Abiotic Origin of Petroleum - Abiotic Oil

Inorganic Origin of Petroleum

   The theory of Inorganic Origin of Petroleum (synonyms: abiogenic, abiotic, abyssal, endogenous, juvenile, mineral, primordial) states that petroleum and natural gas was formed by non-biological processes deep in the Earth, crust and mantle. This contradicts the traditional view that the oil would be a "fossil fuel" produced by remnants of ancient organisms. Oil is a hydrocarbon mixture in which the primary constituent is mainly methane CH₄ (a molecule composed of one carbon atom bonded to four hydrogen atoms). Occurrence of methane is common in Earth's interior, with the possible formation of hydrocarbons at great depths.

   The beginnings of this theory dates from the 19th Century when the French chemist Marcellin Berthelot and the Russian chemist Dmitri Mendeleev proposed to explain the origin of oil and their theories were revived in the decade after 1950.

   Hydrocarbons such as natural gas and oil are primordial materials i.e., were originally embedded to Earth during process of planetary accretion and have no intrinsic connection with biological material near the surface of the Earth. Several studies based on thermodynamics; experiments of high pressure-temperature; many evidences from geophysical, geochemical and geological data, combined with information from space probes and telescopes in Solar System and Universe have clearly demonstrated the abiotic origin of oil.


   The inorganic theory contrasts with the ideas that posit exhaustion of oil (Peak Oil), which assumes that the oil would be formed from biological processes and thus would occur only in small quantities and sets, tending to exhaust. According to the Abiogenic (Abiotic) Theory, hydrocarbons are very abundant on the planet but the search for discovery of commercial accumulations is not simple because it must pass through understanding of geology of the favorable areas and especially understand the real nature of oil and natural gas.

 

Dmitri Mendeleev (1834-1907)

“The capital fact to note is that petroleum was born in the depths of the Earth, and is only there that we must seek its origin” — Dmitri Mendeleev, 1877.

Marcellin Berthelot (1827-1907)

“Do these fuels result always and necessarily in one way from the decomposition of a pre-existing organic substance? Is it thus with the hydrocarbons so frequently observed in volcanic eruptions and emanations, and to which M. Ch. Sainte-Claire Deville has called attention in recent years? Finally, must one assign a parallel origin to carbonaceous matter and to hydrocarbons contained in certain meteorites, and which appear to have an origin foreign to our planet? These are questions on which the opinion of many distinguished geologists does not as yet appear to be fixed.” — Marcellin Berthelot, 1866

 

Comparison between the theories

Oil formation

  There are two theories about the origin of natural hydrocarbons: the biogenic theory and the abiogenic theory. These theories have been intensely debated since 1860 and less often after the discovery of vast oil reserves. 

  The suggestion that the oil would be formed from organic biological detritus buried was originally proposed in 18th Century by Russian scholar scientist Mikhail Vasilyevich Lomonosov, in 1757.

Biogenic (Orthodox): suggestion that remnants of buried plant and animal life (organic detritus) hundreds of meters deep. Action of pressure and temperature with long time, in geologic scale, would convert the kerogen into hydrocarbons (catagenesis).
   It is noteworthy that when was proposed biogenic theory of oil formation has not yet had scientific advance through reports of space research and technology of telescopes and probes, as is now known the abundance of hydrocarbons (oil and natural gas) on Earth, in the Solar System and universe.

Sir Fred Hoyle (1915-2001)

“The suggestion that petroleum might have arisen from some transformation of squashed fish or biological detritus is surely the silliest notion to have been entertained by substantial numbers of persons over an extended period of time.”   —  Sir Fred Hoyle, 1982

Abiogenic: deep deposits of primordial hydrocarbons trapped during formation of the planet. Hundreds of kilometers deep, hydrocarbon molecules (mostly methane) that migrate from the mantle to the crust carrying complex molecules of hydrocarbons. In this fast migration process, primordial gases such as helium and nitrogen may be present and configure as carrier gases.
   Presence of some biological molecules associated with primordial hydrocarbons  is closely related to contamination by microorganisms (Archaea) that feed on hydrocarbons and die into the oil, leaving their parts as fingerprints inside oil at shallower levels in crust. Almost all the hydrocarbons that chemically form oil are stable at great depths and they are primordial and metastable compounds, therefore, oil deposits represent simple displacement of hydrocarbons (oil and natural gas) from its original environment of formation i.e., from Earth's upper mantle to shallower levels in the crust.
    Variation of the abiogenic theory suggests that part of the oil may be formed by reactions like Fischer-Tropsch Synthesis from serpentinization of peridotite of upper mantle, by chemical hydrolysis reactions, producing hydrogen by reacting with other compounds of carbon (methane), carbon dioxide or carbonates in presence of catalysts transition metals such as Iron, Nickel, Vanadium, produces n-alkanes  hydrocarbons which later migrate to shallower levels, mainly in sedimentary basins by tectonic forces.

