Kerogen

en.wikipedia.org/wiki/Kerogen

Not to be confused with Kerosene.

Kerogen is a solid organic matter in sedimentary rocks. Consisting of an estimated 10 16
tons of carbon, it is the most abundant source of organic compounds on earth, exceeding
the total organic content of living matter by 10,000 fold. It is insoluble in normal organic
solvents and it does not have a specific chemical formula. Upon heating, kerogen converts
in part to liquid and gaseous hydrocarbons. Petroleum and natural gas form from
kerogen.[1] Based on its origin, kerogen may be classified as algal, mixed terrestrial and
marine.[2]

History
The name "kerogen" was introduced by the Scottish organic chemist Alexander Crum
Brown in 1906. [3][4][5][6] It means in Greek "wax birth" (Greek: κηρός "wax" and -gen, γένεση
"birth").

Structure of a vanadium porphyrin compound (left) extracted from

petroleum by Alfred E. Treibs, father of organic geochemistry. The
close structural similarity of this molecule and chlorophyll a (right)
helped establish that petroleum was derived from plants.[7]

Composition
Kerogen is a mixture of organic chemical compounds that make up a portion of the organic
matter in sedimentary rocks.[2] As kerogen is a mixture of organic material, rather than a
specific chemical, it cannot be given a chemical formula. Its chemical composition can vary
distinctively from sample to sample. For example, kerogen from the Green River Formation
oil shale deposit of western North America contains elements in the proportions carbon
215 : hydrogen 330 : oxygen 12 : nitrogen 5 : sulfur 1.[8]

Kerogen is insoluble in normal organic solvents because of the high molecular weight
(upwards of 1,000 daltons or 1000 Da; 1 Da = 1 atomic mass unit) of its component
compounds. The soluble portion is known as bitumen. When heated to the right
temperatures in the Earth's crust, (oil window c. 50–150 °C, gas window c. 150–200 °C,

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both depending on how quickly the source rock is heated) some types of kerogen release
crude oil or natural gas, collectively known as hydrocarbons (fossil fuels). When such
kerogens are present in high concentration in rocks such as shale, they form possible
source rocks. Shales rich in kerogens that have not been heated to a warmer temperature to
release their hydrocarbons may form oil shale deposits.

Formation
Kerogen arises from the degradation of living matter, such as diatoms, planktons, spores
and pollens. In this break-down process, large biopolymers from proteins and
carbohydrates dismantle partially or completely. (This break-down process can be viewed
as the reverse of photosynthesis[9]). These dismantled components are units that can then
polycondense to form polymers. This polymerization usually happens alongside the
formation of a mineral component (geopolymer) resulting in a sedimentary rock like
kerogen shale.

The formation of polymers in this way accounts for the large molecular weights and
diverse chemical compositions associated with kerogen. The smallest units are the fulvic
acids, the medium units are the humic, and the largest units are the humins. When organic
matter is contemporaneously deposited with geologic material, subsequent sedimentation
and progressive burial or overburden provide significant pressure and a temperature
gradient. When these humic precursors are subjected to sufficient geothermal pressures
for sufficient geologic time, they begin to undergo certain specific changes to become
kerogen. Such changes are indicative of the maturity stage of a particular kerogen. These
changes include loss of hydrogen, oxygen, nitrogen, and sulfur, which leads to loss of other
functional groups that further promote isomerization and aromatization which are
associated with increasing depth or burial. Aromatization then allows for neat molecular
stacking in sheets, which in turn increases molecular density and vitrinite reflectance
properties, as well as changes in spore coloration, characteristically from yellow to orange
to brown to black with increasing depth.

Kerogen breaks down in the subsurface to generate oil and gas, which form the source of
hydrocarbons in conventional reservoirs. In unconventional resources, many of which are
referred to as shale, the produced hydrocarbons have not been expelled from the source
rock, but instead are stored and transported within the shale. Most kerogens of relevance
to the oil and gas industry are marine (type II). Much of the porosity in shale is hosted
within kerogen,[10] and the recent development of economic shale resources has led to
increased research into the composition of kerogen. Studies using NMR spectroscopy have
found that carbon in kerogen can range from almost entirely aliphatic (sp3 hybridized) to
almost entirely aromatic (sp2 hybridized).[11] with kerogens of higher type and/or higher
thermal maturity typically having higher abundance of aromatic carbon.

Types
Labile kerogen breaks down to form heavy hydrocarbons (i.e., oils), refractory kerogen
breaks down to form light hydrocarbons (i.e., gases), and inert kerogen forms graphite.

