Insight into phototransformation mechanism and toxicity evolution of novel and legacy brominated flame retardants in water: A comparative analysis

Abstract

The novel brominated flame retardants (NBFRs) have become widespread as a consequence of the prohibition on the use of polybrominated diphenyl ethers (PBDEs). However, the transformation mechanism and potential environmental risk are largely unclear. In this study, we have explored the phototransformation behavior of the most abundant NBFRs, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) in water under ultraviolet (UV) irradiation. Meanwhile, the legacy 2,2′,4,4′,6,6′-hexabromodiphenyl ether (BDE155) with similar structure was investigated contrastively. Results show that novel BTBPE is more persistent than legacy BDE155, with nearly four times slower photodegradation rate constants (0.0120 min−1and 0.0447 min−1, respectively). 18 products are identified in the phototransformation of BTBPE. Different from the only debrominated products formed in legacy BDE155 transformation, the ether bond cleavage photoproducts (e.g. bromophenols) are also identified in novel BTBPE transformation. Compound-specific stable isotope analysis (CSIA) confirms the phototransformation mechanism is mainly via debromination accompanying with the breaking of ether bond. Computational toxicity assessment implies that transformation products of BTBPE still have the high kidney risks. Especially the bromophenols formed via the ether bond cleavage could significantly increase the health effects on skin irritation. This study emphasizes the importance of understanding the photolytic behavior and potential risks of novel NBFRs and other structurally similar analogues.