Identification of PCB congeners by collision‐induced dissociation of [M − Cl + O]− from oxygen‐enhanced negative chemical ionization mass spectrometry
1987
Oxygen-enhanced negative chemical ionization MS is sensitive and specific for the detection of polychlorinated biphenyls (PCBs) without isobaric interferences (qualitative or quantitative) from congeners of higher levels of chlorination. The collision-induced dissociation (CID) spectra of the [M − Cl + O]− ion of 40 PCB congeners have been acquired on a triple quadrupole mass spectrometer.
Qualitative relationships between structure of the congener and its CID spectrum suggest that reliable identification of PCB congeners is possible even where capillary column gas chromatographic separation is incomplete. Congeners with hydrogen atoms located para and meta to the biphenyl linkage show most abundant collision-induced loss of HCl, whereas congeners with a penta-chloro phenyl ring show least CID loss of HCl. Congeners IUPAC 105 and 121 have CID spectra suggesting a pathway for sequential loss of HCl and CO neutrals during the collision-induced dissociation of the [M − Cl + O]− ion of these molecules. Unambiguous identification of PCB congeners in natural materials will require a complete set of pure, synthetic PCB congeners: identification problems are illustrated using an extract of Northern Shark (dogfish) liver oil.
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