Expanding the range of halogenated 1′-methyl-1,2′-bipyrroles (MBPs) using GC/ECNI-MS and GC × GC/TOF-MS

Halogenated 1′methyl-1,2′-bipyrroles (MBPs) have been identified worldwide in marine mammals. Here we present the tentative identification of previously undetected MBP congeners in Delpinus delphis blubber using gas chromatography/electron capture negative ion mass spectrometry (GC/ECNI-MS) and comprehensive two-dimensional gas chromatography/time of flight mass spectrometry (GC × GC/TOF-MS). This is the first report of 26 congeners. The presence of numerous partially halogenated congeners suggests that they are either biosynthesized concomitantly with their perhalogenated counterparts or that their dehalogenation products can also bioaccumulate. The newly found compounds fit the geographic trend that has been previously noted. That is, samples from the Atlantic Ocean are dominated by the more brominated congeners while those from the Pacific are dominated by the more chlorinated congeners.