Improved measurement of stable isotope ratios in gas chromatography/mass spectrometry using the microwave-powered chemical reaction interface for mass spectrometry

Abstract

The microwave-powered chemical reaction interface for mass spectrometry (CRIMS) has been successfully used for selective detection of analytes labeled with 13C, 15N and D following capillary gas chromatography separation with good analytical characteristics in biological applications. In this study we evaluated how an advanced data system coupled to a quadrupole mass analyzer could improve precision and sensitivity of stable isotope ratio measurements for 13C and 15N. The enrichments of 13C and 15N are determined by monitoring CO2 (m/z 44 and 45) and NO (m/z 30 and 31). These small molecules are produced from the analyte in the chemical reaction interface in the presence of SO2 as a reactant gas. Using caffeine and its 13C1, 15N2-labeled analog for these quantitative studies, we have found that the Vector 2 system improves overall precision (RSD = 0.6% for both carbon and nitrogen) and sensitivity of stable isotope measurements by at least a factor of two compared to the Vector 1 system, and by more than an order of magnitude compared to our older results. With the optimum system we are now able to measure an atom% enrichment of 0.0044 for 15N and 0.015 for 13C in caffeine in the presence of 300 ng of unlabeled material. This is more than half way between isotopic detection limits of conventional gas chromatography/mass spectrometry and the state-of-the-art, which is a gas chromatograph coupled to a chemical combustor and a dual-collector isotope ratio mass spectrometer.