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Volume 13, issue 11
Atmos. Chem. Phys., 13, 5403–5423, 2013
https://doi.org/10.5194/acp-13-5403-2013
© Author(s) 2013. This work is distributed under
the Creative Commons Attribution 3.0 License.

Special issue: Community Atmosphere-Biosphere Interactions Experiment 2009...

Atmos. Chem. Phys., 13, 5403–5423, 2013
https://doi.org/10.5194/acp-13-5403-2013
© Author(s) 2013. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 03 Jun 2013

Research article | 03 Jun 2013

OH and HO2 radical chemistry during PROPHET 2008 and CABINEX 2009 – Part 1: Measurements and model comparison

S. M. Griffith1,2, R. F. Hansen2,3, S. Dusanter1,4,5, P. S. Stevens1,2,3, M. Alaghmand6, S. B. Bertman7, M. A. Carroll8,9, M. Erickson10, M. Galloway11,*, N. Grossberg12, J. Hottle11, J. Hou13, B. T. Jobson10, A. Kammrath11, F. N. Keutsch11, B. L. Lefer12, L. H. Mielke6,**, A. O'Brien14,***, P. B. Shepson6,15, M. Thurlow14, W. Wallace10, N. Zhang13, and X. L. Zhou13 S. M. Griffith et al.
  • 1School of Public and Environmental Affairs, Indiana University, Bloomington, IN, USA
  • 2Center for Research in Environmental Science, Indiana University, Bloomington, IN, USA
  • 3Department of Chemistry, Indiana University, Bloomington, IN, USA
  • 4Université Lille Nord de France, 59000, Lille, France
  • 5Mines Douai, CE, F59508, Douai, France
  • 6Department of Chemistry, Purdue University, West Lafayette, IN, USA
  • 7Department of Chemistry, Western Michigan University, Kalamazoo, MI, USA
  • 8Department of Chemistry, University of Michigan, Ann Arbor, MI, USA
  • 9Department of Atmospheric, Oceanic, and Space Sciences, University of Michigan, Ann Arbor, MI, USA
  • 10Department of Civil and Environmental Engineering, Washington State University, Pullman, WA, USA
  • 11Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA
  • 12Department of Earth and Atmospheric Sciences, University of Houston, Houston, TX, USA
  • 13School of Public Health, State University of New York at Albany, Albany, NY, USA
  • 14Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA
  • 15Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, IN, USA
  • *now at: Department of Chemistry and Biochemistry, University of San Diego, San Diego, CA, USA
  • **now at: School of Public and Environmental Affairs, Indiana University, Bloomington, IN, USA
  • ***now at: Civil and Environmental Engineering, Princeton University, Princeton, NJ, USA

Abstract. Hydroxyl (OH) and hydroperoxyl (HO2) radicals are key species driving the oxidation of volatile organic compounds that can lead to the production of ozone and secondary organic aerosols. Previous measurements of these radicals in forest environments with high isoprene, low NOx conditions have shown serious discrepancies with modeled concentrations, bringing into question the current understanding of isoprene oxidation chemistry in these environments.

During the summers of 2008 and 2009, OH and peroxy radical concentrations were measured using a laser-induced fluorescence instrument as part of the PROPHET (Program for Research on Oxidants: PHotochemistry, Emissions, and Transport) and CABINEX (Community Atmosphere-Biosphere INteractions EXperiment) campaigns at a forested site in northern Michigan. Supporting measurements of photolysis rates, volatile organic compounds, NOx (NO + NO2 and other inorganic species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism, modified to include the Mainz Isoprene Mechanism (RACM-MIM). The CABINEX model OH predictions were in good agreement with the measured OH concentrations, with an observed-to-modeled ratio near one (0.70 ± 0.31) for isoprene mixing ratios between 1–2 ppb on average. The measured peroxy radical concentrations, reflecting the sum of HO2 and isoprene-based peroxy radicals, were generally lower than predicted by the box model in both years.

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