Kerogen
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Kerogen is solid, insoluble
organic matter Organic matter, organic material, or natural organic matter refers to the large source of carbon-based compounds found within natural and engineered, terrestrial, and aquatic environments. It is matter composed of organic compounds that have c ...
in
sedimentary rock Sedimentary rocks are types of rock that are formed by the accumulation or deposition of mineral or organic particles at Earth's surface, followed by cementation. Sedimentation is the collective name for processes that cause these particles ...
s. Comprising an estimated 1016 tons of carbon, it is the most abundant source of organic compounds on earth, exceeding the total organic content of living matter 10,000-fold. It is insoluble in normal
organic solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
s and it does not have a specific
chemical formula In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, ...
. Upon heating, kerogen converts in part to liquid and gaseous hydrocarbons.
Petroleum Petroleum, also known as crude oil, or simply oil, is a naturally occurring yellowish-black liquid mixture of mainly hydrocarbons, and is found in geological formations. The name ''petroleum'' covers both naturally occurring unprocessed crud ...
and
natural gas Natural gas (also called fossil gas or simply gas) is a naturally occurring mixture of gaseous hydrocarbons consisting primarily of methane in addition to various smaller amounts of other higher alkanes. Low levels of trace gases like carbo ...
form from kerogen. Kerogen may be classified by its origin: lacustrine (e.g.,
algal Algae (; singular alga ) is an informal term for a large and diverse group of photosynthetic eukaryotic organisms. It is a polyphyletic grouping that includes species from multiple distinct clades. Included organisms range from unicellular mic ...
), marine (e.g.,
planktonic Plankton are the diverse collection of organisms found in water (or air) that are unable to propel themselves against a current (or wind). The individual organisms constituting plankton are called plankters. In the ocean, they provide a crucia ...
), and
terrestrial Terrestrial refers to things related to land or the planet Earth. Terrestrial may also refer to: * Terrestrial animal, an animal that lives on land opposed to living in water, or sometimes an animal that lives on or near the ground, as opposed to ...
(e.g.,
pollen Pollen is a powdery substance produced by seed plants. It consists of pollen grains (highly reduced microgametophytes), which produce male gametes (sperm cells). Pollen grains have a hard coat made of sporopollenin that protects the gametophyt ...
and
spore In biology, a spore is a unit of sexual or asexual reproduction that may be adapted for dispersal and for survival, often for extended periods of time, in unfavourable conditions. Spores form part of the life cycles of many plants, algae, f ...
s). The name "kerogen" was introduced by the Scottish
organic chemist Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J. ...
Alexander Crum Brown Alexander Crum Brown FRSE FRS (26 March 1838 – 28 October 1922) was a Scottish organic chemist. Alexander Crum Brown Road in Edinburgh's King's Buildings complex is named after him. Early life and education Crum Brown was born at 4 Belle ...
in 1906,''Oxford English Dictionary'' 3rd Ed. (2003) derived from the Greek for "wax birth" (Greek: κηρός "wax" and -gen, γένεση "birth"). The increased production of
hydrocarbons In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ex ...
from
shale Shale is a fine-grained, clastic sedimentary rock formed from mud that is a mix of flakes of clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4) and tiny fragments (silt-sized particles) of other minerals, especial ...
has motivated a revival of research into the composition, structure, and properties of kerogen. Many studies have documented dramatic and systematic changes in kerogen composition across the range of thermal maturity relevant to the oil and gas industry. Analyses of kerogen are generally performed on samples prepared by acid demineralization with critical point drying, which isolates kerogen from the rock matrix without altering its chemical composition or microstructure.


