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Improved online δ 18 O measurements of nitrogen‐ and sulfur‐bearing organic materials and a proposed analytical protocol
Author(s) -
Qi Haiping,
Coplen Tyler B.,
Wassenaar Leonard I.
Publication year - 2011
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.5088
Subject(s) - reproducibility , chemistry , nitrogen , analytical chemistry (journal) , mass spectrometry , gas chromatography , sulfur , chromatography , spectrometer , organic chemistry , physics , quantum mechanics
It is well known that N 2 in the ion source of a mass spectrometer interferes with the CO background during the δ 18 O measurement of carbon monoxide. A similar problem arises with the high‐temperature conversion (HTC) analysis of nitrogenous O‐bearing samples (e.g. nitrates and keratins) to CO for δ 18 O measurement, where the sample introduces a significant N 2 peak before the CO peak, making determination of accurate oxygen isotope ratios difficult. Although using a gas chromatography (GC) column longer than that commonly provided by manufacturers (0.6 m) can improve the efficiency of separation of CO and N 2 and using a valve to divert nitrogen and prevent it from entering the ion source of a mass spectrometer improved measurement results, biased δ 18 O values could still be obtained. A careful evaluation of the performance of the GC separation column was carried out. With optimal GC columns, the δ 18 O reproducibility of human hair keratins and other keratin materials was better than ±0.15 ‰ (n = 5; for the internal analytical reproducibility), and better than ±0.10 ‰ (n = 4; for the external analytical reproducibility). Copyright © 2011 John Wiley & Sons, Ltd.