Thermal degradation of polybrominated diphenyl ethers over as-prepared Fe3O4 micro/nano-material and hypothesized mechanism.

The thermal degradation of decabromodiphenyl ether (BDE-209) featuring fully substituted bromines was investigated over an as-prepared Fe3O4 micro/nano-material at 300 °C. Degradation followed pseudo-first-order kinetics with kobs = 0.15 min(-1) higher than that for decachlorobiphenyl (CB-209). Twenty-six newly produced polybrominated diphenyl ether (PBDE) congeners were identified using the available PBDE standards, while four PBDE congener products were predicted using third-order polynomial regression equation. Analysis of the products indicated that BDE-209 underwent stepwise hydrodebromination over as-prepared Fe3O4. Similar to the case for CB-209, two initial hydrodebromination steps are favored at the BDE-209 meta-positions, giving the major products BDE-207 and BDE-197. However, the variance about the preferred products began to emerge from the start of heptabromodiphenyl ethers (hepta-BDEs). The majorly produced hepta-BDE isomer with BDE-183 is unbrominated at one ortho-position. However, this is different from the reported degradation of CB-209, which always produced the products chlorinated at all four ortho-positions until the ortho-position had to be removed for the formation of trichlorobiphenyls and dichlorobiphenyl still majorly chlorinated at three or two ortho-positions. The early BDE-209 hydrodebromination steps appear to be strongly influenced by steric effects, whereas subsequent hydrodebromination steps, as more bromine atoms are removed, will be gradually governed more by thermodynamics.