Formation

Kerogen is formed during sedimentary
diagenesis Diagenesis () is the process that describes physical and chemical changes in sediments first caused by water-rock interactions, microbial activity, and compaction after their deposition. Increased pressure and temperature only start to play a ...
from the degradation of living matter. The original organic matter can comprise lacustrine and marine
algae Algae (; singular alga ) is an informal term for a large and diverse group of photosynthetic eukaryotic organisms. It is a polyphyletic grouping that includes species from multiple distinct clades. Included organisms range from unicellular mic ...
and
plankton Plankton are the diverse collection of organisms found in Hydrosphere, water (or atmosphere, air) that are unable to propel themselves against a Ocean current, current (or wind). The individual organisms constituting plankton are called plankt ...
and terrestrial higher-order plants. During diagenesis, large
biopolymers Biopolymers are natural polymers produced by the cells of living organisms. Like other polymers, biopolymers consist of monomeric units that are covalently bonded in chains to form larger molecules. There are three main classes of biopolymers, c ...
from, e.g., proteins,
lipids Lipids are a broad group of naturally-occurring molecules which includes fats, waxes, sterols, fat-soluble vitamins (such as vitamins A, D, E and K), monoglycerides, diglycerides, phospholipids, and others. The functions of lipids include ...
, and carbohydrates in the original organic matter decompose partially or completely. This breakdown process can be viewed as the reverse of
photosynthesis Photosynthesis is a process used by plants and other organisms to convert light energy into chemical energy that, through cellular respiration, can later be released to fuel the organism's activities. Some of this chemical energy is stored i ...
. These resulting units can then polycondense to form
geopolymers Geopolymers are inorganic, typically ceramic, alumino-silicate forming long-range, covalently bonded, non-crystalline (amorphous) networks. Obsidian (volcanic glass) fragments are a component of some geopolymer blends. Commercially produced geopol ...
. The formation of geopolymers in this way accounts for the large
molecular weight A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
s and diverse chemical compositions associated with kerogen. The smallest units are the
fulvic acid Humic substances (HS) are organic compounds that are important components of humus, the major organic fraction of soil, peat, and coal (and also a constituent of many upland streams, dystrophic lakes, and ocean water). For a long era in the 19th an ...
s, the medium units are the humic acids, and the largest units are the
humins Humins are carbon-based macromolecular substances, that can be found in soil chemistry or as a by-product from saccharide-based biorefinery processes. Humins in soil chemistry Soil consists of both mineral (inorganic) and organic components. The ...
. This polymerization usually happens alongside the formation and/or sedimentation of one or more mineral components resulting in a sedimentary rock like
oil shale Oil shale is an organic-rich fine-grained sedimentary rock containing kerogen (a solid mixture of organic chemical compounds) from which liquid hydrocarbons can be produced. In addition to kerogen, general composition of oil shales constitute ...
. When kerogen is contemporaneously deposited with geologic material, subsequent
sedimentation Sedimentation is the deposition of sediments. It takes place when particles in suspension settle out of the fluid in which they are entrained and come to rest against a barrier. This is due to their motion through the fluid in response to the ...
and progressive
burial Burial, also known as interment or inhumation, is a method of final disposition whereby a dead body is placed into the ground, sometimes with objects. This is usually accomplished by excavating a pit or trench, placing the deceased and objec ...
or
