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@ARTICLE{Zaytsev:893672,
      author       = {Zaytsev, Alexander and Breitenlechner, Martin and Novelli,
                      Anna and Fuchs, Hendrik and Knopf, Daniel A. and Kroll,
                      Jesse H. and Keutsch, Frank N.},
      title        = {{A}pplication of chemical derivatization techniques
                      combined with chemical ionization mass spectrometry to
                      detect stabilized {C}riegee intermediates and peroxy
                      radicals in the gas phase},
      journal      = {Atmospheric measurement techniques},
      volume       = {14},
      number       = {3},
      issn         = {1867-8548},
      address      = {Katlenburg-Lindau},
      publisher    = {Copernicus},
      reportid     = {FZJ-2021-02744},
      pages        = {2501 - 2513},
      year         = {2021},
      abstract     = {Short-lived highly reactive atmospheric species, such as
                      organic peroxy radicals (RO2) and stabilized Criegee
                      intermediates (SCIs), play an important role in controlling
                      the oxidative removal and transformation of many natural and
                      anthropogenic trace gases in the atmosphere. Direct
                      speciated measurements of these components are extremely
                      helpful for understanding their atmospheric fate and impact.
                      We describe the development of an online method for
                      measurements of SCIs and RO2 in laboratory experiments using
                      chemical derivatization and spin trapping techniques
                      combined with H3O+ and NH+4 chemical ionization mass
                      spectrometry (CIMS). Using chemical derivatization agents
                      with low proton affinity, such as electron-poor carbonyls,
                      we scavenge all SCIs produced from a wide range of alkenes
                      without depleting CIMS reagent ions. Comparison between our
                      measurements and results from numeric modeling, using a
                      modified version of the Master Chemical Mechanism, shows
                      that the method can be used for the quantification of SCIs
                      in laboratory experiments with a detection limit of
                      1.4×107 molecule cm−3 for an integration time of
                      30 s with the instrumentation used in this study. We show
                      that spin traps are highly reactive towards atmospheric
                      radicals and form stable adducts with them by studying the
                      gas-phase kinetics of the reaction of spin traps with the
                      hydroxyl radical (OH). We also demonstrate that spin trap
                      adducts with SCIs and RO2 can be simultaneously probed and
                      quantified under laboratory conditions with a detection
                      limit of 1.6×108 molecule cm−3 for an integration
                      time of 30 s for RO2 species with the instrumentation used
                      in this study. Spin trapping prevents radical secondary
                      reactions and cycling, ensuring that measurements are not
                      biased by chemical interferences, and it can be implemented
                      for detecting RO2 species in laboratory studies and
                      potentially in the ambient atmosphere.},
      cin          = {IEK-8},
      ddc          = {550},
      cid          = {I:(DE-Juel1)IEK-8-20101013},
      pnm          = {2111 - Air Quality (POF4-211)},
      pid          = {G:(DE-HGF)POF4-2111},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000636627500003},
      doi          = {10.5194/amt-14-2501-2021},
      url          = {https://juser.fz-juelich.de/record/893672},
}