δ¹³C

In geochemistry, paleoclimatology, and paleoceanography δ¹³C (pronounced "delta c thirteen") is an isotopic signature, a measure of the ratio of stable isotopes ¹³C : ¹²C, reported in parts per thousand (per mil, ‰).[1] The measure is also widely used in archaeology for the reconstruction of past diets, particularly to see if marine foods or certain types of plants were consumed [2]

Foraminifera samples

The definition is, in per mil:

${\displaystyle \delta {\ce {^{13}C}}=\left({\frac {\left({\frac {{\ce {^{13}C}}}{{\ce {^{12}C}}}}\right)_{\mathrm {sample} }}{\left({\frac {{\ce {^{13}C}}}{{\ce {^{12}C}}}}\right)_{\mathrm {standard} }}}-1\right)\times 1000}$ ‰

where the standard is an established reference material.

δ¹³C varies in time as a function of productivity, the signature of the inorganic source, organic carbon burial, and vegetation type. Biological processes preferentially take up the lower mass isotope through kinetic fractionation. However some abiotic processes do the same, methane from hydrothermal vents can be depleted by up to 50%.[3]

Reference standard

The standard established for carbon-13 work was the Pee Dee Belemnite (PDB) and was based on a Cretaceous marine fossil, Belemnitella americana, which was from the Peedee Formation in South Carolina. This material had an anomalously high ¹³C:¹²C ratio (0.0112372[4]), and was established as δ¹³C value of zero. Since the original PDB specimen is no longer available, its ¹³C:¹²C ratio can be back-calculated from a widely measured carbonate standard NBS-19, which has a δ¹³C value of +1.95‰.[5] The ¹³C:¹²C ratio of NBS-19 was reported as ${\displaystyle 0.011078/0.988922=0.011202}$.[6] Therefore, one could calculate the ¹³C:¹²C ratio of PDB derived from NBS-19 as ${\displaystyle 0.011202/(1.95/1000+1)=0.011202/1.00195=0.01118}$. Note that this value differs from the widely used PDB ¹³C:¹²C ratio of 0.0112372 used by in isotope forensics[7] and environmental scientists[8]; this discrepancy was previously attributed by a wikipedia author to a sign error in the interconversion between standards, but no citation was provided. Use of the PDB standard gives most natural material a negative δ¹³C.[9] A material with a ratio of 0.010743 for example would have a δ¹³C value of –44‰ from ${\displaystyle (0.010743\div 0.01124-1)\times 1000}$. The standards are used for verifying the accuracy of mass spectroscopy; as isotope studies became more common, the demand for the standard exhausted the supply. Other standards calibrated to the same ratio, including one known as VPDB (for "Vienna PDB"), have replaced the original.[10] The ¹³C:¹²C ratio for VPDB, which the International Atomic Energy Agency (IAEA) defines as δ¹³C value of zero is 0.01123720.[11]

Causes of δ¹³C variations

Methane has a very light δ¹³C signature: biogenic methane of −60‰, thermogenic methane −40‰. The release of large amounts of methane clathrate can impact on global δ¹³C values, as at the Paleocene–Eocene Thermal Maximum.[12]

More commonly, the ratio is affected by variations in primary productivity and organic burial. Organisms preferentially take up light ¹²C, and have a δ¹³C signature of about −25‰, depending on their metabolic pathway. Therefore, an increase in δ¹³C in marine fossils is indicative of an increase in the abundance of vegetation.

An increase in primary productivity causes a corresponding rise in δ¹³C values as more ¹²C is locked up in plants. This signal is also a function of the amount of carbon burial; when organic carbon is buried, more ¹²C is locked out of the system in sediments than the background ratio.

Geologic significance of δ¹³C excursions

C₃ and C₄ plants have different signatures, allowing the abundance of C₄ grasses to be detected through time in the δ¹³C record.[13] Whereas C₄ plants have a δ¹³C of −16 to −10‰, C₃ plants have a δ¹³C of −33 to −24‰.[14]

Mass extinctions are often marked by a negative δ¹³C anomaly thought to represent a decrease in primary productivity and release of plant-based carbon.

