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@ARTICLE{Fuchs:155053,
      author       = {Fuchs, H. and Acir, I.-H. and Bohn, B. and Brauers, T. and
                      Dorn, H.-P. and Häseler, R. and Hofzumahaus, A. and
                      Holland, F. and Kaminski, M. and Li, Xin and Lu, K. and
                      Lutz, A. and Nehr, S. and Rohrer, F. and Tillmann, R. and
                      Wegener, R. and Wahner, A.},
      title        = {{OH} regeneration from methacrolein oxidation investigated
                      in the atmosphere simulation chamber {SAPHIR}},
      journal      = {Atmospheric chemistry and physics},
      volume       = {14},
      number       = {15},
      issn         = {1680-7324},
      address      = {Katlenburg-Lindau},
      publisher    = {EGU},
      reportid     = {FZJ-2014-04244},
      pages        = {7895 - 7908},
      year         = {2014},
      abstract     = {Hydroxyl radicals (OH) are the most important reagent for
                      the oxidation of trace gases in the atmosphere. OH
                      concentrations measured during recent field campaigns in
                      isoprene-rich environments were unexpectedly large. A number
                      of studies showed that unimolecular reactions of organic
                      peroxy radicals (RO2) formed in the initial reaction step of
                      isoprene with OH play an important role for the OH budget in
                      the atmosphere at low mixing ratios of nitrogen monoxide
                      (NO) of less than 100 pptv. It has also been suggested that
                      similar reactions potentially play an important role for RO2
                      from other compounds. Here, we investigate the oxidation of
                      methacrolein (MACR), one major oxidation product of
                      isoprene, by OH in experiments in the simulation chamber
                      SAPHIR under controlled atmospheric conditions. The
                      experiments show that measured OH concentrations are
                      approximately $50\%$ larger than calculated by the Master
                      Chemical Mechanism (MCM) for conditions of the experiments
                      (NO mixing ratio of 90 pptv). The analysis of the OH budget
                      reveals an OH source that is not accounted for in MCM, which
                      is correlated with the production rate of RO2 radicals from
                      MACR. In order to balance the measured OH destruction rate,
                      0.77 OH radicals (1σ error: ± 0.31) need to be
                      additionally reformed from each reaction of OH with MACR.
                      The strong correlation of the missing OH source with the
                      production of RO2 radicals is consistent with the concept of
                      OH formation from unimolecular isomerization and
                      decomposition reactions of RO2. The comparison of
                      observations with model calculations gives a lower limit of
                      0.03 s−1 for the reaction rate constant if the OH source
                      is attributed to an isomerization reaction of MACR-1-OH-2-OO
                      and MACR-2-OH-2-OO formed in the MACR + OH reaction as
                      suggested in the literature (Crounse et al., 2012). This
                      fast isomerization reaction would be a competitor to the
                      reaction of this RO2 species with a minimum of 150 pptv NO.
                      The isomerization reaction would be the dominant reaction
                      pathway for this specific RO2 radical in forested regions,
                      where NO mixing ratios are typically much smaller.},
      cin          = {IEK-8},
      ddc          = {550},
      cid          = {I:(DE-Juel1)IEK-8-20101013},
      pnm          = {233 - Trace gas and aerosol processes in the troposphere
                      (POF2-233) / HITEC - Helmholtz Interdisciplinary Doctoral
                      Training in Energy and Climate Research (HITEC)
                      (HITEC-20170406)},
      pid          = {G:(DE-HGF)POF2-233 / G:(DE-Juel1)HITEC-20170406},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000341103600016},
      doi          = {10.5194/acp-14-7895-2014},
      url          = {https://juser.fz-juelich.de/record/155053},
}