【标题】Unintentional formation of mixed chloro-bromo diphenyl ethers (PBCDEs), dibenzo-p-dioxins and dibenzofurans (PBCDD/Fs) from pyrolysis of polybrominated diphenyl ethers (PBDEs)
【期刊】Chemosphere
【第一作者】梁佳豪
【摘要】This study presents the comprehensive investigation for formation pathways of chloro-bromo-mixed products from the pyrolysis of polybrominated diphenyl ethers (PBDEs). In the study, a total of 23 PBDEs with bromination levels from mono-to deca-were selected. Each PBDE standard was sealed in the glass vial and then heated under 450 ◦C in the muffle furnace to simulate the pyrolysis process. The results demonstrated that PBDEs in the glass vials can unintentionally transform into chloro-bromo diphenyl ethers (PBCDEs) and dibenzo-p-dioxin and dibenzofurans (PBCDD/Fs) during the pyrolysis process. Atmosphere pressure gas chromatography (APGC) coupled with high-resolution mass spectrometry (HRMS) was used to identify these pyrolysis products, which demonstrated that all investigated nPBDEs (n represents the number of bromine substituents) can unintentionally transform into Cl1-(n-1)BDEs, Cl2-(n-2)BDEs, Cl1-(n-1)BDFs, and Cl1-(n-3)BDDs, while some nPBDEs can transform into Cl1-(n-2)PBDD/Fs during pyrolysis. Experimental phenomena assisted with density functional theory (DFT) calculations reveal that Cl atom can substitute at C–Br rather than C–H, and Cl1-(n-1)BDEs can be easily generated by Cl atom attacking at C–Br sites with low energy barriers (3.66–11.9 kcal/mol). In addition, nPBDEs
【文章链接】https://doi.org/10.1016/j.chemosphere.2022.136246