Ozonolysis of α-Pinene and Δ3-Carene Mixtures: Formation of Dimers with Two Precursors

Ditte Thomsen; Lotte Dyrholm Thomsen; Emil Mark Iversen; Thuríđur Nótt Björgvinsdóttir; Sofie Falk Vinther; Jane Tygesen Skønager; Thorsten Hoffmann; Jonas Elm; Merete Bilde; Marianne Glasius

doi:10.1021/acs.est.2c04786

Ozonolysis of α-Pinene and Δ³-Carene Mixtures: Formation of Dimers with Two Precursors

Ditte Thomsen, Lotte Dyrholm Thomsen, Emil Mark Iversen, Thuríđur Nótt Björgvinsdóttir, Sofie Falk Vinther, Jane Tygesen Skønager, Thorsten Hoffmann, Jonas Elm, Merete Bilde, Marianne Glasius^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

12 Citations (Scopus)

Abstract

The formation of secondary organic aerosol (SOA) from the structurally similar monoterpenes, α-pinene and Δ3-carene, differs substantially. The aerosol phase is already complex for a single precursor, and when mixtures are oxidized, products, e.g., dimers, may form between different volatile organic compounds (VOCs). This work investigates whether differences in SOA formation and properties from the oxidation of individual monoterpenes persist when a mixture of the monoterpenes is oxidized. Ozonolysis of α-pinene, Δ3-carene, and a 1:1 mixture of them was performed in the Aarhus University Research on Aerosol (AURA) atmospheric simulation chamber. Here, ∼100 ppb of monoterpene was oxidized by 200 ppb O3 under dark conditions at 20 °C. The particle number concentration and particle mass concentration for ozonolysis of α-pinene exceed those from ozonolysis of Δ3-carene alone, while their mixture results in concentrations similar to α-pinene ozonolysis. Detailed offline analysis reveals evidence of VOC-cross-product dimers in SOA from ozonolysis of the monoterpene mixture: a VOC-cross-product dimer likely composed of the monomeric units cis-caric acid and 10-hydroxy-pinonic acid and a VOC-cross-product dimer ester likely from the monomeric units caronaldehyde and terpenylic acid were tentatively identified by liquid chromatography-mass spectrometry. To improve the understanding of chemical mechanisms determining SOA, it is relevant to identify VOC-cross-products.

Original language	English
Journal	Environmental Science & Technology
Volume	56
Issue	23
Pages (from-to)	16643-16651
Number of pages	9
ISSN	0013-936X
DOIs	https://doi.org/10.1021/acs.est.2c04786
Publication status	Published - Dec 2022

Keywords

aerosol formation
monoterpene oxidation
secondary organic aerosol
sequential spot sampler

Access to Document

10.1021/acs.est.2c04786

Cite this

@article{e3c1343ebb724d398101f2a989fa6f71,

title = "Ozonolysis of α-Pinene and Δ3-Carene Mixtures: Formation of Dimers with Two Precursors",

abstract = "The formation of secondary organic aerosol (SOA) from the structurally similar monoterpenes, α-pinene and Δ3-carene, differs substantially. The aerosol phase is already complex for a single precursor, and when mixtures are oxidized, products, e.g., dimers, may form between different volatile organic compounds (VOCs). This work investigates whether differences in SOA formation and properties from the oxidation of individual monoterpenes persist when a mixture of the monoterpenes is oxidized. Ozonolysis of α-pinene, Δ3-carene, and a 1:1 mixture of them was performed in the Aarhus University Research on Aerosol (AURA) atmospheric simulation chamber. Here, ∼100 ppb of monoterpene was oxidized by 200 ppb O3 under dark conditions at 20 °C. The particle number concentration and particle mass concentration for ozonolysis of α-pinene exceed those from ozonolysis of Δ3-carene alone, while their mixture results in concentrations similar to α-pinene ozonolysis. Detailed offline analysis reveals evidence of VOC-cross-product dimers in SOA from ozonolysis of the monoterpene mixture: a VOC-cross-product dimer likely composed of the monomeric units cis-caric acid and 10-hydroxy-pinonic acid and a VOC-cross-product dimer ester likely from the monomeric units caronaldehyde and terpenylic acid were tentatively identified by liquid chromatography-mass spectrometry. To improve the understanding of chemical mechanisms determining SOA, it is relevant to identify VOC-cross-products.",

keywords = "aerosol formation, monoterpene oxidation, secondary organic aerosol, sequential spot sampler",

