Observable carbon isotope fractionation in the photodegradation of polybrominated diphenyl ethers by simulated sunlight.

In the present study, carbon isotope effects were investigated during the photodegradation of polybrominated diphenyl ethers (PBDEs) by compound-specific stable isotope analysis (CSIA). Five PBDE congeners (BDE 85, 99, 100, 153 and 154) in n-hexane were individually exposed to simulated sunlight for as long as 15 h, except for BDE 100 (24 h). Consecutive debromination of PBDE by photolysis in n-hexane was confirmed by the clear C enrichment of mother congeners and successive depletion of δC values for the photodegradation products with decreasing degree of bromination, which can be attributed to mass-dependent isotope fractionation. The observed variation in the isotope fractionation trends for the para-debrominated products might be linked to the different photocatalytic activities of the PBDE congeners. Higher fractionation was observed for penta-BDEs (ε-2.2 ± 0.45‰ and -2.3 ± 0.26‰ for BDE 85 and BDE 99, respectively) compared to that for hexa-BDEs (ε-1.7 ± 0.41‰, and -1.3 ± 0.12‰ for BDE 153 and BDE 154, respectively). Normal isotope effects (AKIE > 1) observed in our study supports the utility of CSIA for the evaluation of the photodegradation of PBDEs.