Quantitative measurements via co-elution and dual-isotope detection by gas chromatography-mass spectrometry

Abstract

Dual-isotope measurements by gas chromatography-mass spectrometry (GC-MS) which mimic isotope dilution may suffer from irreproducibilities or unduly large uncertainties because of variations in ionization efficacies for the respective forms in the MS source. Such variations are sometimes avoided via extensive pretreatments and high-resolution GC separations. However, in some circumstances, an alternative approach is feasible which instead exploits the advantages of decreasing GC resolution. By forcing both forms of each analyte to co-elute, their ionization efficacies in the MS source will be virtually identical, thereby allowing for highly reproducible relative response ratios to be attained despite dramatically lowered GC resolution. The co-elution results described here are nearly as precise as results from moderate-resolution separations in the absence of interferents. Thus, dual-isotope GC-MS measurements with co-elution of the target analytes and their respective isotopically labeled internal standards offer a powerful alternative to the conventional approach of requiring expensive and labor-intensive additional pretreatments and separations; however, the effects of interferences may be exacerbated by the forced co-elution and must also be considered.