Coal formation

Biogenic (Orthodox): Coal is a material derived from organic detritus (plant material) that was buried and compressed.

 

 Coal mining in Indonesia

Abiogenic: Coal (black only) is a material that may contain presence of organic compounds, but that was filled by inorganic hydrocarbons that migrated by continuous upwelling come from great depth and reached these deposits in the surface and preserving fine debris and cellular tissues of plants. Such a situation may occur in the surface migration of methane and oil on areas of marshes or peat.

   Several metals such as Nickel, Vanadium, Chromium, Cadmium, Mercury, Arsenic, Lead, Selenium, among others, are also present in coal. Many coals are sometimes bituminous and have high sulfur content. As with oil, these metals come from deep inside the Earth (mantle) and black coal only represent stages in high loss of hydrogen of primordial hydrocarbons and intense biodegradation at shallower levels as postulated by the American scientist Thomas Gold. It's interesting that the same biomarkers found in oil are present in coal and represent, of course, parts of prokaryotic archaea that re-worked primordial hydrocarbons.

  Association of biocide and poisonous mercury with coal is also common evidence and it's not rare association of uranium with black coal deposits. In many coal deposits in the world are commonly found thin white layers called tonsteins that consisting of kaolin material, sometimes interpreted as volcanic ash.
   There are some occurrences of coal in Precambrian, Neoproterozoic. According to fossil record of planet Earth there's no superior plant  at that time, then the Proterozoic coal is surely abiotic and represents probably  ancient oil accumulation with high hydrogen loss and biodegradation of primordial hydrocarbons.

   Coal sometimes occurs in thick layers, as shown in the pictures below. It would be hard to imagine a swamp or an area with thick ancient forests accumulated and its volume decreased after the water loss and compaction of the layers to form a thick coal layer.

    Only the brown coal (lignite) should be considered dominantly biogenic.

Coal layer over 100 ft - Powder River, Wyoming, USA

Thick coal layer. See car and person as scale

   It is also common occurrence of coal over oil and gas production areas. See below a comparison between maps of oil and coal occurrences in the United States.

Oil and natural gas production areas in the United States

   Main coal basins in the United States

Modern Abiotic Theories about Oil Formation

   Russian geologist Nikolai Alexandrovitch Kudryavtsev was the first proponent of the modern theory of abiotic oil, in 1951. He argued that no petroleum resembling the chemical composition of natural crudes has ever been made from plant material in the laboratory under conditions resembling those in nature. He analyzed the geology of the Athabasca bituminous sands in Alberta, Canada (Athabasca Tar Sands) and concluded that no "source rocks" could form the enormous volume of oil in those tar sands (reserves currently estimated about 1.7 trillion barrels) and the most plausible explanation is that oil is abiotic, abiogenic, inorganic and that comes from deep inside the Earth through deep faults.

  Kudryavtsev's Rule states that "any region in which hydrocarbons are found at one level will be seen to have hydrocarbons in large or small quantities, but at all levels down to and into the basement rock."

  Kudryavtsev worked with such brilliant scientists as Petr N. Kropotkin, Vladimir B. Porfir'ev, Emmanuil B. Chekaliuk, Vladilen A. Krayushkin, Georgi E. Boyko, Georgi I. Voitov, Grygori N. Dolenko, Iona V. Greenberg, Nikolai S. Beskrovny, Victor F. Linetsky and many others.
  He is considered Father of Modern Abiotic Oil Theory.

 Nikolai A. Kudryavtsev (1893-1971)

Vladimir B. Porfir'yev (1899-1982)

“The overwhelming preponderance of geological evidence compels the conclusion that crude oil and natural petroleum gas have no intrinsic connection with biological matter originating near the surface of the Earth. They are primordial materials which have been erupted from great depths.” -- Vladimir B. Porfir'yev, 1956


   The Russian-Ukrainian Abiotic Theory of Petroleum, based on thermodynamic calculations, was initiated in Ukraine  by the scientist Professor Emmanuil B. Chekaliuk (1967), whose studies indicated that the oil comes from and originates at high pressures and temperatures in the Earth's mantle, without the participation of carbon of organic origin (plants or animals). This theory is supported by several studies conducted experimental laboratory in the United States by Dr. J.F. Kenney and other Russian scientists, Kolesnikov A., Kutcherov V.G., Goncharov A.F., Spanu L. and others.

