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Rapid Autoxidation Forms Highly Oxidized RO 2 Radicals in the Atmosphere
Author(s) -
Jokinen Tuija,
Sipilä Mikko,
Richters Stefanie,
Kerminen VeliMatti,
Paasonen Pauli,
Stratmann Frank,
Worsnop Douglas,
Kulmala Markku,
Ehn Mikael,
Herrmann Hartmut,
Berndt Torsten
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201408566
Subject(s) - autoxidation , isoprene , radical , chemistry , aerosol , photochemistry , atmosphere (unit) , limonene , ozone , atmospheric chemistry , organic chemistry , environmental chemistry , meteorology , chromatography , polymer , physics , essential oil , copolymer
Gas‐phase oxidation routes of biogenic emissions, mainly isoprene and monoterpenes, in the atmosphere are still the subject of intensive research with special attention being paid to the formation of aerosol constituents. This laboratory study shows that the most abundant monoterpenes (limonene and α‐pinene) form highly oxidized RO 2 radicals with up to 12 O atoms, along with related closed‐shell products, within a few seconds after the initial attack of ozone or OH radicals. The overall process, an intramolecular ROO→QOOH reaction and subsequent O 2 addition generating a next R′OO radical, is similar to the well‐known autoxidation processes in the liquid phase (QOOH stands for a hydroperoxyalkyl radical). Field measurements show the relevance of this process to atmospheric chemistry. Thus, the well‐known reaction principle of autoxidation is also applicable to the atmospheric gas‐phase oxidation of hydrocarbons leading to extremely low‐volatility products which contribute to organic aerosol mass and hence influence the aerosol–cloud–climate system.