Computational Study of the Reaction between Biogenic Stabilized Criegee Intermediates and Sulfuric Acid

2007 ◽  
Vol 111 (17) ◽  
pp. 3394-3401 ◽  
Author(s):  
Theo Kurtén ◽  
Boris Bonn ◽  
Hanna Vehkamäki ◽  
Markku Kulmala
Keyword(s):  
Sulfuric Acid ◽  
Computational Study ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

scholarly journals Oxidation of SO<sub>2</sub> by stabilized Criegee intermediate (sCI) radicals as a crucial source for atmospheric sulfuric acid concentrations

2013 ◽  
Vol 13 (7) ◽  
pp. 3865-3879 ◽  
Author(s):  
M. Boy ◽  
D. Mogensen ◽  
S. Smolander ◽  
L. Zhou ◽  
T. Nieminen ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Gas Phase ◽  
Oxidation Mechanism ◽  
Ground Level ◽  
Reaction Rates ◽  
Rate Coefficients ◽  
Dimensional Model ◽  
Sulfuric Acid Production ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

Abstract. The effect of increased reaction rates of stabilized Criegee intermediates (sCIs) with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012) increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO) with SO2 according to the values recommended by Welz et al. (2012) increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

scholarly journals Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber

2018 ◽  
Vol 18 (4) ◽  
pp. 2363-2380 ◽  
Author(s):  
Nina Sarnela ◽  
Tuija Jokinen ◽  
Jonathan Duplissy ◽  
Chao Yan ◽  
Tuomo Nieminen ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Model Comparison ◽  
Cloud Condensation Nuclei ◽  
Measurement Model ◽  
Cloud Chamber ◽  
Oxidation Products ◽  
Atmospheric Oxidation ◽  
European Organization ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

Abstract. Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate α-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H2), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5–6.5 % for HOM formation and 22–32 % for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20–50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

scholarly journals Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions

2021 ◽  
Vol 21 (17) ◽  
pp. 13333-13351
Author(s):  
Alexandre Kukui ◽  
Michel Chartier ◽  
Jinhe Wang ◽  
Hui Chen ◽  
Sébastien Dusanter ◽  
...  
Keyword(s):  
Steady State ◽  
Sulfuric Acid ◽  
Organic Compounds ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Additional Source ◽  
So2 Oxidation ◽  
Criegee Intermediates ◽  
Volatile Organic

Abstract. Reaction of stabilized Criegee intermediates (SCIs) with SO2 was proposed as an additional pathway of gaseous sulfuric acid (H2SO4) formation in the atmosphere, supplementary to the conventional mechanism of H2SO4 production by oxidation of SO2 in reaction with OH radicals. However, because of a large uncertainty in mechanism and rate coefficients for the atmospheric formation and loss reactions of different SCIs, the importance of this additional source is not well established. In this work, we present an estimation of the role of SCIs in H2SO4 formation at a western Mediterranean (Cape Corsica) remote site, where comprehensive field observations including gas-phase H2SO4, OH radicals, SO2, volatile organic compounds (VOCs) and aerosol size distribution measurements were performed in July–August 2013 as a part of the project ChArMEx (Chemistry-Aerosols Mediterranean Experiment). The measurement site was under strong influence of local emissions of biogenic volatile organic compounds, including monoterpenes and isoprene generating SCIs in reactions with ozone, and, hence, presenting an additional source of H2SO4 via SO2 oxidation by the SCIs. Assuming the validity of a steady state between H2SO4 production and its loss by condensation on existing aerosol particles with a unity accommodation coefficient, about 90 % of the H2SO4 formation during the day could be explained by the reaction of SO2 with OH. During the night the oxidation of SO2 by OH radicals was found to contribute only about 10 % to the H2SO4 formation. The accuracy of the derived values for the contribution of OH + SO2 reaction to the H2SO4 formation is limited mostly by a large, at present factor of 2, uncertainty in the OH + SO2 reaction rate coefficient. The contribution of the SO2 oxidation by SCIs to the H2SO4 formation was evaluated using available measurements of unsaturated VOCs and steady-state SCI concentrations estimated by adopting rate coefficients for SCI reactions based on structure–activity relationships (SARs). The estimated concentration of the sum of SCIs was in the range of (1–3) × 103 molec. cm−3. During the day the reaction of SCIs with SO2 was found to account for about 10 % and during the night for about 40 % of the H2SO4 production, closing the H2SO4 budget during the day but leaving unexplained about 50 % of the H2SO4 formation during the night. Despite large uncertainties in used kinetic parameters, these results indicate that the SO2 oxidation by SCIs may represent an important H2SO4 source in VOC-rich environments, especially during nighttime.

scholarly journals Enhancing effect of dimethylamine in sulfuric acid nucleation in the presence of water – a computational study

2010 ◽  
Vol 10 (10) ◽  
pp. 4961-4974 ◽  
Author(s):  
V. Loukonen ◽  
T. Kurtén ◽  
I. K. Ortega ◽  
H. Vehkamäki ◽  
A. A. H. Pádua ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Quantum Chemistry ◽  
Computational Study ◽  
Water Molecules ◽  
Enhancing Effect ◽  
Formation Energies

Abstract. We have studied the hydration of sulfuric acid – ammonia and sulfuric acid – dimethylamine clusters using quantum chemistry. We calculated the formation energies and thermodynamics for clusters of one ammonia or one dimethylamine molecule together with 1–2 sulfuric acid and 0–5 water molecules. The results indicate that dimethylamine enhances the addition of sulfuric acid to the clusters much more efficiently than ammonia when the number of water molecules in the cluster is either zero, or greater than two. Further hydrate distribution calculations reveal that practically all dimethylamine-containing two-acid clusters will remain unhydrated in tropospherically relevant circumstances, thus strongly suggesting that dimethylamine assists atmospheric sulfuric acid nucleation much more effectively than ammonia.

