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Rapid autoxidation forms highly oxidized RO2 radicals in the atmosphere
Tuija Jokinen1, Mikko Sipilä, Stefanie Richters
1Leibniz-Institut für Troposphärenforschung, TROPOS, 04318 Leipzig (Germany); Department of Physics, P.O. Box 64, 00014 University of Helsinki (Finland).
Biogenic emissions like monoterpenes rapidly form highly oxidized radicals in the atmosphere. This autoxidation process generates low-volatility products, significantly impacting organic aerosol mass and climate.
Area of Science:
- Atmospheric Chemistry
- Organic Chemistry
- Environmental Science
Background:
- Gas-phase oxidation of biogenic emissions is crucial for atmospheric aerosol formation.
- Isoprene and monoterpenes are key biogenic volatile organic compounds.
- Understanding oxidation pathways is vital for aerosol-cloud-climate system research.
Purpose of the Study:
- Investigate the gas-phase oxidation mechanisms of abundant monoterpenes.
- Identify the products formed from monoterpene oxidation by ozone and OH radicals.
- Elucidate the role of autoxidation in forming highly oxygenated organic molecules.
Main Methods:
- Laboratory experiments simulating atmospheric oxidation conditions.
- Analysis of reaction products from limonene and α-pinene.
- Characterization of highly oxidized RO2 radicals and closed-shell products.
Main Results:
- Monoterpenes form highly oxidized RO2 radicals (up to 12 O atoms) rapidly.
- Intramolecular ROO→QOOH reaction and O2 addition drive autoxidation.
- Extremely low-volatility products are generated, contributing to organic aerosol.
Conclusions:
- Autoxidation is a key mechanism in atmospheric monoterpene oxidation.
- This process leads to the formation of significant organic aerosol mass.
- Findings are relevant to atmospheric chemistry and the aerosol-cloud-climate system.
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