Elimination of nitrogen interference during online oxygen isotope analysis of nitrogen‐doped organics using the “NiCat” nickel reduction system

Abstract

Accurate online analysis of the δ(18)O values of nitrogen-bearing organic compounds is of interest to several emergent fields, including ecology, forensics and paleontology. During online analysis, high-temperature conversion (HTC) of nitrogen-bearing organics produces N(2) gas which creates isobaric interference with the isotopic measurement. Specifically, N(2) reacts with trace amounts of oxygen in the mass spectrometer source to form (14)N(16)O (m/z 30), which prevents accurate evaluation of the sample (12)C(18)O peak (m/z 30). We present an alternative system to the conventional HTC, which uses a nickel-catalyzed ("NiCat") reduction furnace to convert HTC-produced CO into CO(2), allowing for δ(18)O measurement using signal intensities at m/z 44 and 46. This system yields identical δ(18)O values for nitrogen-doped and undoped sucrose and cellulose compounds up to molar yield ratios of N(2):CO = 0.22. In contrast, our conventional HTC system configured to factory recommendations with the stock gas chromatography (GC) column produced a discrepancy of ~5‰ between nitrogen-doped and undoped samples. Because of its ability to eliminate isobaric interference, the NiCat system is a viable alternative to conventional HTC for δ(18)O measurement, and can be constructed from relatively inexpensive and readily available materials. As an additional advantage, the CO(2) analyte produced by NiCat may be cryofocused, to allow for oxygen-isotope determinations on very small amounts of sample substrate.