The formation of PBDFs from the ortho-disubstituted phenol precursors: A comprehensive theoretical study on the PBDD/Fs formation from 2,4,6-tribromophenol.

Bromophenols are known as direct precursors of the notorious polybrominated dibenzo-p-dioxin/dibenzofurans (PBDD/Fs). There is a long-held viewpoint that only the more toxic dioxin-type products could be formed from the ortho-disubstituted phenols, totally contrary to the experimental observations that both PBDDs and PBDFs are generated. To tackle the issue, the gaseous formation mechanism of PBDD/Fs from 2,4,6-tribromophenol (TBP), a typical ortho-disubstituted phenol, was investigated in this study. Firstly, the reactions between TBP and the active H radical produce three key radical species including the bromophenoxyl radical, the substituted phenyl radical and phenoxyl diradical. The self- and cross-combinations of these radical species and TBP yield not only the dioxin-type products 1,3,6,8-TeBDD and 1,3,7,9-TeBDD, but also the brominated dibenzofurans 1,3,6,8-TeBDF and 2,4,6,8-TeBDF. Notably, the reactions involving the phenyl C sites in the substituted phenyl and phenoxyl diradicals are demonstrated to be both thermodynamically and kinetically more favorable than those involving the bromophenoxyl radical and the TBP molecule. Most importantly, the findings of the present work are of great importance as it provides feasible pathways to form less toxic dibenzofuran-type products from the ortho-disubstituted phenols. These results will improve the understanding of the PBDD/Fs formation mechanism from phenol precursors.