overburden In mining, overburden (also called waste or spoil) is the material that lies above an area that lends itself to economical exploitation, such as the rock, soil, and ecosystem that lies above a coal seam or ore body. Overburden is distinct from tai ...
provide elevated pressure and temperature owing to lithostatic and geothermal gradients in Earth's crust. Resulting changes in the burial temperatures and pressures lead to further changes in kerogen composition including loss of
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
,
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
,
nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
,
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
, and their associated
functional groups In organic chemistry, a functional group is a substituent or moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions regardless of the rest ...
, and subsequent
isomerization In chemistry, isomerization or isomerisation is the process in which a molecule, polyatomic ion or molecular fragment is transformed into an isomer with a different chemical structure. Enolization is an example of isomerization, as is tautomeriz ...
and
aromatization Aromatization is a chemical reaction in which an aromatic system is formed from a single nonaromatic precursor. Typically aromatization is achieved by dehydrogenation of existing cyclic compounds, illustrated by the conversion of cyclohexane int ...
Such changes are indicative of the thermal maturity state of kerogen. Aromatization allows for molecular stacking in sheets, which in turn drives changes in physical characteristics of kerogen, such as increasing molecular density, ''
vitrinite Vitrinite is one of the primary components of coals and most sedimentary kerogens. Vitrinite is a type of maceral, where "macerals" are organic components of coal analogous to the "minerals" of rocks. Vitrinite has a shiny appearance resembling gla ...
reflectance'', and spore coloration (yellow to orange to brown to black with increasing depth/thermal maturity). During the process of thermal maturation, kerogen breaks down in high-temperature pyrolysis reactions to form lower-molecular-weight products including bitumen, oil, and gas. The extent of thermal maturation controls the nature of the product, with lower thermal maturities yielding mainly bitumen/oil and higher thermal maturities yielding gas. These generated species are partially expelled from the kerogen-rich source rock and in some cases can charge into a reservoir rock. Kerogen takes on additional importance in unconventional resources, particularly shale. In these formations, oil and gas are produced directly from the kerogen-rich source rock (i.e. the source rock is also the reservoir rock). Much of the porosity in these shales is found to be hosted within the kerogen, rather than between mineral grains as occurs in conventional reservoir rocks. Thus, kerogen controls much of the storage and transport of oil and gas in shale. Another possible method of formation is that Vanabin containing organisms cleave the core out of
Chlorin In organic chemistry, chlorins are tetrapyrrole pigments that are partially hydrogenated porphyrins. The parent chlorin is an unstable compound which undergoes air oxidation to porphine. The name chlorin derives from chlorophyll. Chlorophyll ...
based compounds such as the magnesium in Chlorophyll and replace it with their vanadium center in order to attach and harvest energy via Light Harvesting Complexes. It is theorized that the bacteria contained in worm castings, ''
Rhodopseudomonas palustris ''Rhodopseudomonas palustris'' is a rod-shaped, Gram-negative purple nonsulfur bacterium, notable for its ability to switch between four different modes of metabolism. ''R. palustris'' is found extensively in nature, and has been isolated from ...
'', do this during it's
Photoautotrophism Photoautotrophs are organisms that use light energy and inorganic carbon to produce organic materials. Eukaryotic photoautotrophs absorb energy through the chlorophyll molecules in their chloroplasts while prokaryotic photoautotrophs use chlorophyl ...
mode of metabolism. Over time colonies of light harvesting bacteria solidify, forming kerogen.


