Kerogen

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Kerogen can be found in oil shale OIL SHALE. IT IS THE KEROGEN IN THIS ROCK WHICH, WHEN HEATED TO 900 F., YIELDS OIL - NARA - 552543.jpg
Kerogen can be found in oil shale

Kerogen is solid, insoluble organic matter in sedimentary rocks. It consists of a variety of organic materials, including dead plants, algae, and other microorganisms, that have been compressed and heated by geological processes. All the kerogen on earth is estimated to contain 1016 tons of carbon. This makes it the most abundant source of organic compounds on earth, exceeding the total organic content of living matter 10,000-fold. [1]

Contents

The type of kerogen present in a particular rock formation depends on the type of organic material that was originally present. Kerogen can be classified by these origins: lacustrine (e.g., algal), marine (e.g., planktonic), and terrestrial (e.g., pollen and spores). The type of kerogen depends also on the degree of heat and pressure it has been subjected to, and the length of time the geological processes ran. The result is that a complex mixture of organic compounds reside in sedimentary rocks, serving as the precursor for the formation of hydrocarbons such as oil and gas. In short, kerogen amounts to fossilized organic matter that has been buried and subjected to high temperatures and pressures over millions of years, resulting in various chemical reactions and transformations.

Kerogen 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. [2] The name "kerogen" was introduced by the Scottish organic chemist Alexander Crum Brown in 1906, [3] [4] [5] [6] derived from the Greek for "wax birth" (Greek: κηρός "wax" and -gen, γένεση "birth").

The increased production of hydrocarbons from shale 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. [7]

Formation

Kerogen is formed during sedimentary diagenesis from the degradation of living matter. The original organic matter can comprise lacustrine and marine algae and plankton and terrestrial higher-order plants. During diagenesis, large biopolymers from, e.g., proteins, lipids, and carbohydrates in the original organic matter, decompose partially or completely. This breakdown process can be viewed as the reverse of photosynthesis. [8] These resulting units can then polycondense to form geopolymers. The formation of geopolymers 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 acids, and the largest units are the humins. This polymerization usually happens alongside the formation and/or sedimentation of one or more mineral components resulting in a sedimentary rock like oil shale.

When kerogen is contemporaneously deposited with geologic material, subsequent sedimentation and progressive burial or overburden 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, oxygen, nitrogen, sulfur, and their associated functional groups, and subsequent isomerization and aromatization 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 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. [9] [10] Thus, kerogen controls much of the storage and transport of oil and gas in shale. [9]

Another possible method of formation is that vanabin-containing organisms cleave the core out of chlorin-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 , do this during its photoautotrophism mode of metabolism. Over time colonies of light harvesting bacteria solidify, forming kerogen [ citation needed ] .

Composition

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. Treibs&Chlorophyll.png
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.

Kerogen is a complex mixture of organic chemical compounds that make up the most abundant fraction of organic matter in sedimentary rocks. [12] 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 oil shale deposit of western North America contains elements in the proportions carbon 215 : hydrogen 330 : oxygen 12 : nitrogen 5 : sulfur 1. [13]

Kerogen is insoluble in normal organic solvents in part because of the high molecular weight 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, 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 organic-rich mudrocks shale, they form possible source rocks. Shales that are rich in kerogen but have not been heated to required temperature to generate hydrocarbons instead may form oil shale 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, which measures carbon speciation. NMR experiments have found that carbon in kerogen can range from almost entirely aliphatic (sp3 hybridized) to almost entirely aromatic (sp2 hybridized), with kerogens of higher thermal maturity typically having higher abundance of aromatic carbon. [14] Another technique is Raman spectroscopy. Raman scattering 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; [15] 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, [16] [17] [18] [19] [20] [21] 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. [22] [23] 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 quinones, ketones, and esters, 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. [22] Similarly, sulfur speciation can be investigated with X-ray absorption near edge structure (XANES) spectroscopy, which is sensitive to sulfur-containing functional groups such as sulfides, thiophenes, and sulfoxides. 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. [24] [25]

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. [9] [26] 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. [27] [28] 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). [29] 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. [30] [31] [32] 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. [33] 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 kerogen breaks down to generate principally liquid hydrocarbons (i.e., oil), refractory kerogen breaks down to generate principally gaseous hydrocarbons, and inert kerogen generates no hydrocarbons but forms graphite.

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 (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. [34]

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. Hence, from the theoretical view, shales containing type I kerogen are the most promising deposits in terms of conventional oil retorting. [35]

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.

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, lignin (a non-carbohydrate polymer formed from phenyl-propane units that binds the strings of cellulose together); terpenes and phenols. Coal 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.

