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@ARTICLE{Luo:1008188,
      author       = {Luo, Hao and Vereecken, Luc and Shen, Hongru and Kang,
                      Sungah and Pullinen, Iida and Hallquist, Mattias and Fuchs,
                      Hendrik and Wahner, Andreas and Kiendler-Scharr, Astrid and
                      Mentel, Thomas F. and Zhao, Defeng},
      title        = {{F}ormation of highly oxygenated organic molecules from the
                      oxidation of limonene by {OH} radical: significant
                      contribution of {H}-abstraction pathway},
      reportid     = {FZJ-2023-02234},
      year         = {2022},
      abstract     = {Highly oxygenated organic molecules (HOM) play a pivotal
                      role in the formation of secondary organic aerosol (SOA).
                      Therefore, the distribution and yields of HOM are
                      fundamental to understand their fate and chemical evolution
                      in the atmosphere, and it is conducive to ultimately assess
                      the impact of SOA on air quality and climate change. In this
                      study, gas-phase HOM formed from the reaction of limonene
                      with OH radical in photooxidation were investigated in the
                      SAPHIR chamber (Simulation of Atmospheric PHotochemistry In
                      a large Reaction chamber) using a time-of-flight chemical
                      ionization mass spectrometer with nitrate reagent ion
                      (NO3−-CIMS). A large number of HOM, including monomers
                      (C9–10) and dimers (C17–20), were detected and
                      classified into various families. Both closed-shell products
                      and open-shell peroxy radicals (RO2), were identified under
                      low NO (0.1 ppt–~0.2 ppb) and high NO conditions (17 ppb).
                      C10 monomers are the most abundant HOM products and account
                      for over 80 $\%$ total HOM. Closed-shell C10 monomers were
                      formed from two peroxy radical familie,
                      C10H15Ox•(x=7–12) and C10H17Ox•(x=8–13), and their
                      respective termination reactions with NO, RO2, and HO2.
                      While C10H17Ox• is likely formed by OH addition to C10H16,
                      the dominant initial step of limonene+OH, C10H15Ox•, is
                      likely formed via H-abstraction by OH. C10H15Ox• and
                      related products contributed 43 $\%$ and 46 $\%$ of C10-HOM
                      at low and high NO, demonstrating that H-abstraction
                      pathways play a significant role in HOM formation in the
                      reaction of limonene+OH. Combining theoretical kinetic
                      calculations, structure activity relationships (SARs),
                      literature data, and the observed RO2 intensities, we
                      proposed tentative mechanisms of HOM formation from both
                      pathways. We further estimated the molar yields of HOM to be
                      3.04−1.64+3.89 $\%$ and 0.82−0.44+1.05 $\%$ at low and
                      high NO, respectively. Our study highlights the importance
                      of H-abstraction by OH and provides yield and tentative
                      pathways in the OH oxidation of limonene to simulate the HOM
                      formation and assess their role in SOA formation.},
      cin          = {IEK-8},
      cid          = {I:(DE-Juel1)IEK-8-20101013},
      pnm          = {2111 - Air Quality (POF4-211)},
      pid          = {G:(DE-HGF)POF4-2111},
      typ          = {PUB:(DE-HGF)25},
      doi          = {10.5194/acp-2022-803},
      url          = {https://juser.fz-juelich.de/record/1008188},
}