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A Van Krevelen diagram is one example of classifying kerogens, where they tend to form
groups when the ratios of hydrogen to carbon and oxygen to carbon are compared.[12]

Type I: Sapropelic
Type 1 oil shales yield larger amount of volatile or extractable compounds than other types
upon pyrolysis. Hence, from the theoretical view, Type 1 kerogen oil shales provide the
highest yield of oil and are the most promising deposits in terms of conventional oil
retorting.[13]

containing alginite, amorphous organic matter, cyanobacteria, freshwater algae, and

land plant resins
Hydrogen:carbon ratio > 1.25
Oxygen:carbon ratio < 0.15
Shows great tendency to readily produce liquid hydrocarbons.
It derives principally from lacustrine algae and forms only in anoxic lakes and several
other unusual marine environments
Has few cyclic or aromatic structures
Formed mainly from proteins and lipids

Type II: Planktonic

Type II kerogen is common in many oil shale deposits. It is based on marine organic
materials, which are formed in reducing environments. Sulfur is found in substantial
amounts in the associated bitumen and generally higher than the sulfur content of Type I or
III. Although pyrolysis of Type II kerogen yields less oil than Type I, the amount acquired is
still sufficient to consider Type II bearing rocks as potential oil sources

Plankton (marine)
Hydrogen:carbon ratio < 1.25
Oxygen:carbon ratio 0.03 to 0.18
Tend to produce a mix of gas and oil.
Several types:
Sporinite: formed from the casings of pollen and spores
Cutinite: formed from terrestrial plant cuticle
Resinite: formed from terrestrial plant resins and animal decomposition resins
Liptinite: formed from terrestrial plant lipids (hydrophobic molecules that are
soluble in organic solvents) and marine algae

They all have great tendencies to produce petroleum and are all formed from lipids
deposited under reducing conditions.

Type II: Sulfurous

Similar to Type II but high in sulfur.

Type III: Humic

Land plants (coastal)

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 Hydrogen:carbon ratio < 1
Oxygen:carbon ratio 0.03 to 0.3
Material is thick, resembling wood or coal.
Tends to produce coal and gas (Recent research has shown that Type III kerogens
can actually produce oil under extreme conditions) [14]
Has very low hydrogen because of the extensive ring and aromatic systems

Kerogen Type III is formed from terrestrial plant matter that is lacking in lipids or waxy
matter. It forms from cellulose, the carbohydrate polymer that forms the rigid structure of
terrestrial plants, lignin, a non-carbohydrate polymer formed from phenyl-propane units that
binds the strings of cellulose together, and terpenes and phenolic compounds in the plant.
Type III kerogen involving rocks are found to be the least productive upon pyrolysis and
probably the least favorable deposits for oil generation

Type IV: Residue

Hydrogen: carbon ratio < 0.5

Type IV kerogen contains mostly decomposed organic matter in the form of polycyclic
aromatic hydrocarbons. They have no potential to produce hydrocarbons. [15]

Extra-terrestrial
Carbonaceous chondrite meteorites contain kerogen-like components. [16] Such material is
thought to have formed the terrestrial planets. Kerogen materials have been detected also
in interstellar clouds and dust around stars.[17]

The Curiosity rover has detected organic deposits similar to kerogen in mudstone samples
in Gale Crater on Mars using a revised drilling technique. The presence of benzene and
propane also indicates the possible presence of kerogen-like materials, from which
hydrocarbons are derived.[18][19][20][21][22][23][24][25][26]

See also
Asphaltene – Heavy organic molecular substances that are found in crude oil,
Oil shale geology
Petroleum geology – The study of the origin, occurrence, movement, accumulation,
and exploration of hydrocarbon fuels
Tholin

