Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions
<p>Reaction of stabilized Criegee intermediates (SCIs) with SO<span class="inline-formula"><sub>2</sub></span> was proposed as an additional pathway of gaseous sulfuric acid (H<span class="inline-formula"><sub>2</sub></span>SO...
| Main Authors: | , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2021-09-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://acp.copernicus.org/articles/21/13333/2021/acp-21-13333-2021.pdf |
| _version_ | 1819110170093944832 |
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| author | A. Kukui M. Chartier J. Wang J. Wang H. Chen H. Chen S. Dusanter S. Sauvage V. Michoud V. Michoud N. Locoge V. Gros T. Bourrianne K. Sellegri J.-M. Pichon |
| author_facet | A. Kukui M. Chartier J. Wang J. Wang H. Chen H. Chen S. Dusanter S. Sauvage V. Michoud V. Michoud N. Locoge V. Gros T. Bourrianne K. Sellegri J.-M. Pichon |
| author_sort | A. Kukui |
| collection | DOAJ |
| description | <p>Reaction of stabilized Criegee intermediates (SCIs) with SO<span class="inline-formula"><sub>2</sub></span> was proposed as an additional pathway of gaseous sulfuric acid
(H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span>) formation in the atmosphere, supplementary to the
conventional mechanism of H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> production by oxidation of
SO<span class="inline-formula"><sub>2</sub></span> 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 H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> formation at a western Mediterranean
(Cape Corsica) remote site, where comprehensive field observations including gas-phase H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span>, OH radicals, SO<span class="inline-formula"><sub>2</sub></span>, 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 H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> via SO<span class="inline-formula"><sub>2</sub></span> oxidation by the SCIs. Assuming the validity of
a steady state between H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> production and its loss by
condensation on existing aerosol particles with a unity accommodation
coefficient, about 90 % of the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> formation during the day
could be explained by the reaction of SO<span class="inline-formula"><sub>2</sub></span> with OH. During the night the
oxidation of SO<span class="inline-formula"><sub>2</sub></span> by OH radicals was found to contribute only about
10 % to the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> formation. The accuracy of the derived values
for the contribution of OH <span class="inline-formula">+</span> SO<span class="inline-formula"><sub>2</sub></span> reaction to the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span>
formation is limited mostly by a large, at present factor of 2, uncertainty in the OH <span class="inline-formula">+</span> SO<span class="inline-formula"><sub>2</sub></span> reaction rate coefficient. The contribution of the SO<span class="inline-formula"><sub>2</sub></span> oxidation by SCIs to the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> 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<span id="page13334"/> estimated
concentration of the sum of SCIs was in the range of (1–3) <span class="inline-formula">×</span> 10<span class="inline-formula"><sup>3</sup></span> molec. cm<span class="inline-formula"><sup>−3</sup></span>. During the day the reaction of SCIs with
SO<span class="inline-formula"><sub>2</sub></span> was found to account for about 10 % and during the night for
about 40 % of the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> production, closing the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span>
budget during the day but leaving unexplained about 50 % of the
H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> formation during the night. Despite large uncertainties in
used kinetic parameters, these results indicate that the SO<span class="inline-formula"><sub>2</sub></span> oxidation
by SCIs may represent an important H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> source in VOC-rich environments, especially during nighttime.</p> |
| first_indexed | 2024-12-22T03:37:27Z |
| format | Article |
| id | doaj.art-6d80619ce9b549f8b1aa2293264ec3c7 |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-22T03:37:27Z |
| publishDate | 2021-09-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-6d80619ce9b549f8b1aa2293264ec3c72022-12-21T18:40:21ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242021-09-0121133331335110.5194/acp-21-13333-2021Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissionsA. Kukui0M. Chartier1J. Wang2J. Wang3H. Chen4H. Chen5S. Dusanter6S. Sauvage7V. Michoud8V. Michoud9N. Locoge10V. Gros11T. Bourrianne12K. Sellegri13J.