News

Oct 30, 2024

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

Nature Physics volume 17, pages 889–893 (2021)Cite this article 3463 Accesses 31 Citations 28 Altmetric Metrics details An Author Correction to this article was published on 15 June 2021 This article

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

3463 Accesses

31 Citations

28 Altmetric

Metrics details

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

This article has been updated

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.

This is a preview of subscription content, access via your institution

Access Nature and 54 other Nature Portfolio journals

Get Nature+, our best-value online-access subscription

$29.99 / 30 days

cancel any time

Subscribe to this journal

Receive 12 print issues and online access

$259.00 per year

only $21.58 per issue

Buy this article

Prices may be subject to local taxes which are calculated during checkout

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.

A Correction to this paper has been published: https://doi.org/10.1038/s41567-021-01293-1

Urey, H. C., Lowenstam, H. A., Epstein, S. & McKinney, C. R. Measurement of paleotemperatures and temperatures of the Upper Cretaceous of England, Denmark, and the Southeastern United States. Geol. Soc. Am. Bull. 62, 399–416 (1951).

Article ADS Google Scholar

Coplen, T. B. et al. New guidelines for δ13C measurements. Anal. Chem. 78, 2439–2441 (2006).

Article Google Scholar

Assonov, S. Summary and recommendations from the International Atomic Energy Agency Technical Meeting on the Development of Stable Isotope Reference Products (21–25 November 2016). Rapid Commun. Mass Spectrom. 32, 827–830 (2018).

Article ADS Google Scholar

Phillips, W. D. The end of artefacts. Nat. Phys. 15, 518 (2019).

Article Google Scholar

Malinovsky, D., Dunn, P. J. H., Holcombe, G., Cowen, S. & Goenaga-Infante, H. Development and characterisation of new glycine certified reference materials for SI-traceable 13C/12C isotope amount ratio measurements. J. Anal. At. Spectrom. 34, 147–159 (2019).

Article Google Scholar

Kerstel, E. in Handbook of Stable Isotope Analytical Techniques (ed. de Groot, P. A.) 759–787 (Elsevier, 2004); https://doi.org/10.1016/B978-044451114-0/50036-3

Brand, W. A. & Coplen, T. B. Stable isotope deltas: tiny, yet robust signatures in nature. Isotopes Environ. Health Stud. 48, 393–409 (2012).

Article Google Scholar

Brenna, J. T., Corso, T. N., Tobias, H. J. & Caimi, R. J. High-precision continuous-flow isotope ratio mass spectrometry. Mass Spectrom. Rev. 16, 227–258 (1997).

3.0.CO;2-J" data-track-item_id="10.1002/(SICI)1098-2787(1997)16:53.0.CO;2-J" data-track-value="article reference" data-track-action="article reference" href="https://doi.org/10.1002%2F%28SICI%291098-2787%281997%2916%3A5%3C227%3A%3AAID-MAS1%3E3.0.CO%3B2-J" aria-label="Article reference 8" data-doi="10.1002/(SICI)1098-2787(1997)16:53.0.CO;2-J">Article ADS Google Scholar

Flores, E., Viallon, J., Moussay, P., Griffith, D. W. T. & Wielgosz, R. I. Calibration strategies for FT-IR and other isotope ratio infrared spectrometer instruments for accurate δ13C and δ18O measurements of CO2 in air. Anal. Chem. 89, 3648–3655 (2017).

Article Google Scholar

Corso, T. N. & Brenna, J. T. High-precision position-specific isotope analysis. Proc. Natl Acad. Sci. USA 94, 1049–1053 (1997).

Article ADS Google Scholar

Webster, C. R. et al. Isotope ratios of H, C, and O in CO2 and H2O of the Martian atmosphere. Science 341, 260–263 (2013).

Article ADS Google Scholar

Crosson, E. R. et al. Stable isotope ratios using cavity ring-down spectroscopy: determination of 13C/12C for carbon dioxide in human breath. Anal. Chem. 74, 2003–2007 (2002).

Article Google Scholar

Zare, R. N. et al. High-precision optical measurements of 13C/12C isotope ratios in organic compounds at natural abundance. Proc. Natl Acad. Sci. USA 106, 10928–10932 (2009).

Article ADS Google Scholar

Long, D. A., Okumura, M., Miller, C. E. & Hodges, J. T. Frequency-stabilized cavity ring-down spectroscopy measurements of carbon dioxide isotope ratios. Appl. Phys. B 105, 471–477 (2011).

Article ADS Google Scholar

Castrillo, A. et al. Amount-ratio determinations of water isotopologues by dual-laser absorption spectrometry. Phys. Rev. A 86, 052515 (2012).

Article ADS Google Scholar

Kiseleva, M., Mandon, J., Persijn, S. & Harren, F. J. M. Line strength measurements and relative isotope ratio 13C/12C measurements in carbon dioxide using cavity ring down spectroscopy. J. Quant. Spectrosc. Radiat. Transf. 204, 152–158 (2018).

Article ADS Google Scholar

Stoltmann, T., Casado, M., Daëron, M., Landais, A. & Kassi, S. Direct, precision measurements of isotopologue abundance ratios in CO2 using molecular absorption spectroscopy: application to Δ17O. Anal. Chem. 89, 10129–10132 (2017).