Composition

Kerogen is a complex mixture of
organic chemical compound In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon chemical bond, bonds. Due to carbon's ability to Catenation, catenate (form chains with other carbon atoms), millions of organic c ...
s that make up the most abundant fraction of organic matter in
sedimentary rock Sedimentary rocks are types of rock that are formed by the accumulation or deposition of mineral or organic particles at Earth's surface, followed by cementation. Sedimentation is the collective name for processes that cause these particles ...
s. As kerogen is a mixture of organic materials, it is not defined by a single chemical formula. Its chemical composition varies substantially between and even within sedimentary formations. For example, kerogen from the
Green River Formation The Green River Formation is an Eocene geologic formation that records the sedimentation in a group of intermountain lakes in three basins along the present-day Green River in Colorado, Wyoming, and Utah. The sediments are deposited in very fine ...
oil shale deposit of western
North America North America is a continent in the Northern Hemisphere and almost entirely within the Western Hemisphere. It is bordered to the north by the Arctic Ocean, to the east by the Atlantic Ocean, to the southeast by South America and the Car ...
contains elements in the proportions
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
215 :
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
330 :
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
12 :
nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
5 :
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
1. Kerogen is insoluble in normal organic solvents in part because of the high
molecular weight A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
of its component compounds. The soluble portion is known as
bitumen Asphalt, also known as bitumen (, ), is a sticky, black, highly viscous liquid or semi-solid form of petroleum. It may be found in natural deposits or may be a refined product, and is classed as a pitch. Before the 20th century, the term a ...
. When heated to the right temperatures in the
earth's crust Earth's crust is Earth's thin outer shell of rock, referring to less than 1% of Earth's radius and volume. It is the top component of the lithosphere, a division of Earth's layers that includes the crust and the upper part of the mantle. The ...
, (''oil window'' c. 50–150 
°C The degree Celsius is the unit of temperature on the Celsius scale (originally known as the centigrade scale outside Sweden), one of two temperature scales used in the International System of Units (SI), the other being the Kelvin scale. The ...
, ''gas window'' c. 150–200 °C, both depending on how quickly the source rock is heated) some types of kerogen release
crude oil Petroleum, also known as crude oil, or simply oil, is a naturally occurring yellowish-black liquid mixture of mainly hydrocarbons, and is found in geological formations. The name ''petroleum'' covers both naturally occurring unprocessed crude ...
or
natural gas Natural gas (also called fossil gas or simply gas) is a naturally occurring mixture of gaseous hydrocarbons consisting primarily of methane in addition to various smaller amounts of other higher alkanes. Low levels of trace gases like carbo ...
, collectively known as
hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...
s (
fossil fuel A fossil fuel is a hydrocarbon-containing material formed naturally in the Earth's crust from the remains of dead plants and animals that is extracted and burned as a fuel. The main fossil fuels are coal, oil, and natural gas. Fossil fuels m ...
s). When such kerogens are present in high concentration in rocks such as organic-rich mudrocks
shale Shale is a fine-grained, clastic sedimentary rock formed from mud that is a mix of flakes of clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4) and tiny fragments (silt-sized particles) of other minerals, especial ...
, they form possible
source rock In petroleum geology, source rock is rock which has generated hydrocarbons or which could generate hydrocarbons. Source rocks are one of the necessary elements of a working petroleum system. They are organic-rich sediments that may have been depo ...
s. Shales that are rich in kerogen but have not been heated to required temperature to generate hydrocarbons instead may form
oil shale Oil shale is an organic-rich fine-grained sedimentary rock containing kerogen (a solid mixture of organic chemical compounds) from which liquid hydrocarbons can be produced. In addition to kerogen, general composition of oil shales constitute ...
