The OH-initiated atmospheric chemical reactions of polyfluorinated dibenzofurans and polychlorinated dibenzofurans: A comparative theoretical study

- Atmospheric oxidation reactions of PFDFs and PCDFs were studied theoretically.
- The OH addition reactions of PFDFs are comparable with those for PCDFs.
- The OH additions of PF(C)DFs become slower with higher fluorination or chlorination.
- The O2 addition reactions of PF(C)DF-OH adducts take place hardly.
- The main oxidation products for PFDFs and PCDFs are substituted dibenzofuranols.

The atmospheric chemical reactions of some polyfluorinated dibenzofurans (PFDFs) and polychlorinated dibenzofurans (PCDFs), initiated by OH radical, were investigated by performing theoretical calculations using density functional theory (DFT) and B3LYP/6-311++G(2df,p) method. The obtained results indicate that OH addition reactions of PFDFs and PCDFs occurring at C1∼4 and CA sites are thermodynamic spontaneous changes and the branching ratio of the PF(C)DF-OH adducts is decided primarily by kinetic factor. The OH addition reactions of PFDFs taking place at fluorinated C1∼4 positions are kinetically comparable with those occurring at nonfluorinated C1∼4 positions, while OH addition reactions of PCDFs occurring at chlorinated C1∼4 sites are negligible. The total rate constants of the addition reactions of PFDFs or PCDFs become smaller with consecutive fluorination or chlorination, and substituting at C1 position has more adverse effects than substitution at other sites. The succedent O2 addition reactions of PF(C)DF-OH adducts are thermodynamic nonspontaneous processes under the atmospheric conditions, and have high Gibbs free energies of activation (ΔrG≠). The substituted dibenzofuranols are the primary oxidation products for PCDFs under the atmospheric conditions. However, other oxidative products may also be available for PFDFs besides substituted dibenzofuranols.

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