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@ARTICLE{Tham:824995,
      author       = {Tham, Yee Jun and Wang, Zhe and Li, Qinyi and Yun, Hui and
                      Wang, Weihao and Wang, Xinfeng and Xue, Likun and Lu, Keding
                      and Ma, Nan and Bohn, Birger and Li, Xin and Kecorius,
                      Simonas and Größ, Johannes and Shao, Min and Wiedensohler,
                      Alfred and Zhang, Yuanhang and Wang, Tao},
      title        = {{S}ignificant concentrations of nitryl chloride sustained
                      in the morning: investigations of the causes and impacts on
                      ozone production in a polluted region of northern {C}hina},
      journal      = {Atmospheric chemistry and physics},
      volume       = {16},
      number       = {23},
      issn         = {1680-7324},
      address      = {Katlenburg-Lindau},
      publisher    = {EGU},
      reportid     = {FZJ-2016-07491},
      pages        = {14959 - 14977},
      year         = {2016},
      abstract     = {Nitryl chloride (ClNO2) is a dominant source of chlorine
                      radical in polluted environment, and can significantly
                      affect the atmospheric oxidative chemistry. However, the
                      abundance of ClNO2 and its exact role are not fully
                      understood under different environmental conditions. During
                      the summer of 2014, we deployed a chemical ionization mass
                      spectrometer to measure ClNO2 and dinitrogen pentoxide
                      (N2O5) at a rural site in the polluted North China Plain.
                      Elevated mixing ratios of ClNO2 (> 350 pptv) were
                      observed at most of the nights with low levels of N2O5
                      (< 200 pptv). The highest ClNO2 mixing ratio of
                      2070 pptv (1 min average) was observed in a plume from a
                      megacity (Tianjin), and was characterized with a faster N2O5
                      heterogeneous loss rate and ClNO2 production rate compared
                      to average conditions. The abundant ClNO2 concentration kept
                      increasing even after sunrise, and reached a peak 4 h
                      later. Such highly sustained ClNO2 peaks after sunrise are
                      discrepant from the previously observed typical diurnal
                      pattern. Meteorological and chemical analysis shows that the
                      sustained ClNO2 morning peaks are caused by significant
                      ClNO2 production in the residual layer at night followed by
                      downward mixing after breakup of the nocturnal inversion
                      layer in the morning. We estimated that
                       ∼  1.7–4.0 ppbv of ClNO2 would exist in the
                      residual layer in order to maintain the observed morning
                      ClNO2 peaks at the surface site. Observation-based box model
                      analysis show that photolysis of ClNO2 produced chlorine
                      radical with a rate up to 1.12 ppbv h−1, accounting
                      for $10–30 \%$ of primary ROx production in the morning
                      hours. The perturbation in total radical production leads to
                      an increase of integrated daytime net ozone production by
                      $3 \%$ (4.3 ppbv) on average, and with a larger increase
                      of $13 \%$ (11 ppbv) in megacity outflow that was
                      characterized with higher ClNO2 and a relatively lower
                      oxygenated hydrocarbon (OVOC) to non-methane hydrocarbon
                      (NMHC) ratio.},
      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:000389208700002},
      doi          = {10.5194/acp-16-14959-2016},
      url          = {https://juser.fz-juelich.de/record/824995},
}