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@ARTICLE{Newland:842440,
      author       = {Newland, Mike J. and Rickard, Andrew R. and Sherwen, Tomás
                      and Evans, Mathew J. and Vereecken, Luc and Muñoz, Amalia
                      and Ródenas, Milagros and Bloss, William J.},
      title        = {{T}he atmospheric impacts of monoterpene ozonolysis on
                      global stabilised {C}riegee intermediate budgets and {SO}2
                      oxidation: experiment, theory and modelling},
      journal      = {Atmospheric chemistry and physics / Discussions},
      volume       = {1095},
      issn         = {1680-7375},
      address      = {Katlenburg-Lindau},
      publisher    = {EGU},
      reportid     = {FZJ-2018-00676},
      pages        = {1 - 65},
      year         = {2017},
      abstract     = {The gas-phase reaction of alkenes with ozone is known to
                      produce stabilised Criegee intermediates (SCIs). These
                      biradical/zwitterionic species have the potential to act as
                      atmospheric oxidants for trace pollutants such as SO2,
                      enhancing the formation of sulfate aerosol with impacts on
                      air quality and health, radiative transfer and climate.
                      However, the importance of this chemistry is uncertain as a
                      consequence of limited understanding of the abundance and
                      atmospheric fate of SCIs. In this work we apply
                      experimental, theoretical and numerical modelling methods to
                      quantify the atmospheric impacts, abundance, and fate, of
                      the structurally diverse SCIs derived from the ozonolysis of
                      monoterpenes, the second most abundant group of unsaturated
                      hydrocarbons in the atmosphere. We have investigated the
                      removal of SO2 by SCI formed from the ozonolysis of three
                      monoterpenes (-pinene, -pinene and limonene) in the presence
                      of varying amounts of water vapour in large-scale simulation
                      chamber experiments. The SO2 removal displays a clear
                      dependence on water vapour concentration, but this
                      dependence is not linear across the range of [H2O] explored.
                      At low [H2O] a strong dependence of SO2 removal on [H2O] is
                      observed, while at higher [H2O] this dependence becomes much
                      weaker. This is interpreted as being caused by the
                      production of a variety of structurally (and hence
                      chemically) different SCI in each of the systems studied,
                      each displaying different rates of reaction with water and
                      of unimolecular rearrangement/decomposition. The determined
                      rate constants, k(SCI+H2O), for those SCI that react
                      primarily with H2O range from
                      4–310 × 10−15 cm3 s−1. For those SCI that
                      predominantly react unimolecularly, determined rates range
                      from 130–240 s−1. These values are in line with
                      previous results for the (analogous) stereo-specific SCI
                      system of syn/anti-CH3CHOO. The experimental results are
                      interpreted through theoretical studies of the SCI
                      unimolecular reactions and bimolecular reactions with H2O,
                      characterised for -pinene and -pinene at the
                      M06-2X/aug-cc-pVTZ level of theory. The theoretically
                      derived rates agree with the experimental results within the
                      uncertainties. A global modelling study, applying the
                      experimental results within the GEOS-Chem chemical transport
                      model, suggests that $> 98 \%$ of the total monoterpene
                      derived global SCI burden is comprised of SCI whose
                      structure determines that they react slowly with water, and
                      whose atmospheric fate is dominated by unimolecular
                      reactions. Seasonally averaged boundary layer concentrations
                      of monoterpene-derived SCI reach up to
                      1.2 × 104 cm−3 in regions of elevated monoterpene
                      emissions in the tropics. Reactions of monoterpene derived
                      SCI with SO2 account for $< 1 \%$ globally but may
                      account for up to $50 \%$ of the gas-phase SO2 removal
                      over areas of tropical forests, with significant localised
                      impacts on the formation of sulfate aerosol, and hence the
                      lifetime and distribution of SO2.},
      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},
      doi          = {10.5194/acp-2017-1095},
      url          = {https://juser.fz-juelich.de/record/842440},
}