deposits. The chemical composition of kerogen has been analyzed by several forms of solid state spectroscopy. These experiments typically measure the speciations (bonding environments) of different types of atoms in kerogen. One technique is 13C
NMR spectroscopy Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic technique to observe local magnetic fields around atomic nuclei. The sample is placed in a magnetic fiel ...
, which measures carbon speciation. NMR experiments have found that carbon in kerogen can range from almost entirely
aliphatic In organic chemistry, hydrocarbons ( compounds composed solely of carbon and hydrogen) are divided into two classes: aromatic compounds and aliphatic compounds (; G. ''aleiphar'', fat, oil). Aliphatic compounds can be saturated, like hexane, ...
( ''sp3'' hybridized) to almost entirely
aromatic In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...
( ''sp2'' hybridized), with kerogens of higher thermal maturity typically having higher abundance of aromatic carbon. Another technique is Raman spectroscopy.
Raman scattering Raman scattering or the Raman effect () is the inelastic scattering of photons by matter, meaning that there is both an exchange of energy and a change in the light's direction. Typically this effect involves vibrational energy being gained by a ...
is characteristic of, and can be used to identify, specific vibrational modes and symmetries of molecular bonds. The first-order Raman spectra of kerogen comprises two principal peaks; a so-called G band ("graphitic") attributed to in-plane vibrational modes of well-ordered ''sp2'' carbon and a so-called D band ("disordered") from symmetric vibrational modes of ''sp2'' carbon associated with lattice defects and discontinuities. The relative spectral position (Raman shift) and intensity of these carbon species is shown to correlate to thermal maturity, with kerogens of higher thermal maturity having higher abundance of graphitic/ordered aromatic carbons. Complementary and consistent results have been obtained with infrared (IR) spectroscopy, which show that kerogen has higher fraction of aromatic carbon and shorter lengths of aliphatic chains at higher thermal maturities. These results can be explained by the preferential removal of aliphatic carbons by cracking reactions during pyrolysis, where the cracking typically occurs at weak C-C bonds beta to aromatic rings and results in the replacement of a long aliphatic chain with a methyl group. At higher maturities, when all labile aliphatic carbons have already been removed—in other words, when the kerogen has no remaining oil-generation potential—further increase in aromaticity can occur from the conversion of aliphatic bonds (such as alicyclic rings) to aromatic bonds. IR spectroscopy is sensitive to carbon-oxygen bonds such as
quinone The quinones are a class of organic compounds that are formally "derived from aromatic compounds uch as benzene or naphthaleneby conversion of an even number of –CH= groups into –C(=O)– groups with any necessary rearrangement of double ...
s, ketones, and
ester In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ar ...
s, so the technique can also be used to investigate oxygen speciation. It is found that the oxygen content of kerogen decreases during thermal maturation (as has also been observed by elemental analysis), with relatively little observable change in oxygen speciation. Similarly, sulfur speciation can be investigated with
X-ray absorption near edge structure X-ray absorption near edge structure (XANES), also known as near edge X-ray absorption fine structure (NEXAFS), is a type of absorption spectroscopy that indicates the features in the X-ray absorption spectra ( XAS) of condensed matter due to the ...
(XANES) spectroscopy, which is sensitive to sulfur-containing functional groups such as sulfides,
thiophene Thiophene is a heterocyclic compound with the formula C4H4S. Consisting of a planar five-membered ring, it is aromatic as indicated by its extensive substitution reactions. It is a colorless liquid with a benzene-like odor. In most of its react ...
s, and
sulfoxide In organic chemistry, a sulfoxide, also called a sulphoxide, is an organosulfur compound containing a sulfinyl () functional group attached to two carbon atoms. It is a polar functional group. Sulfoxides are oxidized derivatives of sulfides. E ...
s. Sulfur content in kerogen generally decreases with thermal maturity, and sulfur speciation includes a mix of sulfides and thiophenes at low thermal maturities and is further enriched in thiophenes at high maturities. Overall, changes in kerogen composition with respect to heteroatom chemistry occur predominantly at low thermal maturities (bitumen and oil windows), while changes with respect to carbon chemistry occur predominantly at high thermal maturities (oil and gas windows).