The evolution of large land plants in the late Devonian led to increased organic carbon burial and consequently a rise in δ¹³C.[15]

See also

• δ¹⁸O
• δ¹⁵N
• δ³⁴S
• Isotopic signature
• Isotope analysis
• Isotope geochemistry
• Isotopic labeling

References

1. Libes, Susan M. (1992). Introduction to Marine Biogeochemistry, 1st edition. New York: Wiley.
2. Schwarcz, Henry P.; Schoeninger, Margaret J. (1991). "Stable isotope analyses in human nutritional ecology". American Journal of Physical Anthropology. 34 (S13): 283–321. doi:10.1002/ajpa.1330340613.
3. McDermott, J.M., Seewald, J.S., German, C.R. and Sylva, S.P., 2015. Pathways for abiotic organic synthesis at submarine hydrothermal fields. Proceedings of the National Academy of Sciences, 112(25), pp.7668–7672.
4. Craig, Harmon (1957-01-01). "Isotopic standards for carbon and oxygen and correction factors for mass-spectrometric analysis of carbon dioxide". Geochimica et Cosmochimica Acta. 12 (1): 133–149. doi:10.1016/0016-7037(57)90024-8. ISSN 0016-7037.
5. Brand, Willi A.; Coplen, Tyler B.; Vogl, Jochen; Rosner, Martin; Prohaska, Thomas (2014-03-20). "Assessment of international reference materials for isotope-ratio analysis (IUPAC Technical Report)". Pure and Applied Chemistry. 86 (3): 425–467. doi:10.1515/pac-2013-1023. hdl:11858/00-001M-0000-0023-C6D8-8. ISSN 1365-3075.
6. Meija, Juris; Coplen, Tyler B.; Berglund, Michael; Brand, Willi A.; De Bièvre, Paul; Gröning, Manfred; Holden, Norman E.; Irrgeher, Johanna; Loss, Robert D. (2016-01-01). "Isotopic compositions of the elements 2013 (IUPAC Technical Report)". Pure and Applied Chemistry. 88 (3): 293–306. doi:10.1515/pac-2015-0503. ISSN 1365-3075.
7. Meier-Augenstein, Wolfram. Stable isotope forensics : methods and forensic applications of stable isotope analysis (Second ed.). Hoboken, NJ. ISBN 978-1-119-08022-0. OCLC 975998493.
8. Michener, Robert; Lajtha, Kate, eds. (2007-07-14). Stable Isotopes in Ecology and Environmental Science. Oxford, UK: Blackwell Publishing Ltd. doi:10.1002/9780470691854. ISBN 978-0-470-69185-4.
9. http://www.uga.edu/sisbl/stable.html#calib Overview of Stable Isotope Research – The Stable Isotope/Soil Biology Laboratory of the University of Georgia Institute of Ecology
10. Miller & Wheeler, Biological Oceanography, p. 186.
11. www-pub.iaea.org/MTCD/publications/PDF/te_825_prn.pdf
12. Panchuk, K.; Ridgwell, A.; Kump, L.R. (2008). "Sedimentary response to Paleocene-Eocene Thermal Maximum carbon release: A model-data comparison". Geology. 36 (4): 315–318. Bibcode:2008Geo....36..315P. doi:10.1130/G24474A.1.
13. Retallack, G.J. (2001). "Cenozoic Expansion of Grasslands and Climatic Cooling". The Journal of Geology. 109 (4): 407–426. Bibcode:2001JG....109..407R. doi:10.1086/320791.
14. O'Leary, M. H. (1988). "Carbon Isotopes in Photosynthesis". BioScience. 38 (5): 328–336. doi:10.2307/1310735. JSTOR 1310735.
15. http://www.lpi.usra.edu/meetings/impact2000/pdf/3072.pdf

Further reading

• Miller, Charles B.; Patricia A. Miller (2012) [2003]. Biological Oceanography (2nd ed.). Oxford: John Wiley & Sons. ISBN 978-1-4443-3301-5.
• Mook, W. G., & Tan, F. C. (1991). Stable carbon isotopes in rivers and estuaries. Biogeochemistry of major world rivers, 42, 245–264.