Offline oxygen isotope analysis of organic compounds with high N:O

Abstract

Although the advantages of online δ(18)O analysis of organic compounds make its broad application desirable, researchers have encountered NO(+) isobaric interference with CO(+) at m/z 30 (e.g. (14)N(16)O(+), (12)C(18)O(+)) when analyzing nitrogenous substrates. If the δ(18)O value of inter-laboratory standards for substrates with high N:O value could be confirmed offline, these materials could be analyzed periodically and used to evaluate δ(18)O data produced online for nitrogenous unknowns. To this end, we present an offline method based on modifications of the methods of Schimmelmann and Deniro (Anal. Chem. 1985; 57: 2644) and Sauer and Sternberg (Anal. Chem. 1994; 66: 2409), whereby all the N(2) from the gas products of a chlorinated pyrolysis was eliminated, resulting in purified CO(2) for analysis via a dual-inlet isotope ratio mass spectrometry system. We evaluated our method by comparing observed δ(18)O values with previously published or inter-laboratory calibrated δ(18)O values for five nitrogen-free working reference materials; finding isotopic agreement to within ±0.2‰ for SIGMA® cellulose, IAEA-CH3 cellulose (C(6)H(10)O(5)) and IAEA-CH6 sucrose (C(12)H(22)O(11)), and within ±1.8‰ for IAEA-601 and IAEA-602 benzoic acids (C(7)H(6)O(2)). We also compared the δ(18)O values of IAEA-CH3 cellulose and IAEA-CH6 sucrose that was nitrogen-'doped' with adenine (C(5)H(5)N(5)), imidazole (C(3)H(4)N(2)) and 2-aminopyrimidine (C(4)H(5)N(3)) with the undoped δ(18)O values for the same substrates; yielding isotopic agreement to within ±0.7‰. Finally, we provide an independent analysis of the δ(18)O value of IAEA-600 caffeine (C(8)H(10)N(4)O(2)), previously characterized using online systems exclusively, and discuss the reasons for an average 1.4‰ enrichment in δ(18)O observed offline relative to the consensus online δ(18)O value.