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Evaluation of OH and HO2 concentrations and their budgets during photooxidation of 2-methyl-3-butene-2-ol (MBO) in the atmospheric simulation chamber SAPHIR

Journal article
Authors A. Novelli
M. Kaminski
M. Rolletter
I. H. Acir
B. Bohn
H. P. Dorn
X. Li
Anna Lutz
S. Nehr
F. Rohrer
R. Tillmann
R. Wegener
F. Holland
A. Hofzumahaus
A. Kiendler-Scharr
A. Wahner
H. Fuchs
Published in Atmospheric Chemistry and Physics
Volume 18
Issue 15
Pages 11409-11422
ISSN 1680-7316
Publication year 2018
Published at Department of Chemistry and Molecular Biology
Pages 11409-11422
Language en
Keywords laser-induced fluorescence, volatile organic-compounds, hydrogen shift, reactions, tropical rain-forest, pearl river delta, peroxy-radicals, tropospheric degradation, isoprene oxidation, ro2 radicals, photolysis, frequencies, Meteorology & Atmospheric Sciences
Subject categories Geochemistry


Several previous field studies have reported unexpectedly large concentrations of hydroxyl and hydroperoxyl radicals (OH and HO2, respectively) in forested environments that could not be explained by the traditional oxidation mechanisms that largely underestimated the observations. These environments were characterized by large concentrations of biogenic volatile organic compounds (BVOC) and low nitrogen oxide concentration. In isoprene-dominated environments, models developed to simulate atmospheric photochemistry generally underestimated the observed OH radical concentrations. In contrast, HO2 radical concentration showed large discrepancies with model simulations mainly in non-isoprene-dominated forested environments. An abundant BVOC emitted by lodgepole and ponderosa pines is 2-methyl- 3-butene-2-ol (MBO), observed in large concentrations for studies where the HO2 concentration was poorly described by model simulations. In this work, the photooxidation of MBO by OH was investigated for NO concentrations lower than 200 pptv in the atmospheric simulation chamber SAPHIR at Forschungszentrum Julich. Measurements of OH and HO2 radicals, OH reactivity (kO(H)), MBO, OH precursors, and organic products (acetone and formaldehyde) were used to test our current understanding of the OH-oxidation mechanisms for MBO by comparing measurements with model calculations. All the measured trace gases agreed well with the model results (within 15 %) indicating a well understood mechanism for the MBO oxidation by OH. Therefore, the oxidation of MBO cannot contribute to reconciling the unexplained high OH and HO2 radical concentrations found in previous field studies.

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