Article Google Scholar

Kääriäinen, T., Richmond, C. A. & Manninen, A. Determining biogenic content of biogas by measuring stable isotopologues 12CH4, 13CH4, and CH3D with mid-infrared direct absorption laser spectrometer. Sensors 18, 496 (2018).

Article Google Scholar

Abe, M. et al. Dual wavelength 3.2-µm source for isotope ratio measurements of 13CH4/12CH4. Opt. Express 23, 21786–21797 (2015).

Article ADS Google Scholar

Craig, H. Isotopic standards for carbon and oxygen and correction factors for mass-spectrometric analysis of carbon dioxide. Geochim. Cosmochim. Acta 12, 133–149 (1957).

Article ADS Google Scholar

Assonov, S., Groening, M., Fajgelj, A., Hélie, J.-F. & Hillaire-Marcel, C. Preparation and characterisation of IAEA-603, a new primary reference material aimed at the VPDB scale realisation for δ13C and δ18O determination. Rapid Commun. Mass Spectrom. 34, e8867 (2020).

Article Google Scholar

Tans, P. & Zellweger, C. (eds) 18th WMO/IAEA Meeting on Carbon Dioxide, Other Greenhouse Gases and Related Tracers Measurement Techniques (GGMT-2015) GAW Report No. 229 (WMO, 2016); https://library.wmo.int/opac/doc_num.php?explnum_id=3074

Coplen, T. B. & Shrestha, Y. Isotope-abundance variations and atomic weights of selected elements: 2016 (IUPAC Technical Report). Pure Appl. Chem. 88, 1203–1224 (2016).

Article Google Scholar

Brand, W. A., Assonov, S. S. & Coplen, T. B. Correction for the 17O interference in δ(13C) measurements when analyzing CO2 with stable isotope mass spectrometry (IUPAC Technical Report). Pure Appl. Chem. 82, 1719–1733 (2010).

Article Google Scholar

Chang, T. L. & Li, W.-J. A calibrated measurement of the atomic weight of carbon. Chin. Sci. Bull. 35, 290–296 (1990).

Google Scholar

Nørgaard, J. V. et al. The International Measurement Evaluation Programme, IMEP-8: carbon and oxygen isotope ratios in CO2. Anal. Bioanal. Chem. 374, 1147–1154 (2002).

Article Google Scholar

Russe, K., Valkiers, S. & Taylor, P. D. P. Synthetic isotope mixtures for the calibration of isotope amount ratio measurements of carbon. Int. J. Mass. Spec. 235, 255–262 (2004).

Article Google Scholar

Valkiers, S. et al. Preparation of synthetic isotope mixtures for the calibration of carbon and oxygen isotope ratio measurements (in carbon dioxide) to the SI. Int. J. Mass. Spec. 264, 10–21 (2007).

Article Google Scholar

Dunn, P. J. H., Malinovsky, D. & Goenaga-Infante, H. Calibration strategies for the determination of stable carbon absolute isotope ratios in a glycine candidate reference material by element analyser-isotope ratio mass spectrometry. Anal. Bioanal. Chem. 407, 3169–3180 (2015).

Article Google Scholar

Skrzypek, G. & Dunn, P. J. H. Absolute isotope ratios defining scales used in isotope ratio mass spectrometers and optical isotope instruments. Rapid Commun. Mass Spectrom. 34, e8890 (2020).

Google Scholar

Yurimoto, H. et al. in Protostars and Planets V (eds Reipurth, B. et al.) 849–862 (Univ. Arizona Press, 2007).

Furukawa, Y. et al. Extraterrestrial ribose and other sugars in primitive meteorites. Proc. Natl Acad. Sci. USA 116, 24440–24445 (2019).

Article ADS Google Scholar

Galli, I. et al. Spectroscopic detection of radiocarbon dioxide at parts-per-quadrillion sensitivity. Optica 3, 385–388 (2016).

Article ADS Google Scholar

Fleisher, A. J., Long, D. A., Liu, Q., Gameson, L. & Hodges, J. T. Optical measurement of radiocarbon below unity fraction modern by linear absorption spectroscopy. J. Phys. Chem. Lett. 8, 4550–4556 (2017).

Article Google Scholar

Prokhorov, I., Kluge, T. & Janssen, C. Optical clumped isotope thermometry of carbon dioxide. Sci. Rep. 9, 4765 (2019).

Article ADS Google Scholar

Truong, G. W. et al. Frequency-agile, rapid scanning spectroscopy. Nat. Photon. 7, 532–534 (2013).

Article ADS Google Scholar

Hodges, J. T., Layer, H. P., Miller, W. W. & Scace, G. Frequency-stabilized single-mode cavity ring-down apparatus for high-resolution absorption spectroscopy. Rev. Sci. Instrum. 75, 849–863 (2004).

Article ADS Google Scholar

Fleurbaey, H., Yi, H., Adkins, E. M., Fleisher, A. J. & Hodges, J. T. Cavity ring-down spectroscopy of CO2 near λ = 2.06 µm: accurate transition intensities for the Orbiting Carbon Observatory-2 (OCO-2) “strong band”. J. Quant. Spectrosc. Radiat. Transf. 252, 107104 (2020).

