scholarly journals Self-Catalytic Reaction of SO3 and NH3 To Produce Sulfamic Acid and Its Implication to Atmospheric Particle Formation

2018 ◽  
Vol 140 (35) ◽  
pp. 11020-11028 ◽  
Author(s):  
Hao Li ◽  
Jie Zhong ◽  
Hanna Vehkamäki ◽  
Theo Kurtén ◽  
Weigang Wang ◽  
...  
Keyword(s):  
Catalytic Reaction ◽  
Sulfamic Acid ◽  
Particle Formation ◽  
Atmospheric Particle

scholarly journals Enhancing Potential of Trimethylamine Oxide on Atmospheric Particle Formation

Atmosphere ◽  
2019 ◽  
Vol 11 (1) ◽  
pp. 35 ◽  
Author(s):  
Nanna Myllys ◽  
Tuomo Ponkkonen ◽  
Sabrina Chee ◽  
James Smith
Keyword(s):  
Cluster Formation ◽  
Particle Formation ◽  
Formation Mechanisms ◽  
Atmospheric Particle ◽  
Dipole Interactions ◽  
Trimethylamine Oxide ◽  
Quantum Chemical Methods ◽  
Low Concentrations ◽  
Stable Clusters ◽  
Level Cluster

The role of an oxidation product of trimethylamine, trimethylamine oxide, in atmospheric particle formation is studied using quantum chemical methods and cluster formation simulations. Molecular-level cluster formation mechanisms are resolved, and theoretical results on particle formation are confirmed with mass spectrometer measurements. Trimethylamine oxide is capable of forming only one hydrogen bond with sulfuric acid, but unlike amines, trimethylamine oxide can form stable clusters via ion–dipole interactions. That is because of its zwitterionic structure, which causes a high dipole moment. Cluster growth occurs close to the acid:base ratio of 1:1, which is the same as for other monoprotic bases. Enhancement potential of trimethylamine oxide in particle formation is much higher than that of dimethylamine, but lower compared to guanidine. Therefore, at relatively low concentrations and high temperatures, guanidine and trimethylamine oxide may dominate particle formation events over amines.

scholarly journals Predicting atmospheric particle formation days by Bayesian classification of the time series features

Tellus B ◽  
2018 ◽  
Vol 70 (1) ◽  
pp. 1-10 ◽  
Author(s):  
M. A. Zaidan ◽  
V. Haapasilta ◽  
R. Relan ◽  
H. Junninen ◽  
P. P. Aalto ◽  
...  
Keyword(s):  
Time Series ◽  
Particle Formation ◽  
Bayesian Classification ◽  
Atmospheric Particle

scholarly journals The charging of neutral dimethylamine and dimethylamine–sulfuric acid clusters using protonated acetone

2015 ◽  
Vol 8 (6) ◽  
pp. 2577-2588
Author(s):  
K. Ruusuvuori ◽  
P. Hietala ◽  
O. Kupiainen-Määttä ◽  
T. Jokinen ◽  
H. Junninen ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Chemical Ionization ◽  
Lower Troposphere ◽  
Particle Formation ◽  
Atmospheric Conditions ◽  
Atmospheric Particle ◽  
Organic Bases ◽  
Atmospheric Nucleation ◽  
Quantum Chemical Methods ◽  
Vapour Concentration

Abstract. Sulfuric acid is generally considered one of the most important substances taking part in atmospheric particle formation. However, in typical atmospheric conditions in the lower troposphere, sulfuric acid and water alone are unable to form particles. It has been suggested that strong bases may stabilize sulfuric acid clusters so that particle formation may occur. More to the point, amines – strong organic bases – have become the subject of interest as possible cause for such stabilization. To probe whether amines play a role in atmospheric nucleation, we need to be able to measure accurately the gas-phase amine vapour concentration. Such measurements often include charging the neutral molecules and molecular clusters in the sample. Since amines are bases, the charging process should introduce a positive charge. This can be achieved by, for example, using chemical ionization with a positively charged reagent with a suitable proton affinity. In our study, we have used quantum chemical methods combined with a cluster dynamics code to study the use of acetone as a reagent ion in chemical ionization and compared the results with measurements performed with a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (CI-APi-TOF). The computational results indicate that protonated acetone is an effective reagent in chemical ionization. However, in the experiments the reagent ions were not depleted at the predicted dimethylamine concentrations, indicating that either the modelling scheme or the experimental results – or both – contain unidentified sources of error.

