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@ARTICLE{Pullinen:885396,
      author       = {Pullinen, Iida and Schmitt, Sebastian and Kang, Sungah and
                      Sarrafzadeh, Mehrnaz and Schlag, Patrick and Andres,
                      Stefanie and Kleist, Einhard and Mentel, Thomas F. and
                      Rohrer, Franz and Springer, Monika and Tillmann, Ralf and
                      Wildt, Jürgen and Wu, Cheng and Zhao, Defeng and Wahner,
                      Andreas and Kiendler-Scharr, Astrid},
      title        = {{I}mpact of {NO}x on secondary organic aerosol ({SOA})
                      formation from α-pinene and β-pinene photooxidation: the
                      role of highly oxygenated organic nitrates},
      journal      = {Atmospheric chemistry and physics},
      volume       = {20},
      number       = {17},
      issn         = {1680-7324},
      address      = {Katlenburg-Lindau},
      publisher    = {EGU},
      reportid     = {FZJ-2020-03793},
      pages        = {10125 - 10147},
      year         = {2020},
      abstract     = {The formation of organic nitrates (ONs) in the gas phase
                      and their impact on mass formation of secondary organic
                      aerosol (SOA) was investigated in a laboratory study for
                      α-pinene and β-pinene photooxidation. Focus was the
                      elucidation of those mechanisms that cause the often
                      observed suppression of SOA mass formation by NOx, and
                      therein the role of highly oxygenated multifunctional
                      molecules (HOMs). We observed that with increasing NOx
                      concentration (a) the portion of HOM organic nitrates
                      (HOM-ONs) increased, (b) the fraction of accretion products
                      (HOM-ACCs) decreased, and (c) HOM-ACCs contained on average
                      smaller carbon numbers.Specifically, we investigated HOM
                      organic nitrates (HOM-ONs), arising from the termination
                      reactions of HOM peroxy radicals with NOx, and HOM
                      permutation products (HOM-PPs), such as ketones, alcohols,
                      or hydroperoxides, formed by other termination reactions.
                      Effective uptake coefficients γeff of HOMs on particles
                      were determined. HOMs with more than six O atoms efficiently
                      condensed on particles (γeff>0.5 on average), and for HOMs
                      containing more than eight O atoms, every collision led to
                      loss. There was no systematic difference in γeff for
                      HOM-ONs and HOM-PPs arising from the same HOM peroxy
                      radicals. This similarity is attributed to the
                      multifunctional character of the HOMs: as functional groups
                      in HOMs arising from the same precursor HOM peroxy radical
                      are identical, vapor pressures should not strongly depend on
                      the character of the final termination group. As a
                      consequence, the suppressing effect of NOx on SOA formation
                      cannot be simply explained by replacement of terminal
                      functional groups by organic nitrate groups.According to
                      their γeff all HOM-ONs with more than six O atoms will
                      contribute to organic bound nitrate (OrgNO3) in the
                      particulate phase. However, the fraction of OrgNO3 stored in
                      condensable HOMs with molecular masses > 230 Da
                      appeared to be substantially higher than the fraction of
                      particulate OrgNO3 observed by aerosol mass spectrometry.
                      This result suggests losses of OrgNO3 for organic nitrates
                      in particles, probably due to hydrolysis of OrgNO3 that
                      releases HNO3 into the gas phase but leaves behind the
                      organic rest in the particulate phase. However, the loss of
                      HNO3 alone could not explain the observed suppressing effect
                      of NOx on particle mass formation from α-pinene and
                      β-pinene.Instead we can attribute most of the reduction in
                      SOA mass yields with increasing NOx to the significant
                      suppression of gas phase HOM-ACCs, which have high molecular
                      mass and are potentially important for SOA mass formation at
                      low-NOx conditions.},
      cin          = {IEK-8},
      ddc          = {550},
      cid          = {I:(DE-Juel1)IEK-8-20101013},
      pnm          = {243 - Tropospheric trace substances and their
                      transformation processes (POF3-243)},
      pid          = {G:(DE-HGF)POF3-243},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000567769500001},
      doi          = {10.5194/acp-20-10125-2020},
      url          = {https://juser.fz-juelich.de/record/885396},
}