TY - JOUR
T1 - Probing the Fate of Highly Oxygenated Molecules in Atmospheric Aerosols
AU - Hao, Peizhi
AU - Ye, Qing
AU - Moo, Zeyi
AU - DeMarsh, Kate
AU - Wang, Yaying
AU - Palm, Brett B.
AU - Zarzana, Kyle J.
AU - Apel, Eric C.
AU - Tyndall, Geoffrey S.
AU - Orlando, John J.
AU - Zhang, Xuan
N1 - Publisher Copyright:
© 2025 American Chemical Society
PY - 2025/7/22
Y1 - 2025/7/22
N2 - This study presents a comprehensive data set tracking the trajectory of highly oxidized molecules (HOMs) produced from the ozonolysis of monoterpenes across the gas to particle conversion process. A particular focus was to examine the ultimate fate of HOMs in suspended particles after the completion of gas phase chemistry. The observed dynamics of HOMs, therefore, provides direct insights into the role of condensed-phase chemistry, if any, in modifying their molecular composition. Individual SOA-bound HOMs exhibited remarkably diverse behaviors, and even certain isomers of identical elemental composition appeared to undergo different transformations. A small group of C8–10and C20HOMs decayed rapidly in hydrated particles, on a time scale akin to those of organic hydroperoxides. On the other hand, a subset of C12–20dimers was found to continuously grow in abundance, and the presence of water substantially enhanced their growth rates. This rising trend was well captured by box model simulations that incorporate the kinetics of condensed-phase chemistry, specifically the peroxyhemiacetal formation pathway. The majority of HOMs remained structurally stable across all hydrous and photolytic conditions investigated in this study. This persistence highlights the potential of HOMs as a widespread and sustained source of cloud condensation nuclei in the atmosphere.
AB - This study presents a comprehensive data set tracking the trajectory of highly oxidized molecules (HOMs) produced from the ozonolysis of monoterpenes across the gas to particle conversion process. A particular focus was to examine the ultimate fate of HOMs in suspended particles after the completion of gas phase chemistry. The observed dynamics of HOMs, therefore, provides direct insights into the role of condensed-phase chemistry, if any, in modifying their molecular composition. Individual SOA-bound HOMs exhibited remarkably diverse behaviors, and even certain isomers of identical elemental composition appeared to undergo different transformations. A small group of C8–10and C20HOMs decayed rapidly in hydrated particles, on a time scale akin to those of organic hydroperoxides. On the other hand, a subset of C12–20dimers was found to continuously grow in abundance, and the presence of water substantially enhanced their growth rates. This rising trend was well captured by box model simulations that incorporate the kinetics of condensed-phase chemistry, specifically the peroxyhemiacetal formation pathway. The majority of HOMs remained structurally stable across all hydrous and photolytic conditions investigated in this study. This persistence highlights the potential of HOMs as a widespread and sustained source of cloud condensation nuclei in the atmosphere.
KW - highly oxidized molecules
KW - monoterpene
KW - secondary organic aerosols
UR - https://www.scopus.com/pages/publications/105010201722
U2 - 10.1021/acs.est.4c07748
DO - 10.1021/acs.est.4c07748
M3 - Article
C2 - 40635568
AN - SCOPUS:105010201722
SN - 0013-936X
VL - 59
SP - 14540
EP - 14551
JO - Environmental Science and Technology
JF - Environmental Science and Technology
IS - 28
ER -