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H-abstraction reactions occurring on electron ionization mass spectrometry(EI-MS) are a long-standing and crucial topic in MS research. Yet some criticalrelevant mechanisms are controversial and ambiguous, and information about theEI-induced H-abstraction reactions of halogenated organic compounds (HOCs) iscompletely in the dark. This study provides a systematic investigation ofH-abstraction reactions of HOCs taking place on EI source using13C6-hexachlorobenzene (13C6-HCB) and 13C6-hexabromobenzene (13C6-HBB) asexemplary compounds by gas chromatography high resolution mass spectrometry(GC-HRMS). The H-abstraction efficiencies were evaluated with the MS signalintensity ratios of ions with H-abstraction relative to the correspondingoriginal ions (without H-abstraction). Ion source temperatures, EI energies andnumbers of heavy isotope atoms (37Cl or 81Br) of isotopologues wereinvestigated in terms of their effects on the H-abstraction efficiencies. TheH-abstraction efficiencies of individual isotopologues generally decreased fromthe first to the last isotopologues of respective ions, and those of individualions were different from each other, with the highest values of 0.017 and 0.444for 13C6-HCB and 13C6-HBB, respectively. The overall H-abstraction efficienciesinvolving all measured ions of 13C6-HCB and 13C6-HBB were 0.004 and 0.128,respectively. EI energies and emission currents could impact the H-abstractionefficiencies. The H-abstraction reactions were inferred to belong toion-molecule reactions. Some strategies were proposed for eliminating oralleviating the interference triggered by the H-abstraction reactions on EI-MSin identification of halogenated organic pollutants (HOPs). Our findingsprovide a better understanding for the EI-induced H-abstraction reactions ofHOCs, and may benefit identification of HOPs in environmental analysis,especially for novel HOPs.

Ascertaining hydrogen-abstraction reaction efficiencies of halogenated organic compounds on electron ionization mass spectrometry