Refinements to the diastereoisomer-specific method for the analysis of hexabromocyclododecane

The emergence of hexabromocyclodoclecane (HBCD) as a bromine-based flame retardant of concern is partly attributable to recent measurements on the environmental occurrence of the individual diastereoisomers (alpha, beta and gamma). These measurements were fuelled by a newly developed liquid chromatography/tandem mass spectrometric (LC/MS/MS)-based analytical method. However, in the course of our recent studies on the environmental fate and behaviour of the diastereoisomers of HBCD, some interesting features of the LC/MS/MS method became apparent. For example, the ion signal of the native ions was found to be dependent on the final extract volume. This was true for both biotic and sediment samples and was found to arise from the suppression of the ion signal due to endogenous material in the extracts that escape clean-up. We have also found differences in the stability of the diastereoisomers in different solvents. If left unaccounted for, both factors can compromise analytical measurement data. By way of a series of controlled experiments conducted at our two laboratories [Department of Fisheries & Oceans Canada (DFO) and Environment Canada (EC)], we illustrate these features and demonstrate that use of newly synthesized labelled HBCD isomers [(13-carbon (C-13) and deuterium (d(18))] can minimize and often circumvent matrix-related effects. Copyright (C) 2005 John Wiley & Sons, Ltd.