scholarly journals Kinetic nucleation and ions in boreal particle formation events

2004 ◽  
Vol 4 (4) ◽  
pp. 3911-3945 ◽  
Author(s):  
L. Laakso ◽  
T. Anttila ◽  
K. E. J. Lehtinen ◽  
P. P. Aalto ◽  
M. Kulmala ◽  
...  
Keyword(s):  
Sulphuric Acid ◽  
Negative Ions ◽  
Particle Formation ◽  
Model Simulations ◽  
Aerosol Dynamics ◽  
Atmospheric Particle ◽  
Relative Contribution ◽  
Charged Aerosol ◽  
Charged Clusters ◽  
Basic Features

Abstract. In order to gain a more comprehensive picture on different mechanisms behind atmospheric particle formation, measurement results from QUEST 2-campaign are analyzed with an aid of an aerosol dynamic model. A special emphasis is laid on air ion and charged aerosol dynamics. Conducted model simulations indicate that kinetic nucleation of ammonia and sulphuric acid together with condensation of sulphuric acid and low-volatile organic vapours onto clusters and particles explain basic features of particle formation events as well as ion characteristics. However, observed excess of negative ions in the diameter range 1.5–3 nm and overcharge of 3–5 nm particles demonstrate that ions are also involved in particle formation. These observations can be explained by preferential condensation of sulphuric acid onto negatively charged clusters and particles. According to model simulations, the relative contribution of ion-based particle formation seem to be smaller than kinetic nucleation of neutral clusters. Conducted model simulations also corroborate the recently-presented hypothesis according to which a large number of so-called thermodynamically stable clusters (TSCs) having a diameter between 1–3 nm exist in the atmosphere. TSCs were found to grow to the observable sizes only under favorable conditions, e.g. when the pre-existing particle concentration was low.

scholarly journals Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

2013 ◽  
Vol 110 (43) ◽  
pp. 17223-17228 ◽  
Author(s):  
S. Schobesberger ◽  
H. Junninen ◽  
F. Bianchi ◽  
G. Lonn ◽  
M. Ehn ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Organic Molecules ◽  
Particle Formation ◽  
Atmospheric Particle

scholarly journals On the formation of sulphuric acid-amine clusters in varying atmospheric conditions and its influence on atmospheric new particle formation

2012 ◽  
Vol 12 (5) ◽  
pp. 11485-11537 ◽  
Author(s):  
P. Paasonen ◽  
T. Olenius ◽  
O. Kupiainen ◽  
T. Kurtén ◽  
T. Petäjä ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Sulphuric Acid ◽  
Acid Concentration ◽  
Formation Rate ◽  
Particle Formation ◽  
Atmospheric Conditions ◽  
New Particle Formation ◽  
Atmospheric Particle ◽  
Atmospheric Observations ◽  
Sulphuric Acid Concentration

Abstract. Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (JA2B2) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid ([H2SO4]), dimethylamine ([DMA]) and trimethylamine ([TMA]), temperature and relative humidity (RH). The modelled formation rates JA2B2 were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients KA2B2 connecting the cluster formation rate and sulphuric acid concentrations as JA2B2 = KA2B2[H2SO4]2 turned out to depend also on amine concentrations, temperature and relative humidity. We tested how the model results change if the clusters with two sulphuric acid and two amine molecules are assumed to act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. We also compared the modelled coefficients KA2B2 with the corresponding coefficients calculated from the atmospheric observations (Kobs) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of JA2B2 as a function of [H2SO4], temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating to particle formation. The observed inverse proportionality of the coefficient Kobs with RH and temperature agreed best with the modelled coefficient KA2B2 related to formation of a~cluster with two H2SO4 and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H2SO4).

scholarly journals Atmospheric particle formation events at Värriö measurement station in Finnish Lapland 1998–2002

2004 ◽  
Vol 4 (3) ◽  
pp. 3535-3563
Author(s):  
H. Vehkamäki ◽  
M. Dal Maso ◽  
T. Hussein ◽  
R. Flanagan ◽  
A. Hyvärinen ◽  
...  
Keyword(s):  
Growth Rate ◽  
Biological Activity ◽  
Gas Phase ◽  
Formation Rate ◽  
Particle Formation ◽  
Meteorological Conditions ◽  
Air Masses ◽  
Atmospheric Particle ◽  
Starting Time ◽  
Finnish Lapland