Type IV: inert/residual

Type IV kerogen comprises mostly inert organic matter in the form of polycyclic aromatic hydrocarbons. They have no potential to produce hydrocarbons. [37]

Kerogen cycle

Kerogen cycle Organic carbon cycle including the flow of kerogen.png
Kerogen cycle

The diagram on the right shows the organic carbon cycle 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 and marine primary productivity. The combined flux of reworked kerogen and biospheric carbon into ocean sediments constitutes total organic carbon burial entering the endogenous kerogen pool. [38] [39]

Extra-terrestrial

Carbonaceous chondrite meteorites contain kerogen-like components. [40] Such material is thought to have formed the terrestrial planets. Kerogenous materials have been detected also in interstellar clouds and dust around stars. [41]

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. [42] [43] [44] [45] [46] [47] [48] [49] [50]

See also

Related Research Articles

<span class="mw-page-title-main">Aliphatic compound</span> Hydrocarbon compounds without aromatic rings

In organic chemistry, hydrocarbons are divided into two classes: aromatic compounds and aliphatic compounds. Aliphatic compounds can be saturated like hexane, or unsaturated, like hexene and hexyne. Open-chain compounds, whether straight or branched, and which contain no rings of any type, are always aliphatic. Cyclic compounds can be aliphatic if they are not aromatic.

<span class="mw-page-title-main">Oil shale</span> Organic-rich fine-grained sedimentary rock containing kerogen

Oil shale is an organic-rich fine-grained sedimentary rock containing kerogen from which liquid hydrocarbons can be produced. In addition to kerogen, general composition of oil shales constitutes inorganic substance and bitumens. Based on their deposition environment, oil shales are classified as marine, lacustrine and terrestrial oil shales. Oil shales differ from oil-bearing shales, shale deposits that contain petroleum that is sometimes produced from drilled wells. Examples of oil-bearing shales are the Bakken Formation, Pierre Shale, Niobrara Formation, and Eagle Ford Formation. Accordingly, shale oil produced from oil shale should not be confused with tight oil, which is also frequently called shale oil.

Petroleum geology is the study of origin, occurrence, movement, accumulation, and exploration of hydrocarbon fuels. It refers to the specific set of geological disciplines that are applied to the search for hydrocarbons.

Catagenesis is a term used in petroleum geology to describe the cracking process which results in the conversion of organic kerogens into hydrocarbons.

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 glass (vitreous). It is derived from the cell-wall material or woody tissue of the plants from which coal was formed. Chemically, it is composed of polymers, cellulose and lignin.

A maceral is a component, organic in origin, of coal or oil shale. The term 'maceral' in reference to coal is analogous to the use of the term 'mineral' in reference to igneous or metamorphic rocks. Examples of macerals are inertinite, vitrinite, and liptinite.

Petroleum geochemistry is the branch of geochemistry which deals with the application of chemical principles in the study of the origin, generation, migration, accumulation, and alteration of petroleum...(John M. Hunt, 1979). Petroleum is generally considered oil and natural gases having various compounds composed of primarily hydrogen and carbon. They are usually generated from the decomposition and/or thermal maturation of organic matter. The organic matter originated from plants and algae. The organic matter is deposited after the death of the plant in sediments, where after considerable time, heat, and pressure the compounds in the plants and algae are altered to oil, gas, and kerogen. Kerogen can be thought of as the remaining solid material of the plant. The sediment - usually clay and/or calcareous (lime) ooze, hardens during this alteration process into rock i.e. shale and/or limestone. The shale or limestone rock containing the organic matter is called the source rock because it is the source, having generated the petroleum.

<span class="mw-page-title-main">Sulfur cycle</span> Biogeochemical cycle of sulfur

The important sulfur cycle is a biogeochemical cycle in which the sulfur moves between rocks, waterways and living systems. It is important in geology as it affects many minerals and in life because sulfur is an essential element (CHNOPS), being a constituent of many proteins and cofactors, and sulfur compounds can be used as oxidants or reductants in microbial respiration. The global sulfur cycle involves the transformations of sulfur species through different oxidation states, which play an important role in both geological and biological processes. Steps of the sulfur cycle are:

<span class="mw-page-title-main">Organic-rich sedimentary rocks</span>

Organic-rich sedimentary rocks are a specific type of sedimentary rock that contains significant amounts (>3%) of organic carbon. The most common types include coal, lignite, oil shale, or black shale. The organic material may be disseminated throughout the rock giving it a uniform dark color, and/or it may be present as discrete occurrences of tar, bitumen, asphalt, petroleum, coal or carbonaceous material. Organic-rich sedimentary rocks may act as source rocks which generate hydrocarbons that accumulate in other sedimentary "reservoir" rocks. Potential source rocks are any type of sedimentary rock that the ability to dispel available carbon from within it. Good reservoir rocks are any sedimentary rock that has high pore-space availability. This allows the hydrocarbons to accumulate within the rock and be stored for long periods of time. Highly permeable reservoir rocks are also of interest to industry professionals, as they allow for the easy extraction of the hydrocarbons within. The hydrocarbon reservoir system is not complete however without a "cap rock". Cap rocks are rock units which have very low porosity and permeability, which trap the hydrocarbons within the units below as they try to migrate upwards.