Microstructure

The microstructure of kerogen also evolves during thermal maturation, as has been inferred by scanning electron microscopy (SEM) imaging showing the presence of abundant internal pore networks within the lattice of thermally mature kerogen. Analysis by gas sorption demonstrated that the internal specific surface area of kerogen increases by an order of magnitude (~ 40 to 400 m2/g) during thermal maturation. X-ray and neutron diffraction studies have examined the spacing between carbon atoms in kerogen, revealing during thermal maturation a shortening of carbon-carbon distances in covalently bonded carbons (related to the transition from primarily aliphatic to primarily aromatic bonding) but a lengthening of carbon-carbon distances in carbons at greater bond separations (related to the formation of kerogen-hosted porosity). This evolution is attributed to the formation of kerogen-hosted pores left behind as segments of the kerogen molecule are cracked off during thermal maturation.


Physical properties

These changes in composition and microstructure result in changes in the properties of kerogen. For example, the skeletal density of kerogen increases from approximately 1.1 g/ml at low thermal maturity to 1.7 g/ml at high thermal maturity. This evolution is consistent with the change in carbon speciation from predominantly aliphatic (similar to wax, density < 1 g/ml) to predominantly aromatic (similar to graphite, density > 2 g/ml) with increasing thermal maturity.


Spatial heterogeneity

Additional studies have explored the spatial heterogeneity of kerogen at small length scales. Individual particles of kerogen arising from different inputs are identified and assigned as different macerals. This variation in starting material may lead to variations in composition between different kerogen particles, leading to spatial heterogeneity in kerogen composition at the micron length scale. Heterogeneity between kerogen particles may also arise from local variations in catalysis of pyrolysis reactions due to the nature of the minerals surrounding different particles. Measurements performed with atomic force microscopy coupled to infrared spectroscopy (AFM-IR) and correlated with organic petrography have analyzed the evolution of the chemical composition and mechanical properties of individual macerals of kerogen with thermal maturation at the nanoscale. These results indicate that all macerals decrease in oxygen content and increase in aromaticity (decrease in aliphalicity) during thermal maturation, but some macerals undergo large changes while other macerals undergo relatively small changes. In addition, macerals that are richer in aromatic carbon are mechanically stiffer than macerals that are richer in aliphatic carbon, as expected because highly aromatic forms of carbon (such as graphite) are stiffer than highly aliphatic forms of carbon (such as wax).


Types

''
Labile Lability refers to something that is constantly undergoing change or is likely to undergo change. Biochemistry In reference to biochemistry, this is an important concept as far as kinetics is concerned in metalloproteins. This can allow for th ...
'' kerogen breaks down to generate principally liquid
hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...
s (i.e.,
oil An oil is any nonpolar chemical substance that is composed primarily of hydrocarbons and is hydrophobic (does not mix with water) & lipophilic (mixes with other oils). Oils are usually flammable and surface active. Most oils are unsaturated ...
), ''
refractory In materials science, a refractory material or refractory is a material that is resistant to decomposition by heat, pressure, or chemical attack, and retains strength and form at high temperatures. Refractories are polycrystalline, polyphase, ...
'' kerogen breaks down to generate principally gaseous hydrocarbons, and '' inert'' kerogen generates no hydrocarbons but forms
graphite Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on large ...
. In organic petrography, the different components of kerogen can be identified by microscopic inspection and are classified as macerals. This classification was developed originally for
coal Coal is a combustible black or brownish-black sedimentary rock, formed as rock strata called coal seams. Coal is mostly carbon with variable amounts of other elements, chiefly hydrogen, sulfur, oxygen, and nitrogen. Coal is formed when dea ...
(a sedimentary rock that is rich in organic matter of terrestrial origin) but is now applied to the study of other kerogen-rich sedimentary deposits. The Van Krevelen diagram is one method of classifying kerogen by 'types', where kerogens form distinct groups when the ratios of hydrogen to carbon and oxygen to carbon are compared.


