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@ARTICLE{Newland:857194,
      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
                      ${SO}\<sub\>2\</sub\>$ oxidation: experiment, theory and
                      modelling},
      journal      = {Atmospheric chemistry and physics},
      volume       = {18},
      number       = {8},
      issn         = {1680-7324},
      address      = {Katlenburg-Lindau},
      publisher    = {EGU},
      reportid     = {FZJ-2018-06431},
      pages        = {6095 - 6120},
      year         = {2018},
      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 SCIs formed from the ozonolysis of three
                      atmospherically important monoterpenes (α-pinene, β-pinene
                      and limonene) in the presence of varying amounts of water
                      vapour in large-scale simulation chamber experiments that
                      are representative of boundary layer conditions. 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 SCIs in each of the systems
                      studied, which displayed different rates of reaction with
                      water and of unimolecular rearrangement or decomposition.
                      The determined rate constants, k(SCI+H2O), for those SCIs
                      that react primarily with H2O range from 4 to
                      310 × 10−15cm3s−1. For those SCIs that
                      predominantly react unimolecularly, determined rates range
                      from 130 to 240s−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 α-pinene and β-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
                      $>97\%$ of the total monoterpene-derived global SCI burden
                      is comprised of SCIs with a structure that determines that
                      they react slowly with water and that their atmospheric fate
                      is dominated by unimolecular reactions. Seasonally averaged
                      boundary layer concentrations of monoterpene-derived SCIs
                      reach up to 1.4 × 104cm−3 in regions of elevated
                      monoterpene emissions in the tropics. Reactions of
                      monoterpene-derived SCIs with SO2 account for $<1\%$
                      globally but may account for up to $60\%$ 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},
      UT           = {WOS:000431293300004},
      doi          = {10.5194/acp-18-6095-2018},
      url          = {https://juser.fz-juelich.de/record/857194},
}