<span class="mw-page-title-main">Asphaltene</span> Heavy organic molecular substances that are found in crude oil

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γ-Carotene (gamma-carotene) is a carotenoid, and is a biosynthetic intermediate for cyclized carotenoid synthesis in plants. It is formed from cyclization of lycopene by lycopene cyclase epsilon. Along with several other carotenoids, γ-carotene is a vitamer of vitamin A in herbivores and omnivores. Carotenoids with a cyclized, beta-ionone ring can be converted to vitamin A, also known as retinol, by the enzyme beta-carotene 15,15'-dioxygenase; however, the bioconversion of γ-carotene to retinol has not been well-characterized. γ-Carotene has tentatively been identified as a biomarker for green and purple sulfur bacteria in a sample from the 1.640 ± 0.003-Gyr-old Barney Creek Formation in Northern Australia which comprises marine sediments. Tentative discovery of γ-carotene in marine sediments implies a past euxinic environment, where water columns were anoxic and sulfidic. This is significant for reconstructing past oceanic conditions, but so far γ-carotene has only been potentially identified in the one measured sample.

<span class="mw-page-title-main">Oil shale geology</span> Branch of geology

Oil shale geology is a branch of geologic sciences which studies the formation and composition of oil shales–fine-grained sedimentary rocks containing significant amounts of kerogen, and belonging to the group of sapropel fuels. Oil shale formation takes place in a number of depositional settings and has considerable compositional variation. Oil shales can be classified by their composition or by their depositional environment. Much of the organic matter in oil shales is of algal origin, but may also include remains of vascular land plants. Three major type of organic matter (macerals) in oil shale are telalginite, lamalginite, and bituminite. Some oil shale deposits also contain metals which include vanadium, zinc, copper, and uranium.

<span class="mw-page-title-main">Bend Arch–Fort Worth Basin</span> Major petroleum producing region in Texas and Oklahoma

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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 deposited in a variety of environments including deep water marine, lacustrine and deltaic. Oil shale can be regarded as an organic-rich but immature source rock from which little or no oil has been generated and expelled. Subsurface source rock mapping methodologies make it possible to identify likely zones of petroleum occurrence in sedimentary basins as well as shale gas plays.

<span class="mw-page-title-main">Pyrobitumen</span> Type of solid, amorphous organic matter

Pyrobitumen is a type of solid, amorphous organic matter. Pyrobitumen is mostly insoluble in carbon disulfide and other organic solvents as a result of molecular cross-linking, which renders previously soluble organic matter insoluble. Not all solid bitumens are pyrobitumens, in that some solid bitumens are soluble in common organic solvents, including CS
2
, dichloromethane, and benzene-methanol mixtures.

Hydrogen isotope biogeochemistry is the scientific study of biological, geological, and chemical processes in the environment using the distribution and relative abundance of hydrogen isotopes. There are two stable isotopes of hydrogen, protium 1H and deuterium 2H, which vary in relative abundance on the order of hundreds of permil. The ratio between these two species can be considered the hydrogen isotopic fingerprint of a substance. Understanding isotopic fingerprints and the sources of fractionation that lead to variation between them can be applied to address a diverse array of questions ranging from ecology and hydrology to geochemistry and paleoclimate reconstructions. Since specialized techniques are required to measure natural hydrogen isotope abundance ratios, the field of hydrogen isotope biogeochemistry provides uniquely specialized tools to more traditional fields like ecology and geochemistry.

<span class="mw-page-title-main">Bisnorhopane</span> Chemical compound

Bisnorhopanes (BNH) are a group of demethylated hopanes found in oil shales across the globe and can be used for understanding depositional conditions of the source rock. The most common member, 28,30-bisnorhopane, can be found in high concentrations in petroleum source rocks, most notably the Monterey Shale, as well as in oil and tar samples. 28,30-Bisnorhopane was first identified in samples from the Monterey Shale Formation in 1985. It occurs in abundance throughout the formation and appears in stratigraphically analogous locations along the California coast. Since its identification and analysis, 28,30-bisnorhopane has been discovered in oil shales around the globe, including lacustrine and offshore deposits of Brazil, silicified shales of the Eocene in Gabon, the Kimmeridge Clay Formation in the North Sea, and in Western Australian oil shales.

Bituminite is an autochthonous maceral that is a part of the liptinite group in lignite, that occurs in petroleum source rocks originating from organic matter such as algae which has undergone alteration or degradation from natural processes such as burial. It occurs as fine-grained groundmass, laminae or elongated structures that appear as veinlets within horizontal sections of lignite and bituminous coals, and also occurs in sedimentary rocks. Its occurrence in sedimentary rocks is typically found surrounding alginite, and parallel along bedding planes. Bituminite is not considered to be bitumen because its properties are different from most bitumens. It is described to have no definite shape or form when present in bedding and can be identified using different kinds of visible and fluorescent lights. There are three types of bituminite: type I, type II and type III, of which type I is the most common. The presence of bituminite in oil shales, other oil source rocks and some coals plays an important factor when determining potential petroleum-source rocks.

<span class="mw-page-title-main">Greater Green River Basin</span> River basin in southwestern Wyoming, United States

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