Gas chromatography and mass spectrometry of methoxylated polybrominated diphenyl ethers (MeO-PBDEs).

Twenty-six methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were characterized by gas chromatography (GC) on four different GC columns with different lengths and polarities, as well as by mass spectrometry using three ionization techniques, electron ionization (EI), electron capture negative ionization (ECNI) and positive ion chemical ionization (PICI). MeO-PBDE congeners with similar retention times on a nonpolar GC column were separated when analyzed on a polar GC column. EI can be used to determine the position of the methoxy substituent (ortho, meta or para) relative to the diphenyl ether oxygen in the MeO-PBDEs. The PICI ionization technique is shown to be valuable to generate structural information of the MeO-PBDEs, i.e. the degree of bromination on both the methoxy-substituted ring and the entirely brominated phenyl ring can be obtained. This structure information can also be achieved for certain MeO-PBDEs with the methoxy group in ortho position to the diphenyl ether bond in ECNI mode. Like other brominated compounds ECNI is preferable when analyzing environmental samples for quantification of MeO-PBDEs because of the formation of bromide ions, which enables low detection limits. Copyright (c) 2006 John Wiley & Sons, Ltd.