References
1. ^ M. Vandenbroucke, C. Largeau (2007). "Kerogen origin, evolution and structure".
Organic Geochemistry. 38: 719–833. doi:10.1016/j.orggeochem.2007.01.001.
2. ^ a b "Kerogen". Oilfield Glossary. Schlumberger.
3. ^ Oxford English Dictionary 3rd Ed. (2003)
4. ^ Cane, R.F. (1976). "The origin and formation of oil shale". In Teh Fu Yen; Chilingar,
George V. Oil Shale. Amsterdam: Elsevier. p. 27. ISBN 978-0-444-41408-3. Retrieved 31
4/6
 May 2009.
5. ^ Hutton, Adrian C.; Bharati, Sunil; Robl, Thomas (1994). "Chemical and Petrographic
Classification of Kerogen/Macerals". Energy Fuels. Elsevier Science. 8 (6): 1478–1488.
doi:10.1021/ef00048a038.
6. ^ D. R. Steuart in H. M. Cadell et al. Oil-Shales of Lothians iii. 142 (1906) "We are
indebted to Professor Crum Brown, F.R.S., for suggesting the term Kerogen to
express the carbonaceous matter in shale that gives rise to crude oil in distillation."
7. ^ Kvenvolden, K. A. (2006). "Organic geochemistry – A retrospective of its first 70
years" (PDF). Org. Geochem. 37: 1–11. doi:10.1016/j.orggeochem.2005.09.001.
8. ^ Robinson, W.E. (1976). "Origin and characteristics of Green River oil shale". In Teh Fu
Yen; Chilingar, George V. Oil Shale. Amsterdam: Elsevier. pp. 61–80. ISBN 978-0-444-
41408-3.
9. ^ Tucker M.E. (1988) Sedimentary Petrology, An Introduction, Blackwell, London.
p197. ISBN 0-632-00074-0
10. ^ Loucks, Robert. "Morphology, genesis, and distribution of nanometer-scale pores in
siliceous mudstones of the Mississippian Barnett Shale". Journal of Sedimentary
Research. 79: 848–861. doi:10.2110/jsr.2009.092.
11. ^ Kelemen, Simon. "Direct characterization of kerogen by X-ray and solid-state 13C
nuclear magnetic resonance methods". Energy Fuels. 21: 1548–1561.
doi:10.1021/ef060321h.
12. ^ Example of a Van Krevelen diagram
13. ^ Tissot, Bernard P.; Welte, Dietrich H. (1984). "Petroleum Formation and Occurrence".
doi:10.1007/978-3-642-87813-8.
14. ^ Krause FF, 2009
15. ^ Weber G., Green J., ‘‘Guide to oil shale’’. NationalConference of State Legislatures.
Washington D.C. USA.p. 21, 1981.
16. ^ Nakamura, T. (2005) "Post-hydration thermal metamorphism of carbonaceous
chondrites", Journal of Mineralogical and Petrological Sciences, volume 100, page
268, [1] (PDF) Retrieved 1 September 2007
17. ^ Papoular, R. (2001) "The use of kerogen data in understanding the properties and
evolution of interstellar carbonaceous dust", Astronomy and Astrophysics, volume
378, pages 597-607, [2] Archived 27 September 2007 at the Wayback Machine. (PDF)
Retrieved 1 September 2007
18. ^ "Ancient organic molecules found on Mars". C&E News. 7 June 2018.
19. ^ Brown, Dwayne; Wendel, JoAnna; Steigerwald, Bill; Jones, Nancy; Good, Andrew (7
June 2018). "Release 18-050 - NASA Finds Ancient Organic Material, Mysterious
Methane on Mars". NASA. Retrieved 7 June 2018.
20. ^ NASA (7 June 2018). "Ancient Organics Discovered on Mars - video (03:17)". NASA.
Retrieved 7 June 2018.
21. ^ Wall, Mike (7 June 2018). "Curiosity Rover Finds Ancient 'Building Blocks for Life' on
Mars". Space.com. Retrieved 7 June 2018.
22. ^ Chang, Kenneth (7 June 2018). "Life on Mars? Rover's Latest Discovery Puts It 'On the
Table' - The identification of organic molecules in rocks on the red planet does not
necessarily point to life there, past or present, but does indicate that some of the
building blocks were present". The New York Times. Retrieved 8 June 2018.
23. ^ Voosen, Paul (7 June 2018). "NASA rover hits organic pay dirt on Mars" . Science.
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 Retrieved 7 June 2018.
24. ^ ten Kate, Inge Loes (8 June 2018). "Organic molecules on Mars". Science. 360
(6393): 1068–1069. doi:10.1126/science.aat2662. Retrieved 8 June 2018.
25. ^ Webster, Christopher R.; et al. (8 June 2018). "Background levels of methane in Mars'
atmosphere show strong seasonal variations". Science. 360 (6393): 1093–1096.
doi:10.1126/science.aaaq0131. Retrieved 8 June 2018.
26. ^ Eigenbrode, Jennifer L.; et al. (8 June 2018). "Organic matter preserved in 3-billion-
year-old mudstones at Gale crater, Mars". Science. 360 (6393): 1096–1101.
doi:10.1126/science.aaas9185. Retrieved 8 June 2018.

External links
European Association of Organic Geochemists
Organic Geochemistry (journal)
Animation illustrating kerogene formation (approx t=50s) "Oil and Gas Formation"
YouTube clip by EarthScience WesternAustralia

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