TY - JOUR

T1 - Particle-phase accretion forms dimer esters in pinene secondary organic aerosol

AU - Kenseth, Christopher M.

AU - Hafeman, Nicholas J.

AU - Rezgui, Samir P.

AU - Chen, Jing

AU - Huang, Yuanlong

AU - Dalleska, Nathan F.

AU - Kjaergaard, Henrik G.

AU - Stoltz, Brian M.

AU - Seinfeld, John H.

AU - Wennberg, Paul O.

N1 - Funding Information: We thank J. D. Crounse and J. A. Thornton for useful discussions and the Thomson group at Northwestern University for providing one of the dimer ester standards. UPLC/(−)ESI-Q-TOF-MS was performed in the Resnick Sustainability Institute Water and Environment Lab at the California Institute of Technology. This work was supported by the National Science Foundation (AGS-1523500, CHE-1800511, and CHE-1905340), the Independent Research Fund Denmark (9040-00142B), the Villum Fonden (VIL50443), and the Alfred P. Sloan Foundation (G-2019-12281). C.M.K. acknowledges support from a National Science Foundation Atmospheric and Geospace Sciences Postdoctoral Research Fellowship (AGS-2132296). Publisher Copyright: Copyright © 2023 The Authors, some rights reserved.

PY - 2023

Y1 - 2023

N2 - Secondary organic aerosol (SOA) is ubiquitous in the atmosphere and plays a pivotal role in climate, air quality, and health. The production of low-volatility dimeric compounds through accretion reactions i a key aspect of SOA formation. However, despite extensive study, the structures and thus the formation mechanisms of dimers in SOA remain largely uncharacterized. In this work, we elucidate the structures of several major dimer esters in SOA from ozonolysis of a-pinene and b-pinene—substantial global SOA sources—through independent synthesis of authentic standards. We show that these dimer esters are formed in the particle phase and propose a mechanism of nucleophilic addition of alcohols to a cyclic acylperoxyhemiacetal. This chemistry likely represents a general pathway to dimeric compounds in ambient SOA

AB - Secondary organic aerosol (SOA) is ubiquitous in the atmosphere and plays a pivotal role in climate, air quality, and health. The production of low-volatility dimeric compounds through accretion reactions i a key aspect of SOA formation. However, despite extensive study, the structures and thus the formation mechanisms of dimers in SOA remain largely uncharacterized. In this work, we elucidate the structures of several major dimer esters in SOA from ozonolysis of a-pinene and b-pinene—substantial global SOA sources—through independent synthesis of authentic standards. We show that these dimer esters are formed in the particle phase and propose a mechanism of nucleophilic addition of alcohols to a cyclic acylperoxyhemiacetal. This chemistry likely represents a general pathway to dimeric compounds in ambient SOA

U2 - 10.1126/science.adi0857

DO - 10.1126/science.adi0857

M3 - Journal article

C2 - 37972156

AN - SCOPUS:85178523258

VL - 382

SP - 787

EP - 792

JO - Science

JF - Science

SN - 0036-8075

IS - 6672

ER -