Preprints
https://doi.org/10.5194/acp-2021-199
https://doi.org/10.5194/acp-2021-199

  01 Apr 2021

01 Apr 2021

Review status: this preprint is currently under review for the journal ACP.

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

Alexandre Kukui1, Michel Chartier1, Jinhe Wang2,3, Hui Chen3,a, Sébastien Dusanter4, Stéphane Sauvage4, Vincent Michoud4,b, Nadine Locoge4, Valérie Gros5, Thierry Bourrianne6, Karine Sellegri7, and Jean-Marc Pichon7 Alexandre Kukui et al.
  • 1Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), CNRS Orléans, France
  • 2Resources and Environment Innovation Research Institute, School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan 250101, China
  • 3ICARE-CNRS, 1 C Av. de la Recherche Scientifique, 45071 Orléans CEDEX 2, France
  • 4IMT Lille Douai, Institut Mines -Télécom, Univ. Lille, Centre for Energy and Environment, F-59000 Lille, France
  • 5Laboratoire des Sciences du Climat et de l'Environnement (LSCE), UMR CNRS-CEA-UVSQ, IPSL, Univ. Paris-Saclay, F91191 Gif Sur Yvette, France
  • 6Centre National de Recherches Météorologiques (CNRM), GMEI, MNP, Météo-France, F-31057 Toulouse, France
  • 7Laboratoire de Météorologie Physique Observatoire de Physique du Globe (LAMP), Clermont-Ferrand, France
  • anow at: Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Institute of Atmospheric Sciences, Fudan University, Shanghai 200438, China
  • bnow at: Université de Paris, Université Paris Est Créteil (UPEC), UMR CNRS 7583, Laboratoire Interuniversitaire des Systèmes Atmosphériques, Paris, France

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 a comprehensive field observations including gas phase H2SO4, OH radicals, SO2, volatile organic compounds (VOCs) and aerosol size distribution measurements have been performed in July–August 2013 as a part of the project ChArMEx. 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, presently of a factor of 2, uncertainty in 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 SCIs concentrations estimated by adopting rate coefficients for SCIs reactions based on structure–activity relationships (SARs). The estimated concentration of the sum of SCIs was in the range of (1–3) × 103 molecule 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 VOCs-rich environments, especially during night-time.

Alexandre Kukui et al.

Status: open (extended)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Review of acp-2021-199', Anonymous Referee #2, 02 May 2021 reply

Alexandre Kukui et al.

Alexandre Kukui et al.

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Short summary
Sulfuric acid, H2SO4, plays a key role in formation of secondary atmospheric aerosol particles. It is generally accepted that the major atmospheric source of H2SO4 is the reaction of OH radicals with SO2. In this study, an importance of additional H2SO4 source via oxidation of SO2 by stabilized Criegee intermediates was estimated based on measurements at a remote site on Cape Corsica. It was found that the oxidation of SO2 by SCI may be an important source of H2SO4, especially during night-time.
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