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Atmospheric oxidation of halogenated aromatics: comparative analysis of reaction mechanisms and reaction kinetics

Kovačević, Goran; Sabljić, Aleksandar (2017) Atmospheric oxidation of halogenated aromatics: comparative analysis of reaction mechanisms and reaction kinetics. Environmental Science: Processes and Impacts, 19 (3). pp. 357-369. ISSN 2050-7887

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Atmospheric transport is the major route for global distribution of semi-volatile compounds such as halogenated aromatics as well as their major exposure route for humans. Their major atmospheric removal process is oxidation by hydroxyl radicals. There is very little information on the reaction mechanism or reaction-path dynamics of atmospheric degradation of halogenated benzenes. Furthermore, the measured reaction rate constants are missing for the range of environmentally relevant temperatures, i.e. 230-330 K. A series of recent theoretical studies have provided those valuable missing information for fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene. Their comparative analysis has provided additional and more general insight into the mechanism of those important tropospheric degradation processes as well as into the mobility, transport and atmospheric fate of halogenated aromatic systems. It was demonstrated for the first time that the addition of hydroxyl radicals to monohalogenated as well as to perhalogenated benzenes proceeds indirectly, via a prereaction complex and its formation and dynamics have been characterized including the respective transition-state. However, in fluorobenzene and chlorobenzene reactions hydroxyl radical hydrogen is pointing approximately to the center of the aromatic ring while in the case of hexafluorobenzene and hexachlorobenzene, unexpectedly, the oxygen is directed towards the center of the aromatic ring. The reliable rate constants are now available for all environmentally relevant temperatures for the tropospheric oxidation of fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene while pentachlorophenol, a well-known organic micropollutant, seems to be a major stable product of tropospheric oxidation of hexachlorobenzene. Their calculated tropospheric lifetimes show that fluorobenzene and chlorobenzene are easily removed from the atmosphere and do not have long-range transport potential while hexafluorobenzene seems to be a potential POP chemical and hexachlorobenzene is clearly a typical persistent organic pollutant.

Item Type: Article
Uncontrolled Keywords: gas-phase reactions; hydroxyl radical reactions; persistent organic pollutants; reaction-rate constants; unimolecular reaction systems; oh-initiated oxidation; reaction-path dynamics; ab-initio; hydrogen abstraction; photochemical data
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Materials Physics
Project titleProject leaderProject codeProject type
Istraživanja Kemijske Reaktivnosti-Aleksandar Sabljić098-0982915-2944MZOS
Depositing User: Goran Kovačević
Date Deposited: 18 May 2017 07:35
DOI: 10.1039/c6em00577b

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