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The determination of biomarker distributions by tandem mass spectrometry
Authors:R.P. Philp   J.-N. Oung   C.P. Yu  S. Lewis
Abstract:The rapid development of biomarker geochemistry and its application to petroleum exploration problems has been due in no small part to gas chromatography-mass spectrometry (GC-MS). The recent availability of hybrid and triple stage quadrupole mass spectrometers have introduced a number of novel ways for the detection and identification of biomarkers present in extremely complex mixtures of organic compounds from various sources including crude oils and source rock extracts.A triple stage quadrupole mass spectrometer has been used in the MS/MS mode with both a gas chromatograph and direct insertion probe as inlet systems, to develop alternative methods for biomarker analyses. Selected ions formed in the ion source of the mass spectrometer are permitted to enter the collision cell where, following collision with an inert gas, the daughter ions are separated using the third quadrupole. In this manner specific parent/daughter ion relationships are utilized to monitor and resolve classes of biomarkers or individual components from within a complex mixture. Furthermore, deuterated analogues of naturally occurring biomarkers can be utilized for quantitation purposes since the parent/daughter relationship for the standard will differ, depending on the number of deuterium atoms present, even though the relative retention times are identical.The ability of MS/MS to resolve components spectrometrically as well as chromatographically greatly enhances the analytical short-column capabilities of this system. In this paper the utilization of GC-MS/MS and the direct insertion probe MS/MS to determine biomarker distributions in crude oils both qualitatively and quantitatively are discussed. The results from the study show that it is possible to use the probe data to rapidly correlate oils on the basis of their source materials and if necessary select samples for more detailed analysis by GC-MS/MS. A major advantage of the direct insertion probe method is speed of analysis although some component resolution is lost. In an effort to minimize this problem and still maintain the rapid analysis time, the use of short columns in the GC is also described. This approach provides the ability to undertake relatively rapid analyses with limited chromatographic resolution but at relatively high levels of sensitivity.
Keywords:biomarkers   GC-MS/MS   quantitation   crude oil correlations
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