Large Discrepancy in the Formation of Secondary Organic Aerosols from Structurally Similar Monoterpenes

TY - JOUR

T1 - Large Discrepancy in the Formation of Secondary Organic Aerosols from Structurally Similar Monoterpenes

AU - Thomsen, Ditte

AU - Elm, Jonas

AU - Rosati, Bernadette

AU - Skønager, Jane Tygesen

AU - Bilde, Merete

AU - Glasius, Marianne

N1 - Publisher Copyright: © 2021 The Authors. Published by American Chemical Society. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/3

Y1 - 2021/3

N2 - The two monoterpenes, Δ3-carene and α-pinene, have very similar chemical structures, which leads to the assumption that the formation of secondary organic aerosol (SOA) is also similar. This study aims to investigate if the formation of SOA from ozonolysis of Δ3-carene and α-pinene is actually analogous. This is addressed by conducting smog chamber studies of Δ3-carene ozonolysis and comparing the results to similar studies of α-pinene. Detailed offline analysis using ultra-high-performance liquid chromatography coupled to mass spectrometry seeks to elucidate differences in the product distribution between Δ3-carene and α-pinene. The experimental findings are supported by quantum chemical calculations of formation free energies of the first-generation oxidation products, cis-3-caric acid and cis-pinic acid. The smog chamber studies and detailed offline analysis show a considerable difference in the SOA formation from Δ3-carene and α-pinene. Δ3-carene produces higher SOA mass and larger particles, whereas α-pinene produces a larger number of smaller particles. This indicates that Δ3-carene oxidation products tend to condense on already existing particles, whereas α-pinene oxidation products to a larger degree contribute to new particle formation. The detailed offline analysis shows a much less diverse product distribution in Δ3-carene SOA compared to α-pinene SOA. In addition, three dimers from Δ3-carene are identified for the first time. The quantum chemical calculations indicate that cis-3-caric acid is expected to be more efficient in condensing on already existing particles compared to cis-pinic acid, which is in good agreement with the experimental results.

AB - The two monoterpenes, Δ3-carene and α-pinene, have very similar chemical structures, which leads to the assumption that the formation of secondary organic aerosol (SOA) is also similar. This study aims to investigate if the formation of SOA from ozonolysis of Δ3-carene and α-pinene is actually analogous. This is addressed by conducting smog chamber studies of Δ3-carene ozonolysis and comparing the results to similar studies of α-pinene. Detailed offline analysis using ultra-high-performance liquid chromatography coupled to mass spectrometry seeks to elucidate differences in the product distribution between Δ3-carene and α-pinene. The experimental findings are supported by quantum chemical calculations of formation free energies of the first-generation oxidation products, cis-3-caric acid and cis-pinic acid. The smog chamber studies and detailed offline analysis show a considerable difference in the SOA formation from Δ3-carene and α-pinene. Δ3-carene produces higher SOA mass and larger particles, whereas α-pinene produces a larger number of smaller particles. This indicates that Δ3-carene oxidation products tend to condense on already existing particles, whereas α-pinene oxidation products to a larger degree contribute to new particle formation. The detailed offline analysis shows a much less diverse product distribution in Δ3-carene SOA compared to α-pinene SOA. In addition, three dimers from Δ3-carene are identified for the first time. The quantum chemical calculations indicate that cis-3-caric acid is expected to be more efficient in condensing on already existing particles compared to cis-pinic acid, which is in good agreement with the experimental results.

KW - dimer

KW - secondary organic aerosol

KW - smog chamber studies

KW - α-pinene

KW - Δ-carene

U2 - 10.1021/acsearthspacechem.0c00332

DO - 10.1021/acsearthspacechem.0c00332

M3 - Journal article

AN - SCOPUS:85103515734

SN - 2472-3452

VL - 5

SP - 632

EP - 644

JO - ACS Earth and Space Chemistry

JF - ACS Earth and Space Chemistry

IS - 3

ER -