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geochemistry Geochemistry is the science that uses the tools and principles of chemistry to explain the mechanisms behind major geological systems such as the Earth's crust and its oceans. The realm of geochemistry extends beyond the Earth, encompassing th ...
,
paleoclimatology Paleoclimatology (British spelling, palaeoclimatology) is the study of climates for which direct measurements were not taken. As instrumental records only span a tiny part of Earth's history, the reconstruction of ancient climate is important to ...
, and
paleoceanography Paleoceanography is the study of the history of the oceans in the geologic past with regard to circulation, chemistry, biology, geology and patterns of sedimentation and biological productivity. Paleoceanographic studies using environment models ...
''δ''13C (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, ‰). 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 The definition is, in per mil: :\delta \ce = \left( \frac - 1 \right) \times 1000 ‰ where the standard is an established reference material. ''δ''13C 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 Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers ( mass num ...
through kinetic fractionation. However some abiotic processes do the same,
methane Methane ( , ) is a chemical compound with the chemical formula (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane ...
from hydrothermal vents can be depleted by up to 50%.


Reference standard

The standard established for carbon-13 work was the Pee Dee Belemnite (PDB) and was based on a
Cretaceous The Cretaceous ( ) is a geological period that lasted from about 145 to 66 million years ago (Mya). It is the third and final period of the Mesozoic Era, as well as the longest. At around 79 million years, it is the longest geological period of ...
marine fossil, '' Belemnitella americana'', which was from the Peedee Formation in
South Carolina )''Animis opibusque parati'' ( for, , Latin, Prepared in mind and resources, links=no) , anthem = " Carolina";" South Carolina On My Mind" , Former = Province of South Carolina , seat = Columbia , LargestCity = Charleston , LargestMetro = ...
. This material had an anomalously high 13C:12C ratio (0.0112372), and was established as ''δ''13C 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 ''δ''13C value of +1.95‰. The 13C:12C ratio of NBS-19 was reported as 0.011078/0.988922=0.011202. Therefore, one could calculate the 13C:12C ratio of PDB derived from NBS-19 as 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 and environmental scientists; 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 ''δ''13C.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 A material with a ratio of 0.010743 for example would have a ''δ''13C value of –44‰ from (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.Miller & Wheeler, ''Biological Oceanography'', p. 186. The 13C:12C ratio for VPDB, which the
International Atomic Energy Agency The International Atomic Energy Agency (IAEA) is an intergovernmental organization that seeks to promote the peaceful use of nuclear energy and to inhibit its use for any military purpose, including nuclear weapons. It was established in 195 ...
(IAEA) defines as ''δ''13C value of zero is 0.01123720.www-pub.iaea.org/MTCD/publications/PDF/te_825_prn.pdf


Causes of ''δ''13C variations

Methane has a very light ''δ''13C signature: biogenic methane of −60‰, thermogenic methane −40‰. The release of large amounts of
methane clathrate Methane clathrate (CH4·5.75H2O) or (8CH4·46H2O), also called methane hydrate, hydromethane, methane ice, fire ice, natural gas hydrate, or gas hydrate, is a solid clathrate compound (more specifically, a clathrate hydrate) in which a large amou ...
can impact on global ''δ''13C values, as at the
Paleocene–Eocene Thermal Maximum The Paleocene–Eocene thermal maximum (PETM), alternatively (ETM1), and formerly known as the "Initial Eocene" or "", was a time period with a more than 5–8 °C global average temperature rise across the event. This climate event o ...
. More commonly, the ratio is affected by variations in
primary productivity In ecology, primary production is the synthesis of organic compounds from atmospheric or aqueous carbon dioxide. It principally occurs through the process of photosynthesis, which uses light as its source of energy, but it also occurs through c ...
and organic burial. Organisms preferentially take up light 12C, and have a ''δ''13C signature of about −25‰, depending on their
metabolic pathway In biochemistry, a metabolic pathway is a linked series of chemical reactions occurring within a cell. The reactants, products, and intermediates of an enzymatic reaction are known as metabolites, which are modified by a sequence of chemical ...
. Therefore, an increase in ''δ''13C in marine fossils is indicative of an increase in the abundance of vegetation. An increase in primary productivity causes a corresponding rise in ''δ''13C 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 ''δ''13C excursions

C3 and C4 plants have different signatures, allowing the abundance of C4 grasses to be detected through time in the ''δ''13C record. Whereas plants have a ''δ''13C of −16 to −10‰, plants have a ''δ''13C of −33 to −24‰.
Mass extinction An extinction event (also known as a mass extinction or biotic crisis) is a widespread and rapid decrease in the biodiversity on Earth. Such an event is identified by a sharp change in the diversity and abundance of multicellular organisms. I ...
s are often marked by a negative ''δ''13C 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 ''δ''13C.http://www.lpi.usra.edu/meetings/impact2000/pdf/3072.pdf


See also

* * * * Isotopic signature *
Isotope analysis Isotope analysis is the identification of isotopic signature, abundance of certain stable isotopes of chemical elements within organic and inorganic compounds. Isotopic analysis can be used to understand the flow of energy through a food w ...
*
Isotope geochemistry Isotope geochemistry is an aspect of geology based upon the study of natural variations in the relative abundances of isotopes of various elements. Variations in isotopic abundance are measured by isotope ratio mass spectrometry, and can reveal ...
*
Isotopic labeling Isotopic labeling (or isotopic labelling) is a technique used to track the passage of an isotope (an atom with a detectable variation in neutron count) through a reaction, metabolic pathway, or cell. The reactant is 'labeled' by replacing specific ...


References


Further reading

* * Mook, W. G., & Tan, F. C. (1991). Stable carbon isotopes in rivers and estuaries. Biogeochemistry of major world rivers, 42, 245–264. {{DEFAULTSORT:Delta18O Bioindicators Carbon Isotopes of carbon Environmental isotopes Geochemistry Paleoclimatology