Preprints
https://doi.org/10.5194/acp-2021-340
https://doi.org/10.5194/acp-2021-340

  30 Apr 2021

30 Apr 2021

Review status: a revised version of this preprint was accepted for the journal ACP and is expected to appear here in due course.

Atmospheric photooxidation and ozonolysis of Δ3-carene and 3-caronaldehyde: Rate constants and product yields

Luisa Lamberta Hantschke, Anna Novelli, Birger Bohn, Changmin Cho, David Reimer, Franz Rohrer, Ralf Tillmann, Marvin Glowania, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs Luisa Lamberta Hantschke et al.
  • Institute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, Germany

Abstract. The oxidation of Δ3-carene and one of its main oxidation products, caronaldehyde, by the OH radical and O3 was investigated in the atmospheric simulation chamber SAPHIR under atmospheric conditions for NOx mixing ratios below 2 ppbv. Within this study, the rate constants of the reaction of Δ3-carene with OH and O3, and of the reaction of caronaldehyde with OH were determined to be (8.0 ± 0.5) × 10−11 cm3 s−1 at 304 K, (4.4 ± 0.2) × 10−17 cm3 s−1 at 300 K and (4.6 ± 1.6) × 10−11 cm3 s−1 at 300 K, respectively, in agreement with previously published values. The yields of caronaldehyde from the reaction of OH and ozone with Δ3-carene were determined to be (0.30 ± 0.05) and (0.06 ± 0.02), respectively. Both values are in reasonably well agreement with reported literature values. An organic nitrate (RONO2) yield from the reaction of NO with RO2 derived from Δ3-carene of (0.25 ± 0.04) was determined from the analysis of the reactive nitrogen species (NOy) in the SAPHIR chamber. The RONO2 yield of the reaction of NO with RO2 derived from the reaction of caronaldehyde with OH was found to be (0.10 ± 0.02). The organic nitrate yields of Δ3-carene and caronaldehyde oxidation with OH are reported here for the first time in the gas phase. An OH yield of (0.65 ± 0.10) was determined from the ozonolysis of Δ3-carene. Calculations of production and destruction rates of the sum of hydroxyl and peroxy radicals (ROx = OH+HO2+RO2) demonstrated that there were no unaccounted production or loss processes of radicals in the oxidation of Δ3-carene for conditions of the the chamber experiments. In an OH free experiment with added OH scavenger, the photolysis frequency of caronaldehyde was obtained from its photolytical decay. The experimental photolysis frequency was a factor of 7 higher than the value calculated from the measured solar acintic flux density, an absorption cross section from the literature and an assumed effective quantum yield of unity for photodissociation.

Luisa Lamberta Hantschke et al.

Status: closed

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2021-340', Anonymous Referee #1, 18 May 2021
  • RC2: 'Comment on acp-2021-340', Anonymous Referee #2, 18 May 2021
  • AC1: 'Responses to the referees on acp-2021-340', Luisa Hantschke, 08 Jul 2021

Status: closed

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2021-340', Anonymous Referee #1, 18 May 2021
  • RC2: 'Comment on acp-2021-340', Anonymous Referee #2, 18 May 2021
  • AC1: 'Responses to the referees on acp-2021-340', Luisa Hantschke, 08 Jul 2021

Luisa Lamberta Hantschke et al.

Data sets

Data set for experiments on 31 May 2020 Hantschke, L., Fuchs, H., Novelli, A., Bohn, B., Cho, C., Reimer, D., Rohrer, F., Tillmann, R., & Glowania, M. https://doi.org/10.25326/QACC-KJ83

Data set for Experiment on 13 June 2019 Hantschke, L., Fuchs, H., Novelli, A., Bohn, B., Cho, C., Reimer, D., Rohrer, F., Tillmann, R., & Glowania, M. https://doi.org/10.25326/BQNH-P286

Data set for Experiment on 21 May 2020 Hantschke, L., Fuchs, H., Novelli, A., Bohn, B., Cho, C., Reimer, D., Rohrer, F., Tillmann, R., & Glowania, M. https://doi.org/10.25326/AGPD-MP70

Data set for Experiment on 27 May 2020 Hantschke, L., Fuchs, H., Novelli, A., Bohn, B., Cho, C., Reimer, D., Rohrer, F., Tillmann, R., & Glowania, M. https://doi.org/10.25326/8K59-JC53

Luisa Lamberta Hantschke et al.

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Short summary
In the present study, the reactions of Δ3-carene with ozone and the hydroxyl radical (OH) and the photolysis and OH reaction caronaldehyde were investigated in the simulation chamber. Reaction rate constants of these reactions were determined. Caronaldehyde yields of the ozonolysis and OH reaction were determined. The organic nitrate yield of the reaction of Δ3-carene and caronaldehyde derived peroxy radicals with NO was determined. The ROx budget (ROx = OH+HO2+RO2) was also investigated.
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