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Absolute 13C/12C isotope amount ratio for Vienna PeeDee Belemnite from infrared absorption spectroscopy

Nature Physics volume 17, pages 889–893 (2021)Cite this article

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An Author Correction to this article was published on 15 June 2021

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Abstract

Measurements of isotope ratios are predominantly made with reference to standard specimens that have been characterized in the past. In the 1950s, the carbon isotope ratio was referenced to a belemnite sample collected by Heinz Lowenstam and Harold Urey1 in South Carolina’s PeeDee region. Due to exhaustion of the sample since then, reference materials that are traceable to the original artefact are used to define the Vienna PeeDee Belemnite scale for stable carbon isotope analysis2. However, these reference materials have also become exhausted or proven to exhibit unstable composition over time3, mirroring issues with the international prototype of the kilogram that led to a revised International System of Units4. A campaign to elucidate the stable carbon isotope ratio of Vienna PeeDee Belemnite is underway5, but independent measurement techniques are required to support it. Here we report an accurate value for the stable carbon isotope ratio inferred from infrared absorption spectroscopy, fulfilling the promise of this fundamentally accurate approach6. Our results agree with a value recently derived from mass spectrometry5 and therefore advance the prospects of International System of Units–traceable isotope analysis. Further, our calibration-free method could improve mass balance calculations and enhance isotopic tracer studies in carbon dioxide source apportionment.

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Fig. 1: AIR-IS.
Fig. 2: AIR-IS measurements of R(13C/12C)sample versus IRMS assignments of δ13C.
Fig. 3: AIR-IS value of R(13C/12C)VPDB.

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Data availability

Source data are provided with this paper, and are additionally available at https://doi.org/10.18434/mds2-2369. All other data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

We acknowledge M. E. Kelley and W. R. Miller Jr, (NIST) for preparing several CO2-in-air gas samples. Funding was provided by the NIST Greenhouse Gas and Climate Science Program. O.L.P. acknowledges partial support from the Quantum Pascal project 18SIB04, which received funding from the EMPIR programme co-financed by the Participating States and the European Union’s Horizon 2020 research and innovations programme. N.F.Z. acknowledges State project 0035-2019-0016.

Author information

Author notes

  1. Hongming Yi

    Present address: Department of Civil and Environmental Engineering, Princeton University, Princeton, NJ, USA

  2. These authors contributed equally: Adam J. Fleisher, Hongming Yi.

Authors and Affiliations

  1. Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA

    Adam J. Fleisher, Hongming Yi, Abneesh Srivastava & Joseph T. Hodges

  2. Department of Physics and Astronomy, University College London, London, UK

    Oleg L. Polyansky

  3. Institute of Applied Physics, Russian Academy of Sciences, Nizhny Novgorod, Russia

    Oleg L. Polyansky & Nikolai F. Zobov

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  1. Adam J. Fleisher
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Contributions

A.J.F. assisted with the experimental design, assembly and characterization; performed data analysis; and wrote the Letter. H.Y. assembled optical instrumentation and performed spectroscopy on the CO2-in-air samples. A.S. performed isotope ratio mass spectrometry on the parent CO2 samples. O.L.P. and N.F.Z. performed quantum chemistry calculations of CO2 transition intensities. J.T.H. conceived the experimental design and assisted with instrumentation, data analysis and reduction. All the authors contributed to the final written Letter.

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Correspondence to Adam J. Fleisher.

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Peer review information Nature Physics thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1 and 2, Discussion and Tables 1–5.

Source data

Source Data Fig. 1

Infrared absorption spectrum of CO2 (Fig. 1b,c).

Source Data Fig. 2

Measurements of R(13C/12C) for several gas samples of CO2 in air (Fig. 2a,b). Upper- and lower-bound δ13C values for some terrestrial and marine sources of carbon (Fig. 2c).

Source Data Fig. 3

Measurements of R(13C/12C) for VPDB (Fig. 3a). Comparison between the value of R(13C/12C)VPDB determined in this work and those available in the literature (Fig. 3c).

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Fleisher, A.J., Yi, H., Srivastava, A. et al. Absolute 13C/12C isotope amount ratio for Vienna PeeDee Belemnite from infrared absorption spectroscopy. Nat. Phys. 17, 889–893 (2021). https://doi.org/10.1038/s41567-021-01226-y

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