Formation and temperature dependence of highly oxygenated organic molecules (HOMs) from δ3-carene ozonolysis

Yuanyuan Luo*, Ditte Thomsen, Emil Mark Iversen, Pontus Roldin, Jane Tygesen Skønager, Linjie Li, Michael Priestley, Henrik B. Pedersen, Mattias Hallquist, Merete Bilde, Marianne Glasius, Mikael Ehn*

*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review

Abstract

δ3-carene is a prominent monoterpene in the atmosphere, contributing significantly to secondary organic aerosol (SOA) formation. However, knowledge about δ3-carene oxidation pathways, particularly regarding their ability to form highly oxygenated organic molecules (HOMs), is still limited. In this study, we present HOM measurements during δ3-carene ozonolysis under various conditions in two simulation chambers. We identified numerous HOMs (monomers: C7-10H10-18O6-14; dimers: C17-20H24-34O6-18) using a chemical ionization mass spectrometer (CIMS). δ3-carene ozonolysis yielded higher HOM concentrations than α-pinene, with a distinct distribution, indicating differences in formation pathways. All HOM signals decreased considerably at lower temperatures, reducing the estimated molar HOM yield from ∼ 3 % at 20 °C to ∼ 0.5 % at 0 °C. Interestingly, the temperature change altered the HOM distribution, increasing the observed dimer-to-monomer ratios from roughly 0.8 at 20 °C to 1.5 at 0 °C. HOM monomers with six or seven O atoms condensed more efficiently onto particles at colder temperatures, while monomers with nine or more O atoms and all dimers condensed irreversibly even at 20 °C. Using the gas- and particle-phase chemistry kinetic multilayer model ADCHAM, we were also able to reproduce the experimentally observed HOM composition, yields, and temperature dependence.

Original languageEnglish
JournalAtmospheric Chemistry and Physics
Volume24
Issue16
Pages (from-to)9459-9473
Number of pages15
ISSN1680-7316
DOIs
Publication statusPublished - 29 Aug 2024

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