Three new calcium formate reference materials for δ13C measurements and a redetermination of the R(13C/12C) ratio for VPDB based on proton nuclear magnetic resonance measurements

Rapid Communications in Mass Spectrometry
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Abstract

Rationale

Isotope ratio mass spectrometry (IRMS) and proton nuclear magnetic resonance (1H NMR) spectroscopy are independent techniques for determining the isotope ratio R(13C/12C) in organic compounds. However, the lack of suitable reference materials has limited intercalibration of results from these methods.

Methods

Three high-purity calcium formate isotopic reference materials were developed, each ideal for accurate isotope ratio measurements by both 1H NMR and isotope-ratio mass spectrometry (IRMS). For each material, R(13C/12C) was determined by 1H NMR, and the relative isotope abundance (δ13CVPDB-LSVEC) by IRMS. The combined IRMS and NMR results were used to determine the R(13C/12C) value of Vienna Peedee belemnite (VPDB).

Results

The combined datasets yield a value for R(13C/12C) of 0.0111050 ± 0.0000047 (k = 2) for VPDB, which is 6.7‰ lower than the commonly cited value of 0.011180, but similar to other recent determinations. These three calcium formate reference materials exhibit high accuracy across both analytical methods and provide robust tools for instrument calibration, method validation, and inter-laboratory comparison in carbon stable isotope ratio analysis.

Conclusions

An accurate R(13C/12C) value for VPDB strengthens the link between relative (δ13CVPDB-LSVEC) values from IRMS and R(13C/12C) isotope ratios from NMR and other techniques. These three calcium formate isotopic reference materials (USGS106, USGS107, and USGS108) are available from the US Geological Survey and provide reference materials for calibration, method validation, and inter-laboratory comparison in carbon isotope ratio analysis.

Suggested Citation

Hoffman, D.W., Rasmussen, C., Schimmelmann, A., Reid, L.T., Qi, H., and Coplen, T.B., 2026, Three new calcium formate reference materials for δ13C measurements and a redetermination of the R(13C/12C) ratio for VPDB based on proton nuclear magnetic resonance measurements: Rapid Communications in Mass Spectrometry, v. 40, no. 18, e70132, 9 p., https://doi.org/10.1002/rcm.70132.

Publication type Article
Publication Subtype Journal Article
Title Three new calcium formate reference materials for δ13C measurements and a redetermination of the R(13C/12C) ratio for VPDB based on proton nuclear magnetic resonance measurements
Series title Rapid Communications in Mass Spectrometry
DOI 10.1002/rcm.70132
Volume 40
Issue 18
Publication Date July 01, 2026
Year Published 2026
Language English
Publisher Wiley
Contributing office(s) WMA - Laboratory & Analytical Services Division
Description e70132, 9 p.
Additional publication details