-M. Pichon14Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), CNRS Orléans, FranceLaboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), CNRS Orléans, FranceResources and Environment Innovation Research Institute, School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan, 250101, ChinaICARE-CNRS, 1 C Av. de la Recherche Scientifique, 45071 Orléans CEDEX 2, FranceICARE-CNRS, 1 C Av. de la Recherche Scientifique, 45071 Orléans CEDEX 2, Francenow at: Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Institute of Atmospheric Sciences, Fudan University, Shanghai 200438, ChinaIMT Lille Douai, Institut Mines-Télécom, Univ. Lille, Centre for Energy and Environment, 59000 Lille, FranceIMT Lille Douai, Institut Mines-Télécom, Univ. Lille, Centre for Energy and Environment, 59000 Lille, FranceIMT Lille Douai, Institut Mines-Télécom, Univ. Lille, Centre for Energy and Environment, 59000 Lille, Francenow at: Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), UMR CNRS 7583, Université Paris Est Créteil (UPEC) et Université Paris Diderot (UPD), Créteil, FranceIMT Lille Douai, Institut Mines-Télécom, Univ. Lille, Centre for Energy and Environment, 59000 Lille, FranceLaboratoire des Sciences du Climat et de l'Environnement (LSCE), UMR CNRS-CEA-UVSQ, IPSL, Univ. Paris-Saclay, 91191 Gif-sur-Yvette, FranceCentre National de Recherches Météorologiques (CNRM), GMEI, MNP, Météo-France, 31057 Toulouse, FranceLaboratoire de Météorologie Physique Observatoire de Physique du Globe (LAMP), Clermont-Ferrand, FranceLaboratoire de Météorologie Physique Observatoire de Physique du Globe (LAMP), Clermont-Ferrand, France<p>Reaction of stabilized Criegee intermediates (SCIs) with SO<span class="inline-formula"><sub>2</sub></span> was proposed as an additional pathway of gaseous sulfuric acid (H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span>) formation in the atmosphere, supplementary to the conventional mechanism of H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> production by oxidation of SO<span class="inline-formula"><sub>2</sub></span> 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 H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> formation at a western Mediterranean (Cape Corsica) remote site, where comprehensive field observations including gas-phase H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span>, OH radicals, SO<span class="inline-formula"><sub>2</sub></span>, 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 H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> via SO<span class="inline-formula"><sub>2</sub></span> oxidation by the SCIs. Assuming the validity of a steady state between H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> production and its loss by condensation on existing aerosol particles with a unity accommodation coefficient, about 90 % of the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> formation during the day could be explained by the reaction of SO<span class="inline-formula"><sub>2</sub></span> with OH. During the night the oxidation of SO<span class="inline-formula"><sub>2</sub></span> by OH radicals was found to contribute only about 10 % to the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> formation. The accuracy of the derived values for the contribution of OH <span class="inline-formula">+</span> SO<span class="inline-formula"><sub>2</sub></span> reaction to the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> formation is limited mostly by a large, at present factor of 2, uncertainty in the OH <span class="inline-formula">+</span> SO<span class="inline-formula"><sub>2</sub></span> reaction rate coefficient. The contribution of the SO<span class="inline-formula"><sub>2</sub></span> oxidation by SCIs to the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> 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<span id="page13334"/> estimated concentration of the sum of SCIs was in the range of (1–3) <span class="inline-formula">×</span> 10<span class="inline-formula"><sup>3</sup></span> molec. cm<span class="inline-formula"><sup>−3</sup></span>. During the day the reaction of SCIs with SO<span class="inline-formula"><sub>2</sub></span> was found to account for about 10 % and during the night for about 40 % of the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> production, closing the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> budget during the day but leaving unexplained about 50 % of the H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> formation during the night. Despite large uncertainties in used kinetic parameters, these results indicate that the SO<span class="inline-formula"><sub>2</sub></span> oxidation by SCIs may represent an important H<span class="inline-formula"><sub>2</sub></span>SO<span class="inline-formula"><sub>4</sub></span> source in VOC-rich environments, especially during nighttime.</p>https://acp.copernicus.org/articles/21/13333/2021/acp-21-13333-2021.pdf |
| spellingShingle | A. Kukui M. Chartier J. Wang J. Wang H. Chen H. Chen S. Dusanter S. Sauvage V. Michoud V. Michoud N. Locoge V. Gros T. Bourrianne K. Sellegri J.-M. Pichon Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions Atmospheric Chemistry and Physics |
| title | Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions |
| title_full | Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions |
| title_fullStr | Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions |
| title_full_unstemmed | Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions |
| title_short | Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions |
| title_sort | role of criegee intermediates in the formation of sulfuric acid at a mediterranean cape corsica site under influence of biogenic emissions |
| url | https://acp.copernicus.org/articles/21/13333/2021/acp-21-13333-2021.pdf |
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