 

Emmanuil B. Chekaliuk (1909-1990)

“Statistical thermodynamic analysis has established clearly that hydrocarbon molecules which comprise petroleum require very high pressures for their spontaneous formation, comparable to the pressures required for the same of diamond. In that sense, hydrocarbon molecules are the high-pressure polymorphs of the reduced carbon system as is diamond of elemental carbon. Any notion which might suggest that hydrocarbon molecules spontaneously evolve in the regimes of temperature and pressure characterized by the near-surface of the Earth, which are the regimes of methane creation and hydrocarbon destruction, does not even deserve consideration.” —  Emmanuil B. Chekaliuk, 1968

   The American scientist, astronomer and astrophysicist Thomas Gold was one of the most prominent proponents of abiogenic theory in the Western. He claims that oil is a primordial material, formed deep inside the Earth and other planets also (especially in the form as methane). The rise of methane, sometimes along with helium and nitrogen, act as carrier gases, bring together heavier hydrocarbons and reach shallower in the crust, where  deep microbial life interact with  the hydrocarbons and contaminates the primordial oil. He proposed The Deep Hot Biosphere theory, based on Deep-Earth Gas Theory according to previous ideas about the origin of oil from studies of eminent Russian-Ukrainian scientists and others and his own experience as an astrophysicist, astronomer, cosmologist to explain and solve the paradox of petroleum and other phenomena connected with the origin and evolution of natural primordial hydrocarbons.

Thomas Gold (1920-2004)

“Hydrocarbons are not biology reworked by geology  (as the traditional view would hold), but rather geology reworked by biology.”  —  (Thomas Gold, 1920 - 2004)

    One of the predictions of abiogenic theories is that other Solar System planets and their satellites (moons) have oceans of hydrocarbons (methane, ethane). These hydrocarbons would be present or during the formation of the solar system or were products of subsequent chemical reactions. The hydrocarbons are present in the nebulae, commonly as complex Polycyclic Aromatic Hydrocarbons (PAH's).

Hydrocarbons are very common in the Solar System and universe

 

 Image of Orion Nebula images from the Hubble Space Telescope (HST) and Spitzer Space Telescope (SST). The colors in yellow due to Polycyclic Aromatic Hydrocarbons (PAH's) that are common in nebulae, comets. These aromatic compounds are also part of the oil.

   The American Association of Petroleum Geologists (AAPG) has conducted conferences on issues about the origin of oil (biogenic/Abiogenic) and involvement in exploration and oil production.

 

Evidences that support Abiotic Theory of oil formation

 

Supergiant oil and gas fields                                                                      

  Russian geologist Nikolai Alexandrovitch Kudryavtsev was a prominent advocate of the Abiogenic Theory. He presented many examples of that, substantial and sometimes commercial quantities of hydrocarbons were found in the basement crystalline rocks or in sediments directly to them overlapping.

   He cited cases in Kansas and California (United States), in western Venezuela and Morocco. He also indicated that the oil reservoirs in sedimentary strata are often related to significant deep fractures in the basement immediately below these accumulations. This is also evidenced in the supergiant fields such as Ghawar in Saudi Arabia; Athabasca oil sands, in Canada; Orinoco oil sands, in Venezuela; Panhandle-Hugoton gas field, in Texas, Kansas and Oklahoma that also produces helium in commercial quantities; Tengiz in Kazakhstan; Prudhoe Bay oilfield in North Slope, Alaska;  Lula field, in Brazil; White Tiger oilfield, Vietnam and many others as the supergiant South Pars/North Dome field or North Field which is the world's largest natural gas condensate field located in the Persian Gulf, shared between Iran and Qatar.

   In the Last Soldier oil field (Wyoming, USA), Kudryavtsev established that in all horizons of the geological section, sandstones of the Cambrian to Cretaceous cover the basement and have reservoirs of oil. A flow of oil was also obtained in the basement. Gaseous hydrocarbons, he noted, are not rare in igneous and metamorphic rocks of the Canadian Shield. Petroleum in Precambrian gneiss is found on the western shore of Lake Baikal in Russia. He noted that oil is present in large or small quantities, but in all horizons below any petroleum accumulation, apparently totally independent of the variability of the conditions of formation of these horizons. This nomination has become known as "Kudryavtsev's Rule" and many examples of it have been recorded in various parts of the world. He concluded that commercial accumulations of oil are simply found where permeable zones are covered with impermeable ones.

