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Published April 19, 2016 | Supplemental Material
Journal Article Open

Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils

Abstract

An international project developed, quality-tested, and determined isotope−δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope−δ scales. The RMs span a range of δ^2H_(VSMOW-SLAP) values from −210.8 to +397.0 mUr or ‰, for δ^(13)C_(VPDB-LSVEC) from −40.81 to +0.49 mUr and for δ^(15)N_(Air) from −5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C_(16) n-alkanes, n-C_(20)-fatty acid methyl esters (FAMEs), glycines, and L-valines, together with polyethylene powder and string, one n-C_(17)-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a ^2H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ2H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain ^(13)C and carbon-bound organic ^2H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

Additional Information

© 2016 American Chemical Society. Received: November 19, 2015; Accepted: March 14, 2016; Published: March 14, 2016. We are indebted to Marilyn Fogel, Libby Stern, and Michael Wieser for assisting with the initiation of this project. Stefanie Poppenhäger (Amino GmbH, Frellstedt, Germany; www.amino.de) donated pure L-valine. Tetyana Gilevska, Henk Jansen, Steffen Kümmel, and Harald Lowag provided analytical assistance. The manuscript benefited from constructive reviews by L. I. Wassenaar, Linda Stalker, and two anonymous reviewers. This project was supported by U.S. National Science Foundation Grant EAR-1052927. The National Deuteration Facility is partly supported by the National Collaborative Research Infrastructure Strategy (NCRIS), an initiative of the Australian Government. The support of the U.S. Geological Survey National Research Program made this report possible. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. The authors declare no competing financial interest.

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