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@ARTICLE{Eger:902295,
      author       = {Eger, Philipp G. and Vereecken, Luc and Sander, Rolf and
                      Schuladen, Jan and Sobanski, Nicolas and Fischer, Horst and
                      Karu, Einar and Williams, Jonathan and Vakkari, Ville and
                      Petäjä, Tuukka and Lelieveld, Jos and Pozzer, Andrea and
                      Crowley, John N.},
      title        = {{I}mpact of pyruvic acid photolysis on acetaldehyde and
                      peroxy radical formation in the boreal forest: theoretical
                      calculations and model results},
      journal      = {Atmospheric chemistry and physics},
      volume       = {21},
      number       = {18},
      issn         = {1680-7324},
      address      = {Katlenburg-Lindau},
      publisher    = {EGU},
      reportid     = {FZJ-2021-04158},
      pages        = {14333 - 14349},
      year         = {2021},
      abstract     = {Based on the first measurements of gas-phase pyruvic acid
                      (CH3C(O)C(O)OH) in the boreal forest, we derive effective
                      emission rates of pyruvic acid and compare them with
                      monoterpene emission rates over the diel cycle. Using a
                      data-constrained box model, we determine the impact of
                      pyruvic acid photolysis on the formation of acetaldehyde
                      (CH3CHO) and the peroxy radicals CH3C(O)O2 and HO2 during an
                      autumn campaign in the boreal forest.The results are
                      dependent on the quantum yield (φ) and mechanism of the
                      photodissociation of pyruvic acid and the fate of a likely
                      major product, methylhydroxy carbene (CH3COH). With the box
                      model, we investigate two different scenarios in which we
                      follow the present IUPAC (IUPAC Task Group on Atmospheric
                      Chemical Kinetic Data Evaluation, 2021) recommendations with
                      φ = 0.2 (at 1 bar of air), and the main photolysis
                      products $(60 \%)$ are acetaldehyde + CO2 with
                      $35 \%$ C–C bond fission to form HOCO and CH3CO
                      (scenario A). In the second scenario (B), the formation of
                      vibrationally hot CH3COH (and CO2) represents the main
                      dissociation pathway at longer wavelengths $(∼ 75 \%)$
                      with a $∼ 25 \%$ contribution from C–C bond fission
                      to form HOCO and CH3CO (at shorter wavelengths). In scenario
                      2 we vary φ between 0.2 and 1 and, based on the results of
                      our theoretical calculations, allow the thermalized CH3COH
                      to react with O2 (forming peroxy radicals) and to undergo
                      acid-catalysed isomerization to CH3CHO.When constraining the
                      pyruvic acid to measured mixing ratios and independent of
                      the model scenario, we find that the photolysis of pyruvic
                      acid is the dominant source of CH3CHO with a contribution
                      between $∼ 70 \%$ and $90 \%$ to the total
                      production rate. We find that the photolysis of pyruvic acid
                      is also a major source of the acetylperoxy radical, with
                      contributions varying between $∼ 20 \%$ and $60 \%$
                      dependent on the choice of φ and the products formed. HO2
                      production rates are also enhanced, mainly via the formation
                      of CH3O2. The elevated production rates of CH3C(O)O2 and HO2
                      and concentration of CH3CHO result in significant increases
                      in the modelled mixing ratios of CH3C(O)OOH, CH3OOH, HCHO,
                      and H2O2.},
      cin          = {IEK-8},
      ddc          = {550},
      cid          = {I:(DE-Juel1)IEK-8-20101013},
      pnm          = {2111 - Air Quality (POF4-211)},
      pid          = {G:(DE-HGF)POF4-2111},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000703045500001},
      doi          = {10.5194/acp-21-14333-2021},
      url          = {https://juser.fz-juelich.de/record/902295},
}