  Kudryavtsev introduced a number of other relevant considerations as arguments. Columns of flames have been seen during the eruptions of some volcanoes, sometimes reaching 500 meters high, as during the eruption of Mount Merapi, in Sumatra in 1932. The eruptions of mud volcanoes have released huge amounts of methane so that even the most prolific gas field overlying has been exhausted long ago. The water from the mud volcanoes of bearing some chemicals such as Iodine (I), bromine (Br) and boron (B) that could not be derived from the sediments and next that exceed the concentrations present in seawater at hundreds of times. Mud volcanoes are often associated with volcanic lava (magma) and when near the latter, the mud volcanoes emit non-combustible gases as carbon dioxide, whereas when farther away emit methane.

Mud volcanoes, Salse di Nirano, north Italy

   He knew the occurrence of oil in basement rocks of the Kola Peninsula (Russia) and oil leaks on the Siljan impact structure, Sweden. He noted, as mentioned above, that the immense quantities of hydrocarbons in the Athabasca Oil Sands (Tar Sands), Canada would have to contain a vast amount of "source rocks" according to the conventional model, when indeed, none was found.

        Maps of the Athabasca Tar Sands oil sands, Alberta, Canada. 

The estimated reserves are 1.7 trillion barrels of oil

Athabasca Tar (oil) Sands mining, Alberta, Canadá

 

Map of supergiant Ghawar Field in Saudi Arabia. This field is 230 km long. 

The estimated reserves are 250 billion barrels

 

Horst basement with deep faults below the Ghawar Field

Seismic section in the southern part of Ghawar field. Note the deep fault in the basement, through which 

hydrocarbons migrate and accumulate in the overlying sedimentary reservoirs

The South Pars/North Dome field is the world's largest natural gas and holds an estimated 

1,800 trillion cubic feet (1,800 Tcf - 51 trillion cubic metres) of in-situ natural gas and some 

50 billion barrels (7.9 billion cubic metres) of natural gas condensates 

and covers an area of 9,700 square kilometres (3,700 sq mi) 

Methane and extraterrestrial hydrocarbons                                                                

   Methane and many other hydrocarbons have been detected in several regions of the solar system. Methane is a common constituent of the cosmos and it was, together other volatiles, incorporated and imprisoned in the Earth during its formation. Alternatively carbon also it could have been enriched the Earth through chondritic meteorites. A special class of meteorites designated carbonaceous chondrites containing about 3% of its weight in carbon, show various complex carbon-based compounds such as porphyrins, amino acids, purine and pyrimidine bases, and carboxylic acids. This implies a strong evidence for presence of hydrocarbons in the deep past times of planetary bodies that have disintegrated. In 2004, the Cassini-Huygens Mission (NASA and ESA) confirmed abundant hydrocarbons (methane and ethane) on Titan, a satellite (moon) of Saturn as previously suggested by astrophysicist Thomas Gold. Titan has hundreds of times more liquid hydrocarbons than all oil and natural gas reserves on Earth according data from Cassini-Huygens Mission.

 

  Radar composition image of the  region around the north pole of Titan.  

Most of sea and methane lakes are in the northern hemisphere 

    Titan, a moon of Saturn. Contains lakes and seas of 

    liquid hydrocarbons,  mainly  methane and ethane 

                                 

Titan's atmosphere is mostly nitrogen (98.4%), with the rest being methane (1.6%), and a trace of hydrogen (0.1%). 

There are also trace amounts of ethane, acetylene, propane, cyanoacetylene, hydrogen cyanide, carbon dioxide, 

carbon monoxide, cyanogen, argon and helium. Energy from the Sun should have converted all traces of methane 

in Titan's atmosphere into more complex hydrocarbons within 50 million years. This indicates that methane must be 

somehow replenished by some source in/on Titan. 

Methane has been detected on:

Jupiter, Mars, Saturn (and its moons Iapetus, Titan, Enceladus), Neptune (Triton), Uranus (Ariel, Miranda, Oberon, Titania, Umbriel), Pluto, Comet Halley, Comet Hyakutake and cosmic dust, Nebulae and Interstellar gas.

