CARBON ISOTPES

➢ Carbon (Z =6) is fourth in abundance among the elements of the solar system
after H, He, and O (Anders and Grevesse, 1989).

➢ The two stable isotopes of C and their abundances and masses are:

12
6𝐶: 98.9%, 12.000000 amu

13
6𝐶: 1.1%, 13.003355 amu
➢ 13C/ 12C ratio is 1.083612.

➢ Atomic weight of C is 12.011036.

➢ Mass of 13C is 8.36% greater than that of 12C, which causes the C isotopes
to be fractionated by chemical and biological processes in nature.

➢ Radioactive cosmogenic 14C is produced by an (n,p) reaction on stable 14N in the atmosphere.
➢ The isotopic composition of C is expressed by the δ13C parameter—

( 13C/ 12C) −(13C/ 12C)

spl std
δ13C = X 103 %
( C/ 12C)s𝑡𝑑
13

➢ The standard for stable carbon isotope work is

Pee Dee Belemnite (PDB), which is a calcium
carbonate fossil cephalopod from the
Cretaceous Pee Dee Formation of South Carolina, USA.

➢ H. Craig introduced the PDB standard in 1957

(PDB = sample taken from an internal calcite structure
from a fossil Belemnitella americana from the Cretaceous
Pee Dee Formation in South Carolina.
➢ 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‰

➢ The 13C:12C ratio of NBS-19 was reported as 0.011202.

➢ Other standards calibrated to the same ratio, including one known

as VPDB (for "Vienna PDB"), have replaced the original

➢ The 13C:12C ratio for VPDB, which the International Atomic Energy Agency (IAEA)
defines as δ13C value of zero is 0.01123720.
➢ Positive δ13C values signify that the C is enriched in 13C relative to the standard.

➢ Negative δ13C values imply depletion in 13C.

➢ The fractionation factor for C isotopes is:

a 13 R
α b ( C) = R𝑎
𝑏

➢ Where, a and b are C-bearing compounds or phases in isotopic equilibrium at a specified T.

➢ R is the isotopic 13C/ 12C ratio.

➢ When green plants absorb CO2 molecules during photosynthesis, they prefer
12C over 13C.

➢ Negative δ13C organic matter of photosynthetic plants

and herbivores and carnivorous animals.

➢ Zero δ13C Marine calcite and aragonite

Carbon is the principal ingredient of the biosphere and also occurs in
rocks, in the atmosphere, hydrosphere etc and therefore, plays an important
role in the geochemical processes that occur at or near the surface of the earth.
BIOSPHERE

➢ Photosynthesis is a complex biochemical process which converts

atmospheric CO2 and H2O into the organic matter of green plants.

6CO2 + 6H2O C6H12O6 + 6O2

➢ The C that is fixed in plant tissue as a result of this

process is variably depleted in 13C relative to PDB.

➢ Consequently organic matter of biogenic origin has

a negative δ13C values, including biosphere,
coal, petroleum, and natural gas of Phanerozoic age,
and amorphous C as well as graphite of Precambrian age.
CARBON DIOXIDE

➢ The δ13C value of CO2 in the atmosphere average value of about -

7.7%

➢ But varies seasonally in response to preferential absorption of 12C by plants.

➢ Average δ13C value due to annual -27%

combustion of fossil fuel
The amplitude of seasonal variations of δ13C values of atmospheric CO2 in the
northern hemisphere decreases with decreasing latitude from N to S.

Seasonal amplitude of δ13C in atmospheric CO

• Point Barrow (Alaska 71 ֯ N) :0.9%

• Mauna Loa (Hawaii 20 ֯ N): 0.4%

• Christmas Island (Indian Ocea 4֯ N): 0.15%

➢ The concentration of CO2 in atmosphere of the Earth has varied in
geological past in consonance with the average global temperature.