Type I: Algal/Sapropelic

Type I kerogens are characterized by high initial hydrogen-to-carbon (H/C) ratios and low initial oxygen-to-carbon (O/C) ratios. This kerogen is rich in lipid-derived material and is commonly, but not always, from algal organic matter in lacustrine (freshwater) environments. On a mass basis, rocks containing type I kerogen yield the largest quantity of hydrocarbons upon
pyrolysis The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements ''py ...
. Hence, from the theoretical view, shales containing type I kerogen are the most promising deposits in terms of conventional oil retorting. *
Hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
:
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
atomic ratio > 1.25 *
Oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
:carbon atomic ratio < 0.15 * Derived principally from
lacustrine A lake is an area filled with water, localized in a basin, surrounded by land, and distinct from any river or other outlet that serves to feed or drain the lake. Lakes lie on land and are not part of the ocean, although, like the much larger ...
alga Algae (; singular alga ) is an informal term for a large and diverse group of photosynthetic eukaryotic organisms. It is a polyphyletic grouping that includes species from multiple distinct clades. Included organisms range from unicellular mi ...
e, deposited in
anoxic The term anoxia means a total depletion in the level of oxygen, an extreme form of hypoxia or "low oxygen". The terms anoxia and hypoxia are used in various contexts: * Anoxic waters, sea water, fresh water or groundwater that are depleted of diss ...
lake sediments and rarely in marine environments * Composed of
alginite Alginite is a component of some types of kerogen alongside amorphous organic matter. Alginite consists of organic-walled marine microfossils, distinct from inorganic (silica)-walled microfossils that comprise diatomaceous earth. Alginite is a co ...
, amorphous organic matter,
cyanobacteria Cyanobacteria (), also known as Cyanophyta, are a phylum of gram-negative bacteria that obtain energy via photosynthesis. The name ''cyanobacteria'' refers to their color (), which similarly forms the basis of cyanobacteria's common name, blu ...
, freshwater
algae Algae (; singular alga ) is an informal term for a large and diverse group of photosynthetic eukaryotic organisms. It is a polyphyletic grouping that includes species from multiple distinct clades. Included organisms range from unicellular mic ...
, and lesser of land plant
resin In polymer chemistry and materials science, resin is a solid or highly viscous substance of plant or synthetic origin that is typically convertible into polymers. Resins are usually mixtures of organic compounds. This article focuses on natu ...
s * Formed mainly from
protein Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residues. Proteins perform a vast array of functions within organisms, including catalysing metabolic reactions, DNA replication, respo ...
and
lipid Lipids are a broad group of naturally-occurring molecules which includes fats, waxes, sterols, fat-soluble vitamins (such as vitamins A, D, E and K), monoglycerides, diglycerides, phospholipids, and others. The functions of lipids include ...
precursors * Has few
cyclic Cycle, cycles, or cyclic may refer to: Anthropology and social sciences * Cyclic history, a theory of history * Cyclical theory, a theory of American political history associated with Arthur Schlesinger, Sr. * Social cycle, various cycles in s ...
or
aromatic In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...
structures * Shows great tendency to readily produce liquid hydrocarbons (oil) under heating


Type II: Planktonic

Type II kerogens are characterized by intermediate initial H/C ratios and intermediate initial O/C ratios. Type II kerogen is principally derived from marine organic materials, which are deposited in reducing sedimentary environments. The sulfur content of type II kerogen is generally higher than in other kerogen types and sulfur is found in substantial amounts in the associated bitumen. Although pyrolysis of type II kerogen yields less oil than type I, the amount yielded is still sufficient for type II-bearing sedimentary deposits to be petroleum source rocks. * Hydrogen:carbon atomic ratio < 1.25 * Oxygen:carbon atomic ratio 0.03 - 0.18 * Derived principally from marine plankton and algae * Produces a mixture oil and gas under heating


Type II-S: Sulfurous

Similar to type II but with high sulfur content.


Type III: Humic

Type III kerogens are characterized by low initial H/C ratios and high initial O/C ratios. Type III kerogens are derived from terrestrial plant matter, specifically from precursor compounds including
cellulose Cellulose is an organic compound with the formula , a polysaccharide consisting of a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units. Cellulose is an important structural component of the primary cell w ...
, lignin (a non-carbohydrate polymer formed from phenyl-propane units that binds the strings of cellulose together);
terpene Terpenes () are a class of natural products consisting of compounds with the formula (C5H8)n for n > 1. Comprising more than 30,000 compounds, these unsaturated hydrocarbons are produced predominantly by plants, particularly conifers. Terpenes ...
s and
phenol Phenol (also called carbolic acid) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile. The molecule consists of a phenyl group () bonded to a hydroxy group (). Mildly acidic, it req ...
s.
Coal Coal is a combustible black or brownish-black sedimentary rock, formed as rock strata called coal seams. Coal is mostly carbon with variable amounts of other elements, chiefly hydrogen, sulfur, oxygen, and nitrogen. Coal is formed when dea ...
is an organic-rich sedimentary rock that is composed predominantly of this kerogen type. On a mass basis, Type III kerogens generate the lowest oil yield of principal kerogen types. * Hydrogen:carbon atomic ratio < 1 * Oxygen:carbon atomic ratio 0.03 - 0.3 * Has low hydrogen content because of abundant aromatic carbon structures * Derived from terrestrial (land) plants * Tends to produce gas under heating (Recent research has shown that Type III kerogens can actually produce oil under extreme conditions)