Abstract. We have identified 147 clear 8 nm diameter particle formation events at the SMEAR I station in Värriö, northern Finland during calendar years 1998–2002. The events have been classified in detail according to the particle formation rate, growth rate, event starting time, different gas phase species concentrations and pre-existing particle concentrations as well as various meteorological conditions. Most of the events occurred during the spring months between March and May, suggesting that increasing biological activity might produce the precursor gases for particle formation. The apparent 8 nm particle formation rates were around 0.1/cm3s, and they were uncorrelated with growth rates that vary between 0.5 and 10 nm/h. The air masses, which had clearly elevated sulphur dioxide concentrations above 1.6 ppb came, as expected, from the direction of Nikel and Monschegorsk smelteries. Only 15 formation events can be explained by the pollution plume from these sources.

scholarly journals On the formation of sulphuric acid – amine clusters in varying atmospheric conditions and its influence on atmospheric new particle formation

2012 ◽  
Vol 12 (19) ◽  
pp. 9113-9133 ◽  
Author(s):  
P. Paasonen ◽  
T. Olenius ◽  
O. Kupiainen ◽  
T. Kurtén ◽  
T. Petäjä ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Sulphuric Acid ◽  
Acid Concentration ◽  
Formation Rate ◽  
Particle Formation ◽  
Atmospheric Conditions ◽  
New Particle Formation ◽  
Atmospheric Particle ◽  
Atmospheric Observations ◽  
Sulphuric Acid Concentration

Abstract. Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (JA2B2) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid ([H2SO4]), dimethylamine ([DMA]) and trimethylamine ([TMA]), temperature and relative humidity (RH). We also tested how the model results change if we assume that the clusters with two sulphuric acid and two amine molecules would act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. The modelled formation rates JA2B2 were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients KA2B2 connecting the cluster formation rate and sulphuric acid concentrations as JA2B2=KA2B2[H2SO4]2 turned out to depend also on amine concentrations, temperature and relative humidity. We compared the modelled coefficients KA2B2 with the corresponding coefficients calculated from the atmospheric observations (Kobs) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of JA2B2 as a function of [H2SO4], temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating in particle formation. The observed inverse proportionality of the coefficient Kobs with RH and temperature agreed best with the modelled coefficient KA2B2 related to formation of a cluster with two H2SO4 and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H2SO4).

scholarly journals Ideas and perspectives: on the emission of amines from terrestrial vegetation in the context of new atmospheric particle formation

2015 ◽  
Vol 12 (11) ◽  
pp. 3225-3240 ◽  
Author(s):  
J. Sintermann ◽  
A. Neftel
Keyword(s):  
Particle Formation ◽  
Direct Impact ◽  
Terrestrial Vegetation ◽  
Atmospheric Particle ◽  
Vegetative Plant ◽  
Agricultural Emissions ◽  
Pollination Strategy ◽  
Species Specific ◽  
Open Question ◽  
The 19Th Century

Abstract. In this article we summarise recent science which shows how airborne amines, specifically methylamines (MAs), play a key role in new atmospheric particle formation (NPF) by stabilising small molecule clusters. Agricultural emissions are assumed to constitute the most important MA source, but given the short atmospheric residence time of MAs, they can hardly have a direct impact on NPF events observed in remote regions. This leads us to the presentation of existing knowledge focussing on natural vegetation-related MA sources. High MA contents as well as emissions by plants was already described in the 19th century. Strong MA emissions predominantly occur during flowering as part of a pollination strategy. The behaviour is species-specific, but examples of such species are common and widespread. In addition, vegetative plant tissue exhibiting high amounts of MAs might potentially lead to significant emissions. The decomposition of organic material constitutes another, potentially ubiquitous, source of airborne MAs. These mechanisms would provide sources, which could be crucial for the amine's role in NPF, especially in remote regions. Knowledge about vegetation-related amine emissions is, however, very limited, and thus it is also an open question how global change and the intensified cycling of reactive nitrogen over the last 200 years have altered amine emissions from vegetation with a corresponding effect on NPF.

scholarly journals Global atmospheric particle formation from CERN CLOUD measurements

Science ◽  
2016 ◽  
Vol 354 (6316) ◽  
pp. 1119-1124 ◽  
Author(s):  
E. M. Dunne ◽  
H. Gordon ◽  
A. Kurten ◽  
J. Almeida ◽  
J. Duplissy ◽  
...  
Keyword(s):  
Particle Formation ◽  
Atmospheric Particle
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