➢ For example, Ice deposited in Antartica and Greenland during—

Glacial stages of the Pleistocene Epoch lower CO2

Interglacial stages higher CO2

➢ Climatic cooling allows more CO2 to dissolve in the oceans, thus

reducing the concentration of atmospheric CO2 and thereby intensifying
global cooling.
GREEN PLANTS

The isotope fractionation of C during photosynthesis takes place in

three steps:

1. Preferential absorption of 12CO2 molecules from the atmosphere by diffusion

through the cell membrane depending on the concentration of CO2 in the ambient air.
Consequently the air adjacent to green plants is enriched in during 13CO2 daytime.

2. Preferential conversion of 12CO2 (dissolved in cytoplasm) into phosphoglyceric acid.

3. Synthesis of different organic compounds from phosphoglyceric acid

The δ13C values of plant tissue depend on the metabolic
processes by means of which C is incorporated into plants.

• The δ13C values of plants that metabolize CO2

by Calvin cycle (C3 plants: most plants on land) range from -23 to -34%

• Plants that use Hatch-Slack process

(C4 plants: aquatic, desert, saltmarsh plants) -6 to -23%

• Plants that employ crassulacean acid metabolism

(CAM plants) -11 to -33%

• Algae and bacteria exceed the range of C

isotope compositions of
C3, C4, CAM plants
FOSSIL FUELS

➢ Coal, petroleum and natural gas are strongly depleted in 13C consistent with their
derivation from organic matter produced by photosynthetic organisms.

➢ Since photosynthesis is energized by EM radiation from the sun, all forms of fossil
fuels are deposits of solar energy.

➢ Combustion of these materials by humans

after the start of the Industrial Revolution
at circa 1860 AD has emitted large quantities
of CO2 to the atmosphere.
Bituminous coal

➢ Plants decompose to form peat and subsequently to lignite, bituminous coal,

anthracite,
and even graphite depending on the T and P applied over long periods of time.

➢ Most deposits of bituminous coal are of post-Devonian age.

➢ The δ13C value of bituminous coal has

an average of about -25% (PDB).

➢ The depletion of coal in 13C is consistent

with its derivation from photosynthetic
plants.
Methanogenic calcite

➢ The chemical evolution of peat into lignite and bituminous coal takes place by
progressive loss of H in the form of CH4 gas that is enriched in 1H and 12C relative to
residual organic matter.

➢ Methane emanating from + O dissolved in precipitate as calcite

“cleats”
coal beds groundwater in joints and bedding planes

➢ Such methanogenic calcite has higly negative δ13C values.

➢ For example, δ13C values of epigenetic calcite in Triassic coal of southern Victoria
Land
in Antartica ranges from -15.6 to -16.9% (PDB) compared to an average of -24.9% in
Petroleum and natural gas

➢ Petroleum is a naturally occurring liquid composed of a mixture of hydrocarbon

molecules.

➢ These molecules are strongly depleted in 13C relative to PDB.

➢ It has a negative δ13C values between -18 and -34% (Stahl 1979).

➢ Evidently, petroleum is more depleted in 13C than coal.

➢ The process of petroleum formation starts with deposition
of organic matter in marine and non-marine basins.

➢ Following burial, the organic matter is converted into kerogen

during diagenesis of the sediment
to form carbonaceous shales.

➢ When these rocks are exposed to

increased T for sufficient length of
time, the kerogen decomposes into
liquid or gaseous hydrocarbons.
The hydrocarbons are then transported from its
source rock into the adjacent reservoir rocks,
where they are trapped allowing them
to accumulate in oil pools.
Maturation of organic matter at increasing T

➢ The maturation of organic matter at increasing T causes

the resulting kerogen to become enriched in 13C because
12C-12C bonds are weaker than the bonds formed by 13C.

➢ Therefore, the δ13C value of methane derived from kerogen

changes from about -55% (kerogen of low maturity) to about
-35% (methane derived from overcooked kerogen).
Collinearity of different hydrocarbons with its source rock

➢ Stahl (1979) described a case where petroleum in

Jurassic and Tertiary reservoir rocks in the Canadian Arctic
formed nearly identical oil type-curves.

➢ This suggests that the oil in both pools originated from

the same source.