Anaerobic biotransformation of two novel brominated flame retardants: Kinetics, isotope fractionation and reaction mechanisms.

Abstract

1,2,5,6-tetrabromocyclooctane (TBCO) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), as safer alternatives to traditional brominated flame retardants, have been extensively detected in various environmental media and pose emerging risks. However, much less is known about their fate in the environment. Anaerobic microbial transformation is a key pathway for the natural attenuation of contaminants. This study investigated, for the first time, the microbial transformation behaviors of β-TBCO and DPTE by Dehalococcoides mccartyi strain CG1. The results indicated that both β-TBCO and DPTE could be easily transformed by D. mccartyi CG1 with kobs values of 0.0218±0.0015 h-1 and 0.0089±0.0003 h-1, respectively. In particular, β-TBCO seemed to undergo dibromo-elimination and then epoxidation to form 4,5-dibromo-9-oxabicyclo[6.1.0]nonane, while DPTE experienced debromination at the benzene ring (ortho-bromine being removed prior to para-bromine) rather than at the carbon chain. Additionally, pronounced carbon and bromine isotope fractionations were observed during biotransformation of β-TBCO and DPTE, suggesting that C-Br bond breaking is the rate-limiting step of their biotransformation. Finally, coupled with identified products and isotope fractionation patterns, β-elimination (E2) and Sn2-nucleophilic substitution were considered the most likely microbial transformation mechanisms for β-TBCO and DPTE, respectively. This work provides important information for assessing the potential of natural attenuation and environmental risks of β-TBCO and DPTE.