: Acid Synergy in Sulfuric Acid–Methanesulfonic Acid–Base Cluster Formation DOI Creative Commons
Jonas Elm

ACS Omega, Journal Year: 2022, Volume and Issue: 7(17), P. 15206 - 15214

Published: April 20, 2022

Acid-base molecular clusters are an important stage in atmospheric new particle formation. While such most likely multicomponent nature, there very few reports on consisting of multiple acid molecules and base molecules. By applying state-of-the-art quantum chemical methods, we herein study electrically neutral (SA)1(MSA)1(base)0-2 with = ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA) ethylenediamine (EDA). The cluster structures obtained using a funneling approach employing the ABCluster program, semiempirical PM7 calculations ωB97X-D/6-31++G(d,p) calculations. final binding free energies calculated at DLPNO-CCSD(T0)/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level theory quasi-harmonic approximation. Based geometries thermochemistry (at 298.15 K 1 atm), find that mixed (SA)1(MSA)1(base)1-2 more resemble (SA)2(base)1-2 compared to (MSA)2(base)1-2 clusters. Hence, some steric hindrance lack hydrogen bond capacity previously observed is diminished corresponding Cluster kinetics simulations reveal presence MSA molecule enhances formation potential by up factor 20. We SA-MSA-DMA have highest potential, thus, this system should be further extended larger sizes future studies.

Language: Английский

Citations

36
Clusteromics IV: The Role of Nitric Acid in Atmospheric Cluster Formation DOI Creative Commons
Yosef Knattrup, Jonas Elm

ACS Omega, Journal Year: 2022, Volume and Issue: 7(35), P. 31551 - 31560

Published: Aug. 23, 2022

Nitric acid (NA) has previously been shown to affect atmospheric new particle formation; however, its role still remains highly uncertain. Through the employment of state-of-the-art quantum chemical methods, we study (acid)1-2(base)1-2 and (acid)3(base)2 clusters containing at least one nitric sulfuric (SA) or methanesulfonic (MSA) with bases ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylenediamine (EDA). The initial cluster configurations are generated using ABCluster program. PM7 ωB97X-D/6-31++G(d,p) calculations used reduce number relevant configurations. thermochemical parameters calculated level theory quasi-harmonic approximation, final single-point energies high-level DLPNO-CCSD(T0)/aug-cc-pVTZ calculations. enhancing effect from presence on formation is studied data dynamics simulations. We find that when NA in excess compared other acids, it a substantial potential.

Language: Английский

Citations

27
Amine-Enhanced Methanesulfonic Acid-Driven Nucleation: Predictive Model and Cluster Formation Mechanism DOI
Yu Liu, Hong‐Bin Xie, Fangfang Ma

et al.

Environmental Science & Technology, Journal Year: 2022, Volume and Issue: 56(12), P. 7751 - 7760

Published: May 20, 2022

Atmospheric amines are considered to be an effective enhancer for methanesulfonic acid (MSA)-driven nucleation. However, out of the 195 detected atmospheric amines, enhancing potential (EP) has so far only been studied five amines. This severely hinders understanding contribution MSA-driven Herein, a two-step procedure was employed probe EP various on Initially, formation free energies (ΔG) 50 MSA-amine dimer clusters were calculated. Based calculated ΔG values, robust quantitative structure-activity relationship (QSAR) model built and utilized predict values remaining 145 The QSAR identified two guanidino-containing compounds as potentially strongest Second, by employing larger selecting guanidine (Gud) representative. results indicate that Gud indeed EP. Gud-MSA system presents unique clustering mechanism, proceeding via initial (Gud)1(MSA)1 cluster, subsequently cluster collisions with either or (Gud)2(MSA)2 cluster. developed identification provide foundation comprehensively evaluating

Language: Английский

Citations

24
Measurement report: Occurrence of aminiums in PM2.5 during winter in China – aminium outbreak during polluted episodes and potential constraints DOI Creative Commons
Yu Xu, Tang Liu, Yi-Jia Ma

et al.

Atmospheric chemistry and physics, Journal Year: 2024, Volume and Issue: 24(18), P. 10531 - 10542

Published: Sept. 23, 2024

Abstract. Amines and aminiums play an important role in particle formation, liquid-phase reactions, climate change have attracted considerable attention over the years. Here, we investigated concentrations compositions of PM2.5 11 Chinese cities during winter, focusing on characteristics polluted days key factors influencing aminium outbreak. Monomethylaminium was dominant species most cities, except Taiyuan Guangzhou, followed by dimethylaminium. Diethylaminium dominated total Guangzhou. Thus, main amine sources Guangzhou were significantly different from those other cities. The (TAs) increased days, while relatively weak outbreaks occurred Xi'an Beijing. Additionally, TAs Beijing insignificantly correlated with major acidic aerosol components, opposite pattern observed nine acid–base chemistry associated formation all Based sensitivity analysis : ammonium ratio to changes, as well excluding effects relative humidity atmospheric oxidation, proposed possibility competitive uptake ammonia versus amines aerosols or displacement (constraining outbreaks). Overall, this study deepens understanding spatiotemporal differences characteristic China. However, particles form relevant require further mechanistic research.

Language: Английский

Citations

4