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@ARTICLE{Konrad:44669,
      author       = {Konrad, S. and Schmitz, T. and Buers, H.-J. and Houben, N.
                      and Mannschreck, K. and Mihelcic, D. and Müsgen, P. and
                      Pätz, H.-W. and Holland, F. and Hofzumahaus, A. and
                      Schäfer, H.-J. and Schröder, S. and Volz-Thomas, A. and
                      Bächmann, K. and Schlomski, S. and Moortgat, G. and
                      Grossmann, D.},
      title        = {{H}ydrocarbon measurements at {P}abstthum during the
                      {BERLIOZ} campaign and modeling of free radicals},
      journal      = {Journal of Geophysical Research},
      volume       = {108},
      issn         = {0148-0227},
      address      = {Washington, DC},
      publisher    = {Union},
      reportid     = {PreJuSER-44669},
      pages        = {D4},
      year         = {2003},
      note         = {Record converted from VDB: 12.11.2012},
      abstract     = {The Photochemistry Experiment in BERLIOZ (PHOEBE) was
                      conducted in July/August 1998 at a rural site located near
                      the small village Pabstthum, about 50 km NW of downtown
                      Berlin. More than 60 nonmethane hydrocarbons (NMHC) in the
                      range of C-2-C-10 were measured using two in situ gas
                      chromatography (GC) systems. The first (GC1) was capable of
                      measuring C-2-C-10 hydrocarbons with a relatively high
                      separation efficiency but low time resolution (80-90 min),
                      while GC2 provided quasi-continuous measurements of C-5-C-10
                      hydrocarbons with a time resolution of 20 min but with a
                      poorer separation efficiency than GC1. The advantages of
                      both systems were joined by interpolation between two data
                      points of GC1 with the pattern given by GC2. For compounds
                      that could not be reliably measured with GC2, patterns of
                      compounds with similar reactivity were used. Air masses with
                      the lowest photochemical age as estimated from the
                      toluene/benzene ratio and the highest hydrocarbon mixing
                      ratios were observed on 20 and 21 July when air was advected
                      from the direction of Berlin. Alkanes were the most abundant
                      hydrocarbons (similar $to60\%)$ on a molecular basis,
                      followed by alkenes and aromatics. The reactivity of the
                      hydrocarbons toward OH was dominated by the alkenes
                      $(>60\%),$ with isoprene and a-pinene constituting the major
                      part. The hydrocarbon data were used together with the other
                      trace gases measured at Pabstthum to simulate OH, HO2, and
                      RO2 concentrations with the condensed chemical box model
                      RACM. Relatively good agreement of the simulated radical
                      concentrations with the spectroscopic measurements made at
                      Pabstthum is observed for NOx mixing ratios >5 ppb, whereas
                      the model overestimates OH and HO2 by $100\%$ and $40\%,$
                      respectively, at low NOx. The discrepancy between measured
                      and modeled OH does not correlate with the concentration of
                      particles. The RO2 concentrations are in good agreement with
                      the measurements over the entire range of NOx. Sensitivity
                      studies show that peroxyacetyl nitrate ( PAN) is an
                      important radical source and that missing volatile organic
                      compound (VOC) reactivity is an unlikely explanation for the
                      overestimation of HOx: By doubling of the VOC reactivity, OH
                      and HO2 can be brought into agreement. However, the model
                      then overestimates the organic RO2 concentrations by almost
                      a factor of 2. Another important finding is that RACM
                      overestimates the measured NO/NO2 ratio by $25\%.$ This and
                      the overestimation of HO2 lead to an overprediction of the
                      local ozone formation rate by about $40\%$ at low NOx mixing
                      ratios.},
      keywords     = {J (WoSType)},
      cin          = {ICG-II},
      ddc          = {550},
      cid          = {I:(DE-Juel1)VDB48},
      pnm          = {Chemie und Dynamik der Geo-Biosphäre},
      pid          = {G:(DE-Juel1)FUEK257},
      shelfmark    = {Meteorology $\&$ Atmospheric Sciences},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000182897800001},
      doi          = {10.1029/2001JD000866},
      url          = {https://juser.fz-juelich.de/record/44669},
}