author = "Ditte Thomsen and Thomsen, {Lotte Dyrholm} and Iversen, {Emil Mark} and Bj{\"o}rgvinsd{\'o}ttir, {Thur{\'i}{\d}ur N{\'o}tt} and Vinther, {Sofie Falk} and Sk{\o}nager, {Jane Tygesen} and Thorsten Hoffmann and Jonas Elm and Merete Bilde and Marianne Glasius",

year = "2022",

month = dec,

doi = "10.1021/acs.est.2c04786",

language = "English",

volume = "56",

pages = "16643--16651",

journal = "Environmental Science & Technology",

issn = "0013-936X",

publisher = "American Chemical Society",

number = "23",

}

Ozonolysis of α-Pinene and Δ³-Carene Mixtures: Formation of Dimers with Two Precursors. / Thomsen, Ditte ; Thomsen, Lotte Dyrholm ; Iversen, Emil Mark et al.
In: Environmental Science & Technology, Vol. 56, No. 23, 12.2022, p. 16643-16651.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - Ozonolysis of α-Pinene and Δ3-Carene Mixtures

T2 - Formation of Dimers with Two Precursors

AU - Thomsen, Ditte

AU - Thomsen, Lotte Dyrholm

AU - Iversen, Emil Mark

AU - Björgvinsdóttir, Thuríđur Nótt

AU - Vinther, Sofie Falk

AU - Skønager, Jane Tygesen

AU - Hoffmann, Thorsten

AU - Elm, Jonas

AU - Bilde, Merete

AU - Glasius, Marianne

PY - 2022/12

Y1 - 2022/12

N2 - The formation of secondary organic aerosol (SOA) from the structurally similar monoterpenes, α-pinene and Δ3-carene, differs substantially. The aerosol phase is already complex for a single precursor, and when mixtures are oxidized, products, e.g., dimers, may form between different volatile organic compounds (VOCs). This work investigates whether differences in SOA formation and properties from the oxidation of individual monoterpenes persist when a mixture of the monoterpenes is oxidized. Ozonolysis of α-pinene, Δ3-carene, and a 1:1 mixture of them was performed in the Aarhus University Research on Aerosol (AURA) atmospheric simulation chamber. Here, ∼100 ppb of monoterpene was oxidized by 200 ppb O3 under dark conditions at 20 °C. The particle number concentration and particle mass concentration for ozonolysis of α-pinene exceed those from ozonolysis of Δ3-carene alone, while their mixture results in concentrations similar to α-pinene ozonolysis. Detailed offline analysis reveals evidence of VOC-cross-product dimers in SOA from ozonolysis of the monoterpene mixture: a VOC-cross-product dimer likely composed of the monomeric units cis-caric acid and 10-hydroxy-pinonic acid and a VOC-cross-product dimer ester likely from the monomeric units caronaldehyde and terpenylic acid were tentatively identified by liquid chromatography-mass spectrometry. To improve the understanding of chemical mechanisms determining SOA, it is relevant to identify VOC-cross-products.

AB - The formation of secondary organic aerosol (SOA) from the structurally similar monoterpenes, α-pinene and Δ3-carene, differs substantially. The aerosol phase is already complex for a single precursor, and when mixtures are oxidized, products, e.g., dimers, may form between different volatile organic compounds (VOCs). This work investigates whether differences in SOA formation and properties from the oxidation of individual monoterpenes persist when a mixture of the monoterpenes is oxidized. Ozonolysis of α-pinene, Δ3-carene, and a 1:1 mixture of them was performed in the Aarhus University Research on Aerosol (AURA) atmospheric simulation chamber. Here, ∼100 ppb of monoterpene was oxidized by 200 ppb O3 under dark conditions at 20 °C. The particle number concentration and particle mass concentration for ozonolysis of α-pinene exceed those from ozonolysis of Δ3-carene alone, while their mixture results in concentrations similar to α-pinene ozonolysis. Detailed offline analysis reveals evidence of VOC-cross-product dimers in SOA from ozonolysis of the monoterpene mixture: a VOC-cross-product dimer likely composed of the monomeric units cis-caric acid and 10-hydroxy-pinonic acid and a VOC-cross-product dimer ester likely from the monomeric units caronaldehyde and terpenylic acid were tentatively identified by liquid chromatography-mass spectrometry. To improve the understanding of chemical mechanisms determining SOA, it is relevant to identify VOC-cross-products.

KW - aerosol formation

KW - monoterpene oxidation

KW - secondary organic aerosol

KW - sequential spot sampler

U2 - 10.1021/acs.est.2c04786

DO - 10.1021/acs.est.2c04786

M3 - Journal article

C2 - 36355568

SN - 0013-936X

VL - 56

SP - 16643

EP - 16651

JO - Environmental Science & Technology

JF - Environmental Science & Technology

IS - 23