Formation of 1,3,8-tribromodibenzo- p -dioxin and 2,4,6,8-tetrabromodibenzofuran in the oxidation of synthetic hydroxylated polybrominated diphenyl ethers by iron and manganese oxides under dry conditions

Abstract

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are ubiquitous and highly toxic emerging endocrine disruptors found in surface and subsurface soils and clay deposits. Seriously, they could be easily transformed to the more toxic dioxins (PBDD/Fs) in photochemical processes and incineration, but the spontaneous formation of PBDD/Fs has rarely been reported. This study focused on the formation of 1,3,8-tribromodibenzo-p-dioxin (1,3,8-TrBDD) and 2,4,6,8-tetrabromodibenzofuran (2,4,6,8-TeBDF) from 2′-OH-BDE-68 and 2,2′-diOH-BB-80 under the oxidization of iron and manganese oxides (goethite and MnO_x). Approximately 0.09 μmol/kg (2.33%) and 0.17 μmol/kg (4.15%) were transformed to 1,3,8-TrBDD and 2,4,6,8-TeBDF by goethite in 8 days and a higher conversion 0.15 μmol/kg (3.77%) and 0.23 μmol/kg (5.74%) were observed for MnO_x in 4 days. However, the formation of PBDD/Fs, probably proceeding via Smiles rearrangements and bromine elimination processes, was greatly inhibited by the presence of water. Transformation of OH-PBDEs by goethite and MnO_x was accompanied by release of Fe and Mn ions and the possible pathways for the formation of reaction products were proposed. In view of the ubiquity of OH-PBDEs and metal oxides in the environment, oxidation of OH-PBDEs mediated by goethite and MnO_x is likely an abiotic route for the formation of PBDD/Fs.