Methane in Mars

An interesting approach about possibility of crude oil in Mars can be found at the link below:

Oil in Mars?

Cosmic and Planetary abundance of carbon                                                              

   The element carbon (C) is the fourth in order of cosmological abundance, preceded only by hydrogen (H), helium (He) and oxygen (O). The available carbon in the nebula that gave rise to the solar system was built to Earth in the process of planetesimal accretion. The primary geochemical differentiation made heavier elements stay concentrated in the nucleus. Partial melting processes in the continued evolution of the mantle, crust, hydrosphere and atmosphere. Most of the primordial carbon remained in the Earth's mantle.
   Tectonic processes of high-magnitude enable rise of volatiles from the mantle to shallower crustal levels on Earth. Reactivation of the megastructures in sedimentary basins over its geological history may also promote the upwelling and migration of hydrocarbons.

 

Cosmic abundance of the elements

According to studies performed by Massachusetts Institute of Technology (MIT) to estimate the distribution of carbon on Earth is:

Biosphere, oceans, atmosphere ....... 3.7 x 10e+18 moles

Crust

Organic carbon .............................. 1100 x 10e+18 moles

Carbonates .................................... 5200 x 10e+18 moles

Mantle ....................................... 100000 x 10e+18 moles

Earth's Carbon Budget (MIT)

   Earth's mantle contains according that estimating about 20 times more carbon than in the superficial layers of the planet. This carbon within the mantle is in the oxidized form such as carbon dioxide, carbonates; and not oxidized as diamonds, hydrocarbons (oil and natural gas) and possibly metal carbides.

   There is a serious problem when we use the word "organic carbon" or organic chemistry. Dr. Thomas Gold reminds us that we can read a whole book of organic chemistry without mentioning any organism (biology). A rock that contains carbon does not mean that all or part of this carbon is of biological origin, i.e. carbon of real organic biological origin, fossil. This carbon may have migrated in the form as hydrocarbons and inorganic interacted with the rock at low pressure, including reworking by deep biosphere, by microorganisms that feed on hydrocarbons (archaea) which also leave their fingerprints as (biomarkers). Therefore, also the so-called geochemical analyzes of total organic carbon (TOC) in rocks such as shales, actually, do not refer to the organic carbon content of biological origin (as the traditional view would hold), but the analysis of carbon originating from primordial and allocthonous hydrocarbons that migrated from deep sources and are present in these laminates shales. This then leads to a wrong reasoning for suggesting that hydrocarbons would be formed miraculously inside the so-called "source rocks". Therefore unconventional hydrocarbon accumulations in United States such as shale gas (e.g. in Marcellus, Barnett, Bakken, Eagle Ford, Fayetteville, Woodford, Niobrara and all others) and also oil shale as Green River are simply microporous reservoirs and not source-rocks. Other high-order nonsense is to imagine that heat by intrusions of magmas that form igneous rocks such as diabase sills would form hydrocarbons in contact with carbonaceous shales.

   In the process of migration from greater depths hydrocarbons rise to shallower crustal levels carried by helium (He) and Nitrogen (N₂), through cracks in the basement, where subtle decompression occurs. They can stay in porous rocks, fractures and accumulation occurs also trapped in rocks as laminated shales with high microporosity, since the initial migration stages are mostly gas and high pressure systems aided by presence of helium can fix hydrocarbons within these shales.

    It should be noted that the material of biological origin the Earth's surface has a low rate of preservation, initially due decomposition by microorganisms and mainly by oxidation processes. Also in biological detritus dominate biological molecules and other carbohydrate oxidized and no properly hydrocarbon compounds, such as molecules that are dominated in oil and natural gas. Hydrocarbons present in shales are very rich in hydrogen and incompatible with intrinsic biological derivation.

   Presence of complex molecules with high molecular weight, for instance, asphaltenes and helium gas, sulfur, and metals such as nickel and vanadium are also not linked to biological materials.