New Particle Formation Involving Charged Sulfuric Acid – Ammonia Clusters

2020 ◽  
Author(s):  
Vitus Besel ◽  
Jakub Kubečka ◽  
Theo Kurtén ◽  
Hanna Vehkamäki
Keyword(s):  
Sulfuric Acid ◽  
Computational Study ◽  
Cluster Formation ◽  
Chem Phys ◽  
Particle Formation ◽  
Empirical Method ◽  
Particle Nucleation ◽  
New Particle Formation ◽  
Charged Clusters ◽  
Ammonia Clusters

&lt;div&gt; &lt;p&gt;The bulk of aerosol particles in the atmosphere are formed by gas-to-particle nucleation (Merikanto et al., 2009). However, the exact process of single molecules forming cluster, which subsequently can grow into particles, remains largely unknown. Recently, sulfuric acid has been identified to play a key role in this new particle formation enhanced by other compounds such as organic acids (Zhang, 2010) or ammonia (Anttila et al., 2005). To identify the characteristics of cluster formation and nucleation involving sulfuric acid and ammonia in neutral, positive and negative modes, we conducted a computational study. We used a layered approach for configurational sampling of the molecular clusters starting from utilizing a genetic algorithm in order to explore the whole potential energy surface (PES) with all plausible geometrical minima, however, with very unreliable energies. The structures were further optimized with a semi-empirical method and, then, at the &amp;#969;B97X-D DFT level of theory. After each step, the optimized geometries were filtered to obtain the global minimum configuration. Further, a high level of theory (DLPNO-CCSD(T)) was used for obtaining the electronic energies, in addition to performing DFT frequency analysis, to calculate the Gibbs free energies of formation. These were passed to the Atmospheric Cluster Dynamics Code (ACDC) (McGrath et al., 2012) for studying the evolution of cluster populations. We determined the global minima for the following sulfuric acid - ammonia clusters: (H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;m&lt;/sub&gt;(NH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;n&lt;/sub&gt; with m=n, m=n+1 and n=m+1 for neutral clusters, (H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;m&lt;/sub&gt;(HSO&lt;sub&gt;4&lt;/sub&gt;)&lt;sup&gt;&amp;#8722;&lt;/sup&gt;(NH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;n&lt;/sub&gt; with m=n and n=m+1 for positively charged clusters, and (H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;m&lt;/sub&gt;(NH&lt;sub&gt;4&lt;/sub&gt;)&lt;sup&gt;+&lt;/sup&gt;(NH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;n&lt;/sub&gt; with m=n and m=n+1 for negatively charged clusters. Further, we present the formation rates, steady state concentrations and fluxes of these clusters calculated using ACDC and discuss how a new configurational sampling procedure, more precise quantum chemistry methods and parameters, such as symmetry and a quasiharmonic approach, impact these ACDC results in comparison to previous studies.&lt;/p&gt; &lt;/div&gt;&lt;div&gt; &lt;p&gt;&lt;em&gt;References:&lt;br&gt;&lt;/em&gt;&lt;em&gt;J. Merikanto, D. V. Spracklen, G. W. Mann, S. J. Pickering, and K. S. Carslaw (2009). Atmos. Chem.&amp;#160; Phys., 9, 8601-8616. &lt;br&gt;R. Zhang (2010). Science, 328, 1366-1367. &lt;br&gt;T. Anttila, H. Vehkam&amp;#228;ki, I. Napari, M. Kulmala (2005). Boreal Env. Res., 10, 523. &lt;br&gt;M.J. McGrath, T. Olenius, I.K. Ortega, V. Loukonen, P.&amp;#160; Paasonen, T. Kurten, M. Kulmala (2012). Atmos. Chem. Phys., 12, 2355. &lt;br&gt;&lt;/em&gt;&lt;/p&gt; &lt;/div&gt;

Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Sulfur Dioxide: Ab Initio and DFT Study

2010 ◽  
Vol 114 (47) ◽  
pp. 12452-12461 ◽  
Author(s):  
Lei Jiang ◽  
Yi-sheng Xu ◽  
Ai-zhong Ding
Keyword(s):  
Sulfur Dioxide ◽  
Ab Initio ◽  
Dft Study ◽  
Criegee Intermediates ◽  
Ab Initio And Dft ◽  
Stabilized Criegee Intermediates

Theoretical studies of the hydration reactions of stabilized Criegee intermediates from the ozonolysis of β-pinene

RSC Advances ◽  
2014 ◽  
Vol 4 (54) ◽  
pp. 28490 ◽  
Author(s):  
Xiao-Xiao Lin ◽  
Yi-Rong Liu ◽  
Teng Huang ◽  
Kang-Ming Xu ◽  
Yang Zhang ◽  
...  
Keyword(s):  
Theoretical Studies ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

CIMS Sulfuric Acid Detection Efficiency Enhanced by Amines Due to Higher Dipole Moments: A Computational Study

2013 ◽  
Vol 117 (51) ◽  
pp. 14109-14119 ◽  
Author(s):  
Oona Kupiainen-Määttä ◽  
Tinja Olenius ◽  
Theo Kurtén ◽  
Hanna Vehkamäki
Keyword(s):  
Sulfuric Acid ◽  
Detection Efficiency ◽  
Computational Study ◽  
Dipole Moments
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