Temperature Zonal Combustion Reactor for the 15-Nitrogen and 13-Carbon Isotopic Determination of Enriched Biosynthetic Materials

Abstract

A temperature distribution was imposed on a solid−gas reactor to help accomplish the 15-nitrogen or 13-carbon isotopic determination of biosynthetic materials such as algal protein-15N. The temperature zonal combustion reactor (TZCR) can operate offline from its mass spectrometer, and this reactor facilitates the stable isotopic determination of highly enriched biomaterials (>95 atom % isotope). The reactor structure is a glass pipe comprising a quartz segment, transition segments, and threaded sockets. Precise positioning of the reactor within a tubular furnace establishes a longitudinal temperature distribution that is used to drive solid−gas chemistry in distinct zones: sample, catalyst, and sorbent. The TZCR module typically includes a reactor pipe, gastight valve, sample, reactants, reactant containers, and furnace. An important advantage of TZCR-mass spectrometer is preliminary vacuum heat treatment of the crude sample to remove volatile impurities before sample combustion (enabling isotopic enrichment determination of the analyte). For the determination of 15N enrichment, sample combustion at 650 °C in oxygen was supplemented by Fe3O4 catalyst near 500 °C and Li2O at 25 °C that concertedly promoted the intrareactor depletion of CO, CO2, and H2O. As a result, the primary gaseous product was dinitrogen. After 15N sample conversion, the reactor was coupled to a quadrupole MS for product analysis (N2+ ions for 15N determination). Accordingly, uniformly enriched biomaterials were analyzed such as algal protein-15N that measured 99.0 ± 0.12 atom % 15N. By adapting the methodology for 13C determination, lyophilized algal cells-13C were determined to be 99.1 ± 0.06 atom % 13C. Stable isotope enrichments were computed by minimizing the numeric differences between theoretical and actual MS signals.