Proposed molecular structure of asphaltene (Altamirano et al., 1986)

Asphaltene is a very complex Polycyclic Aromatic Hydrocarbon with high molecular weight

   Many people linked to geosciences claim that oil and or gas would be formed, for instance, in carbonaceous shales, which are argillaceous thin bedded and laminated rocks. However, oil, gas or bitumen that may be associated with a shale can be allochthonous material and therefore not formed in situ. The hydrocarbons that migrate to the laminated rocks also promote conservation of fossils and the high abundance of these latter may be related to local emanation of hydrocarbons that reached earlier fossiliferous layers. If not consider these arguments above leads to confusion and misinterpretation that oil would form from biologic sources and its origin would produce the so-called "fossil fuels" (sic) which is nonsense.
  Unconventional shale gas actually is not originated intrinsically within shales. These carbonaceous shales as for instance those from Appalachian basin are not source of gas, but merely reservoirs of primordial gases which migrated from great depths, by deep faults, reach these shales at basin level and are disseminated in their micropores and microfractures. This area is also stage of high upwelling of hydrocarbons where occur several coal mines, conventional gas and oil fields, within-plate earthquakes, Mississippi Valley-Type deposits associated to hydrothermal dolomite HTD.

Cold planetary formation                                                                                             

   In the late Nineteenth Century it was believed that early Earth was extremely hot, completely melted during its formation. Many planetary scientists now believe that formation of the Earth was relatively cold. Recent studies in older zircons (4.4 billion years) suggest that surface of planet had low temperatures, enough to maintain liquid water. The Moon possibly would have formed shortly after Earth's accretion processes by a giant impact by a Mars-sized body.

Existence of hydrocarbons deposits                                                                           

   The conventional oil reserves would disappear in no more than a million years, based on the rate of escape of hydrocarbons to the surface (seeps, seepage). If there are a limited number of sources of hydrocarbon deposits in the context of geologic time, it would be a surprising and amazing coincidence to know that there still are now. If deposits are feeding on themselves, their present existence becomes less surprising.
   The crucial issue for the concept of the organic model is how it could support any mechanism to supply oil reserves faster than its exhaustion. Geological facts collected from all oil basins testify that, geologically, the fields of oil and gas are formed very quickly, which contradicts the time required for maturation of organic rocks is based concepts as biogenic. This is a crucial observation for this traditional model.
   Some believe that biogenic origin has a difficult mission for the hydrocarbon deposits were not as plentiful as the sources are largely abiogenic. Thinking that mantle volatiles are alleged as rare in the superficial layers of the Earth is interesting to note that solid rock of the lower crust and upper mantle cover vast desert areas (as examples granulitic belts and ophiolite). In addition, outcrops of rocks off the mantle of the ocean floor and throughout the global system of mid-ocean ridges are plentiful on this planet. Also, it is often assumed that earthquakes cause massive discharges of hydrocarbons (e.g. oil seeps''catastrophic''oil slicks in the oceans) due to rupture of impermeable rocks, however, it is considered that the constant fluid seeps always migrate to the surface that day-to-day, called the ''cold'' outgassing such moves as much or even more help in relation to catastrophic events.
   Some think that this argument would be somewhat strange because there is evidence of fossils in tar pits (lakes of bitumen) covering a wide range of periods and therefore many of them are important sources of fossils. This certainly proves the fossil organic matter replenishment through geological time (hundreds of millions of years) with which the biogenic origin alone explains(sic). However, this has nothing in common with the rapid formation of gas and oil fields (around 10 to 40 thousand years), and geologically rapid deterioration.
  Hydrocarbons disappear quickly while there was dissipation, evaporation, and deep oxidation and intense biodegradation. So the clue to solving this problem lies in the global balance of carbon and hydrogen flows and exchange rates. When scientists and researchers give attention to these facts and better understand the Earth system, integrating the knowledge of physics, astrophysics and astronomy will be clear that hydrocarbons (oil and natural gas) are primordial materials, and therefore prior to emergence of life.

Methane on Earth                                                                                                         

   Methane gas (CH₄) is typically found on Earth, if not in natural gas deposits, deposits of methane hydrate under high pressure in the abyssal plains of oceans, often reworked by bacteria levels in most shallow gas hydrates frozen soils under permafrost or from degradation of biogenic materials. Methane is a greenhouse gas that causes greenhouse effect, about 20 times more potent than CO₂ (carbon dioxide).
   It is possible that the major extinctions of life that occurred in Earth's history are due to the increase of methane in the atmosphere through geological processes, such as strong sea level fall or meteorite impacts, which could destabilize gas hydrates in the oceans. It is possible that this situation would have occurred either during the Permo-Triassic crisis, with fragmentation of the supercontinental masses or, for instance, also by meteorite impacts during the transition from the Cretaceous to Paleogene (Old Lower Tertiary).
   Methane reacts with oxygen to produce carbon dioxide when it interacts close to the volcanoes of magma (lava). Methane reacts with water, oxygen and calcium to form carbonate cements and concretions in sedimentary reservoirs of oil.
   Microbial life that live inside the Earth or near the sea- bottom  feed on methane, creating spectacular ecosystems, with bizarre life forms and still little studied, such as chemosynthetic communities that associated deepwater coral mounds.
   Primordial methane interacts with argillaceous rocks rich in organic matter (kerogen) and can produce smaller contributions to formation of hydrocarbon oil, due to production of real biomarker (e.g. hopanes, terpanes which are derived from cell walls of bacteria) and unsaturated (alkenes), but not exactly oil. Methane can also interact with peat swamps forming deposits of coal, bringing great depths metals like mercury (as methyl or dimethyl mercury compounds), arsenic, nickel, vanadium, cadmium, lead, selenium, uranium, among others.

