Biotransformation of hexabromocyclododecanes with hexachlorocyclohexane-transforming Sphingobium chinhatense strain IP26

Bacterial evolution has resulted in the appearance of several Sphingomonadacea strains that gained the ability to metabolize hexachlorocyclohexanes (HCHs). HCHs have been widely used as pesticides but were banned under the Stockholm Convention on persistent organic pollutants (POPs) in 2009. Here we present evidence for bacterial transformation reactions of hexabromocyclododecanes (HBCDs), which are structurally related to HCHs. HBCDs were used as flame retardants. They are now also considered as POPs and their production and use is restricted since 2013. Racemic alpha-, beta-, and gamma-HBCDs and their mixture were exposed to Sphingobium chinhatense IP26 in resting cell assays in parallel to beta-HCH. All HBCD stereoisomers were converted with (-)beta-HBCD being the best and both alpha-HBCD enantiomers the poorest substrates. HBCD conversion rates were 27-430 times slower than that of beta-HCH. Three generations of hydroxylated transformation products were observed, 7 pentabromocyclododecanol isomers (PeBCD- ols), 11 tetrabromocyclododecadiols (TeBCD-diols) and 3 tribromocyclododecatriols (TrBCD-triols). The conversion of (+)alpha-, (-)beta- and (-)gamma-HBCD was faster than those of their enantiomers. Therefore the respective enantiomeric excess increased to 3 +/- 1%, 36 +/- 1% and 6 +/- 2% during 48 h of bacterial exposure. PeBCD-ols appeared first, followed by TeBCD-diols and TrBCD-triols indicating stepwise hydrolytic dehalogenation reactions. In conclusion, severe HCH pollution at geographically distinct dumpsites triggered bacterial evolution to express enzymes transforming such compounds. We used S. chinhatense IP26 bacteria to transform structurally related HBCDs, also regulated under the Stockholm Convention. Such bacteria might be useful for bioremediation but the toxicity of the numerous transformation products observed must be assessed in advance. (C) 2017 Elsevier Ltd. All rights reserved.