Atmospheric photooxidation and ozonolysis of Δ 3-carene and 3-caronaldehyde: rate constants and product yields

Hantschke, Luisa; Novelli, Anna; Bohn, Birger; Cho, Changmin; Reimer, David; Rohrer, Franz; Tillmann, Ralf; Glowania, Marvin; Hofzumahaus, Andreas; Kiendler-Scharr, Astrid; Wahner, Andreas; Fuchs, Hendrik

The oxidation of inline-formulaΔ3-carene and one of its main oxidation products, caronaldehyde, by the inline-formulaOH radical and inline-formulaO3 was investigated in the atmospheric simulation chamber SAPHIR under atmospheric conditions for inline-formulaNOx mixing ratios below inline-formula2inline-formulappbv. Within this study, the rate constants of the reaction of inline-formulaΔ3-carene with inline-formulaOH and inline-formulaO3 and of the reaction of caronaldehyde with inline-formulaOH were determined to be inline-formula M12inlinescrollmathml ( normal 8.0 ± normal 0.5 ) × normal 10 - normal 11 89pt15ptsvg-formulamathimg6d57794042b8058842d25c1e4f14befa acp-21-12665-2021-ie00001.svg89pt15ptacp-21-12665-2021-ie00001.png inline-formulacm3 s−1 at inline-formula304inline-formulaK, inline-formula M16inlinescrollmathml ( normal 4.4 ± normal 0.2 ) × normal 10 - normal 17 89pt15ptsvg-formulamathimgcb5c5f2d74cd002b6408bf8d3f9b3e59 acp-21-12665-2021-ie00002.svg89pt15ptacp-21-12665-2021-ie00002.png inline-formulacm3 s−1 at inline-formula300inline-formulaK and inline-formula M20inlinescrollmathml ( normal 4.6 ± normal 1.6 ) × normal 10 - normal 11 89pt15ptsvg-formulamathimg2b450bfd508a10cb6d05262cda6108d6 acp-21-12665-2021-ie00003.svg89pt15ptacp-21-12665-2021-ie00003.png inline-formulacm3 s−1 at inline-formula300inline-formulaK, in agreement with previously published values. The yields of caronaldehyde from the reaction of inline-formulaOH and ozone with inline-formulaΔ3-carene were determined to be inline-formula0.30±0.05 and inline-formula0.06±0.02, respectively. Both values are in reasonably good agreement with reported literature values. An organic nitrate (inline-formulaRONO2) yield from the reaction of inline-formulaNO with inline-formulaRO2 derived from inline-formulaΔ3-carene of inline-formula0.25±0.04 was determined from the analysis of the reactive nitrogen species (inline-formulaNOinline-formulay) in the SAPHIR chamber. The inline-formulaRONO2 yield of the reaction of inline-formulaNO with inline-formulaRO2 derived from the reaction of caronaldehyde with inline-formulaOH was found to be inline-formula0.10±0.02. The organic nitrate yields of inline-formulaΔ3-carene and caronaldehyde oxidation with inline-formulaOH are reported here for the first time in the gas phase. An inline-formulaOH yield of inline-formula0.65±0.10 was determined from the ozonolysis of inline-formulaΔ3-carene. Calculations of production and destruction rates of the sum of hydroxyl and peroxy radicals (inline-formula M45inlinescrollmathml chem normal RO x = chem normal OH + chem normal HO normal 2 + chem normal RO normal 2 117pt13ptsvg-formulamathimg3cfb6ac81805f4c4be8eb47e351f13c0 acp-21-12665-2021-ie00004.svg117pt13ptacp-21-12665-2021-ie00004.png ) demonstrated that there were no unaccounted production or loss processes of radicals in the oxidation of inline-formulaΔ3-carene for conditions of the chamber experiments. In an inline-formulaOH-free experiment with added inline-formulaOH 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 actinic flux density, an absorption cross section from the literature and an assumed effective quantum yield of unity for photodissociation.



Hantschke, Luisa / Novelli, Anna / Bohn, Birger / et al: Atmospheric photooxidation and ozonolysis of Δ3-carene and 3-caronaldehyde: rate constants and product yields. 2021. Copernicus Publications.


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