Hopanes are a class of isoprenoids present in small quantities in oil. Its origin is related to traces of cell walls of bacteria (archaea) that feed and die in the midst of abiogenic primordial hydrocarbons. These traces are called biomarkers

   Methane (and the same or carbonates from methane oxidized) can polymerize inside the Earth through reactions catalyzed Fischer-Tropsch type synthesis, forming liquid and gaseous hydrocarbons (oil) by serpentinization of peridotite (dunite) of the mantle produces hydrogen in presence of metal catalysts such as nickel, iron, etc.

   Sudden shifts large amounts of methane in Earth's interior can cause large earthquakes, sometimes accompanied by helium and radon gas, as pointed out by scientist Thomas Gold. The sudden escape of methane to the surface land surface or on the seas can also be a cause of some plane crashes and shipwrecks. Loss of support could occur if the route of vessels or aircraft coincides with a large flux of methane which would result in a decrease in the density of air or water and displacement of oxygen that can cause fail in combustion engines.

   Methane has a wide range of thermodynamic stability. Experiments of high pressure and temperature confirm this statement.

Unusual deposits                                                                                                         

   Hydrocarbon deposits are found in areas condemned by orthodox traditional biogenic theory. Some oil fields are being fed back from deep sources, although this is not a rule for a "biogenic source rock" deep.

  Example noted of oil field that refilling was reported in Eugene Island, Block 330, in the Gulf of Mexico. The Russians also have found refilling at Romashkinokoye supergiant oilfield, like the Americans also saw the same phenomenon in Prudhoe Basin, North Slope, Alaska. This is a common phenomenon in most fields of oil and natural gas. When the critical pressure is exceeded or when an earthquake occur can be replenishment of the reservoirs if which the structural framework allows it.

   In the White Tiger oilfield, Vietnam, and many oilfields in Russia, oil and natural gas are produced from reservoirs in granites or gneisses of the basement, with some wells showing presence of hydrocarbons over a thousand feet below the top of the granitic basement. In the case of Vietnam, there is no "source rock" below and according suggestion of the biogenic view would have to be a migration of tens of kilometers to the oil migrated laterally, when through a logical analysis, becomes easy to conclude according abiogenic view that migration of hydrocarbons is from the deep fault affecting the basement and allow communication with the mantle as all natural hydrocarbon accumulations (oil and natural gas fields).

Model of White Tiger Field, Vietnam. Oil production is done in fractured granitic rock of the basement, 
more than 1000 meters below the top

   The "black shales" of the Archean Pilbara Craton (3.25 Ga), Australia, have fluid inclusion oil and pyrobitumen. There is much evidence of bitumen in very old rocks, mainly associated mineralizations. The primordial hydrocarbons also may lead metal compounds and deposit them by hydrothermal processes.

Microbes deep inside the Earth                                                                                   

   Microbial life has been discovered 4.2 kilometers deep in Alaska and 5.2 kilometers in Sweden. Metanophillic organisms are known a long time and recently found microbial life in Yellowstone Park, USA, and are based on the metabolism of hydrogen. Other bodies deep and warm environments (extremophiles bacteria, archaea) remain to be discovered and those who support extreme environments such as hypersaline lakes. Proponents of  Abiogenic Theory or inorganic origin of oil indicates that the deep biosphere is responsible for biomarkers present in the oil, i.e., these biomarkers are actually organic contaminants of natural hydrocarbons. According to scientist Thomas Gold, the deep biosphere biomass surpasses all mass of surface biosphere and, of course, primordial hydrocarbons are the food of these deep microbes.

