The oxidation mechanism of polychlorinated dibenzo-p-dioxins under the atmospheric conditions - A theoretical study |
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Authors: | Liming Wang Aili Tang |
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Affiliation: | School of Chemistry & Chemical Engineering, South China University of Technology, Guangzhou 510640, China |
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Abstract: | The atmospheric polychlorinated dibenzo-p-dioxins (PCDDs) partition appreciably in the gas phase, where they undergo rapid oxidation. The atmospheric oxidation mechanisms of a few PCDDs, initiated by OH radical, are studied using density functional theory calculations. The oxidations start with OH-addition to the aromatic rings, dominantly at γ-sites, followed by the non-chlorinated β-sites; while additions to the α-sites or chlorinated sites are negligible. For PCDDs with all β-sites being chlorinated, formation of PCDD-γ-OH adducts become virtually the only reaction path. Under the atmospheric conditions, the PCDD-β/γ-OH adducts combine with O2 slowly at rates <1 s−1. Instead, the PCDD-β-OH adducts will react with O2 through hydrogen abstraction at rates <50 s−1, forming PCDD-β-ol, and the PCDD-γ-OH adducts will decompose to the substituted phenoxy radicals by fused-ring C-O bond cleavage at rates of 103 ∼ 105 s−1. The reaction mechanisms of PCDDs are drastically different from the peroxy mechanism for the atmospheric oxidations of benzene and dibenzofuran. |
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Keywords: | Dibenzo-p-dioxins Atmospheric oxidation mechanism Potential Energy Surfaces PCDD-OH adducts |
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