A numerical scheme to diagnose interferences in gas chromatography–mass spectrometry quantitation of coeluting isotopically labeled and unlabeled counterparts with partially overlapping ion profiles

Quantitation of chromatographically coeluting compounds with partially overlapping mass profiles is a challenging task, especially if only a low-resolution mass spectrometer is available. To examine whether theoretical predictions can be utilized to determine the appropriate concentration ranges of the coeluting compounds that satisfy the non-interfering condition, we utilized an algorithm based upon a two-component model to compare the experimentally measured and predicted quantitation errors. Selected unlabeled and 13C-labeled polychlorinated biphenyl (PCB) congeners were investigated as model compounds. Standard solutions containing various concentration ratios of the unlabeled and 13C-labeled PCB congeners were analyzed, and the data were used to compare with theoretical predictions derived from the chlorine isotopic distributions (35Cl and 37Cl). Good agreements between experimental predictions and theoretical predictions were found on the magnitude of interferences for quantitation of 13C-labeled PCB congeners, as well as on the variability of the quantitation errors with the concentration ratio of 13C-labeled and unlabeled PCB counterparts. In addition, the magnitude of interferences considered in the present study was highly dependent upon the number of coexisting ions included for quantitation and their relative abundances in the mass spectrum. All these results suggest that the magnitude of interferences in quantifying a pair of coeluting compounds with partially overlapping mass spectral profiles can be effectively determined and minimized by carefully selecting the concentration ratio of the coeluting compounds and/or the number of quantitation ions. Finally, the selection of the experimental parameters to satisfy the non-interfering condition can be made purely on the basis of theoretical considerations.