Article Google Scholar

Fleisher, A. J. et al. Twenty-five-fold reduction in measurement uncertainty for a molecular line intensity. Phys. Rev. Lett. 123, 043001 (2019).

Article ADS Google Scholar

Rhoderick, G. C. et al. Development of a Northern Continental Air standard reference material. Anal. Chem. 88, 3376–3385 (2016).

Article Google Scholar

NOAA Central Calibration Laboratory Reference Gas Calibration Results for NIST Standard Reference Material 1720 Northern Continental Air Serial Number CC324315 (accessed 17 February 2021); https://www.esrl.noaa.gov/gmd/ccl/refgas.html

Milton, M. J. T., Guenther, F., Miller, W. R. & Brown, A. S. Validation of the gravimetric values and uncertainties of independently prepared primary standard gas mixtures. Metrologia 43, L7–L10 (2006).

Article ADS Google Scholar

Srivastava, A. & Verkouteren, R. M. Metrology for stable isotope reference materials: 13C/12C and 18O/16O isotope ratio value assignment of pure carbon dioxide gas samples on the Vienna PeeDee Belemnite-CO2 scale using dual-inlet mass spectrometry. Anal. Bioanal. Chem. 410, 4153–4163 (2018).

Article Google Scholar

Verkouteren, R. M. & Klinedinst, D. B. Value Assignment and Uncertainty Estimation of Selected Light Stable Isotope Reference Materials: RMs 8543–8545, RMs 8562–8564, and RM 8566 NIST Special Publication 260-149 (NIST, 2004); https://www.nist.gov/document-10350

Coplen, T. B. Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results. Rapid Commun. Mass Spectrom. 25, 2538–2560 (2011).

Article ADS Google Scholar

Polyansky, O. L. et al. High-accuracy CO2 line intensities determined from theory and experiment. Phys. Rev. Lett. 114, 243001 (2015).

Article ADS Google Scholar

Huang, X., Schwenke, D. W., Tashkun, S. A. & Lee, T. J. An isotopic-independent highly accurate potential energy surface for CO2 isotopologues and an initial 12C16O2 infrared line list. J. Chem. Phys. 136, 124311 (2012).

Article ADS Google Scholar

Tennyson, J. et al. DVR3D: a program suite for the calculation of rotation–vibration spectra of triatomic molecules. Comput. Phys. Commun. 163, 85–116 (2004).

Article ADS Google Scholar

Conway, E. K., Kyuberis, A. A., Polyansky, O. L., Tennyson, J. & Zobov, N. F. A highly accurate ab initio dipole moment surface for the ground electronic state of water vapour for spectra extending into the ultraviolet. J. Chem. Phys. 149, 084307 (2018).

Article ADS Google Scholar

Mizus, I. I. et al. High-accuracy water potential energy surface for the calculation of infrared spectra. Phil. Trans. R. Soc. A 376, 20170149 (2018).

Article ADS Google Scholar

Werner, H.-J., Knowles, P. J., Knizia, G., Manby, F. R. & Schütz, M. Molpro: a general-purpose quantum chemistry program package. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2, 242–253 (2012).

Article Google Scholar

Long, D. A. et al. High-accuracy near-infrared carbon dioxide intensity measurements to support remote sensing. Geophys. Res. Lett. 47, e2019GL086344 (2020).

Article ADS Google Scholar

Wübbeler, G., Víquez, G. J. P., Jousten, K., Werhahn, O. & Elster, C. Comparison and assessment of procedures for calculating the R(12) line strength of the ν1 + 2ν2 + ν3 band of CO2. J. Chem. Phys. 135, 204304 (2011).

Article ADS Google Scholar

Yi, H., Liu, Q., Gameson, L., Fleisher, A. J. & Hodges, J. T. High-accuracy 12C16O2 line intensities in the 2 μm wavelength region measured by frequency-stabilized cavity ring-down spectroscopy. J. Quant. Spectrosc. Radiat. Transf. 206, 367–377 (2018).

Article ADS Google Scholar

Lodi, L. & Tennyson, J. Line lists for H218O and H217O based on empirical line positions and ab initio intensities. J. Quant. Spectrosc. Radiat. Transf. 113, 850–858 (2012).

Article ADS Google Scholar

Download references

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.

Hongming Yi

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

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

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

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

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

Oleg L. Polyansky

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

Oleg L. Polyansky & Nikolai F. Zobov

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

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.

Correspondence to Adam J. Fleisher.

The authors declare no competing interests.

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

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

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

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

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).

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).

Reprints and permissions

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

Download citation

Received: 06 September 2020

Accepted: 17 March 2021

Published: 26 April 2021

Issue Date: August 2021

DOI: https://doi.org/10.1038/s41567-021-01226-y

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

Analytical and Bioanalytical Chemistry (2024)

Scientific Reports (2023)

Nature Catalysis (2022)

Analytical and Bioanalytical Chemistry (2022)

Analytical and Bioanalytical Chemistry (2022)