Photochemistry of a major commercial polybrominated diphenyl ether flame retardant congener: 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE153)

The photochemistry of a major commercial polybrominated diphenyl ether (PBDE) flame retardant congener, 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE153), was investigated in acetonitrile, distilled water, and seawater. After a short irradiation period in acetonitrile at 302 nm, the major photoproducts of BDE153 included 2,2',4,4',5-(BDE99), 2,2',4,5,5'-(BDE101), and 2,4,4',5,5'-(BDE118) substituted penta-BDEs as primary photohydrodebromination products, 2,2',4,4'-(BDE47), 3,3',4,4'-(BDE77), 2,3',4,4'-(BDE66), and 2,2',4,5'-(BDE49) substituted tetra-BDEs as secondary photohydrodebromination products, a suite of non-2,3,7,8-substituted mono- through penta-brominated dibenzofurans, and three tetrabrominated 2-hydroxybiphenyl congeners. By comparison, irradiation in distilled water and seawater gave increased relative photohydrodebromination contributions and no evidence for the formation of brominated dibenzofurans or 2-hydroxybiphenyls. In all solvent systems, subsequent degradation of primary and secondary photoproducts under continuing irradiation led to a steadily decreasing reaction mass balance. The results suggest a short photochemical half-life for BDE153 in aquatic systems, with rapid photohydrodebromination to some of the most prevalent penta- and tetra-brominated diphenyl ether congeners typically observed in environmental matrices.