Type IV: Inert/Residual

Type IV kerogen comprises mostly inert organic matter in the form of
polycyclic aromatic hydrocarbon A polycyclic aromatic hydrocarbon (PAH) is a class of organic compounds that is composed of multiple aromatic rings. The simplest representative is naphthalene, having two aromatic rings and the three-ring compounds anthracene and phenanthrene. ...
s. They have no potential to produce hydrocarbons. * Hydrogen:carbon atomic ratio < 0.5


Kerogen cycle

The diagram on the right shows the organic
carbon cycle The carbon cycle is the biogeochemical cycle by which carbon is exchanged among the biosphere, pedosphere, geosphere, hydrosphere, and Earth's atmosphere, atmosphere of the Earth. Carbon is the main component of biological compounds as well as ...
with the flow of kerogen (black solid lines) and the flow of biospheric carbon (green solid lines) showing both the fixation of atmospheric CO2 by
terrestrial Terrestrial refers to things related to land or the planet Earth. Terrestrial may also refer to: * Terrestrial animal, an animal that lives on land opposed to living in water, or sometimes an animal that lives on or near the ground, as opposed to ...
and marine primary productivity. The combined flux of reworked kerogen and biospheric carbon into ocean sediments constitutes
total organic carbon Total organic carbon (TOC) is the amount of carbon found in an organic compound and is often used as a non-specific indicator of water quality or cleanliness of pharmaceutical manufacturing equipment. TOC may also refer to the amount of organi ...
burial entering the endogenous kerogen pool.


Extra-terrestrial

Carbonaceous chondrite
meteorite A meteorite is a solid piece of debris from an object, such as a comet, asteroid, or meteoroid, that originates in outer space and survives its passage through the atmosphere to reach the surface of a planet or Natural satellite, moon. When the ...
s contain kerogen-like components. Such material is thought to have formed the
terrestrial planet A terrestrial planet, telluric planet, or rocky planet, is a planet that is composed primarily of silicate rocks or metals. Within the Solar System, the terrestrial planets accepted by the IAU are the inner planets closest to the Sun: Mercury, ...
s. Kerogen materials have been detected also in interstellar clouds and dust around
star A star is an astronomical object comprising a luminous spheroid of plasma (physics), plasma held together by its gravity. The List of nearest stars and brown dwarfs, nearest star to Earth is the Sun. Many other stars are visible to the naked ...
s. The ''Curiosity'' rover has detected organic deposits similar to kerogen in
mudstone Mudstone, a type of mudrock, is a fine-grained sedimentary rock whose original constituents were clays or muds. Mudstone is distinguished from '' shale'' by its lack of fissility (parallel layering).Blatt, H., and R.J. Tracy, 1996, ''Petrology. ...
samples in
Gale Crater Gale is a crater, and probable dry lake, at in the northwestern part of the Aeolis quadrangle on Mars. It is in diameter and estimated to be about 3.5–3.8 billion years old. The crater was named after Walter Frederick Gale, an amateur ast ...
on
Mars Mars is the fourth planet from the Sun and the second-smallest planet in the Solar System, only being larger than Mercury (planet), Mercury. In the English language, Mars is named for the Mars (mythology), Roman god of war. Mars is a terr ...
using a revised drilling technique. The presence of
benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...
and propane also indicates the possible presence of kerogen-like materials, from which hydrocarbons are derived.Archived a
Ghostarchive
and th
Wayback Machine


See also

* * * *


References

Marakushev, S. A., Belonogova O. V. (2021), An inorganic origin of the “oil-source” rocks carbon substance, Georesursy = Georesources, 23, 164–176, https://doi.org/10.18599/grs.2021.3.19


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 {{Molecules detected in outer space Petroleum Oil shale geology Petrology