                    Microbial life feed by primordial hydrocarbons in depths.  An artistic conception of Deep Hot Biosphere  
(The Deep Hot Biosphere, Thomas Gold, 1999)

Helium                                                                                                                          

   Association of helium in natural gas fields and oil is quite common. While ³He is a primordial gas found in mantle, ⁴He is also generated from the radioactive decay of uranium.

  Helium is commonly associated with very light oils, often accompanied by nitrogen and methane in natural gas deposits. These gases aid in the migration of liquid oil  and other gases from deep levels in mantle to shallower levels in crust.

   No known biological process produces helium, so its close relationship with oil is a strong argument favorable for abiogenic theory. Commercial accumulations of helium are generally rare, however, are always associated with oil and natural gas. In the  Panhandle-Hugoton gas field, in Texas-Kansas-Oklahoma, there is significant production of helium. There are also other helium bearing gas fields such as in Algeria, Russia and Qatar-Iran with important content.

  Retention of helium requires specific conditions, such as, existence of an extremely effective seal rock overlying reservoir, usually salt sequences (also called "evaporites"). The radiogenic helium formed in crustal levels would not itself enough pressure to embed from the rocks beside the reservoirs of methane and light oils. The most logical assumption is therefore that migration comes from its deep (mantle) bringing other complex hydrocarbons. Sometimes helium occurs associated with carbon dioxide gas, both primordial.

Trace element and associated metals                                                                          

   Nickel (Ni), Vanadium (V), Lead (Pb), arsenic (As), cadmium (Cd), Mercury (Hg), Cobalt (Co), Chromium (Cr), and other metals are often found in petroleum, mainly Nickel and Vanadium. Some heavy oils, such as some crude oil from Venezuela, have up to reach 45% of Vanadium (pentoxide) in the ashes, values which are even commercials. These metals and their paragenesis are common in Earth's mantle.

   These trace elements are also called "abiomarkers", or non-biomarkers and  by study of the paragenesis of these metals would be possible to establish signatures for identification of origin of crude oil (petroleum).

   Presence of mercury (Hg) is remarkable in many gas fields and also oil, oil shales, black coal and also peat. Mercury, as already mentioned, can migrate in the form as organometallic compounds such as methyl or dimethyl mercury. It is a highly toxic element, biocide, and has no intrinsic relationship with biological activity. Even mercury present in peat could come from upwelling through deep faults below that bring methane to the near surface levels and not by the anthropic industrial pollution.

   Analysis of 22 trace elements in 77 oils, chemically correlate best with composition of chondritic meteorites, serpentinized peridotite in the mantle and fertile primitive mantle than oceanic crust or continental, and show no correlation with the distributions of the chemicals in seawater (Szatmari et al., 2005). For an interesting and extensive approach about trace metals in petroleum see Mantle-like Trace Element Composition of Petroleum – Contributions from Serpentinizing Peridotites, see Szatmari et al., 2011.

 

Comparison of average trace element of Brazil's 67 oil (ppb) with chondrite, UB-N serpentinized mantle, primitive mantle, spinel peridotite mantle and depleted mantle (ppm). The correlations are better with the serpentinized mantle. Szatmari et al. (2007)

Diamondoids                                                                                                                

   Tiny diamondoids occur in petroleum (oil, gas and condensate). Diamondoids are molecules that have a similar arrangement of the structure of atoms as diamonds, that is the cubic crystalline system, and suspected that its origin is also linked to the same environments of origin of kimberlites and lamproites, which can carry natural diamonds, from the ultra high pressures and temperature in the Earth's mantle, bringing them to the surface. These diamondoids found more abundantly in condensates, which are very light oils. Diamondoids are excellent raw material for nanotechnology, especially higher diamondoids. They are probably the most noble products present in natural hydrocarbons.

Diamondoid tiny crystals have an ubiquitous presence in hydrocarbons, mainly in gas and condensates

 

Hydrogen                                                                                                                      

   Petroleum is composed mainly of alkanes (n-alkanes, paraffins). Sir Robert Robinson, British scientist and Nobel Laureate in Chemistry (1947) studied the makeup of the natural oil in great detail nnand concluded that there was much excess hydrogen and therefore it would be difficult its origin as product of organic detritus from plants or animals. Olefins (alkenes), which are unsaturated hydrocarbons, are what should be expected if the source was organic. He then wrote:

Sir Robert Robinson (1886-1975)

“Actually it cannot be too strongly emphasized that petroleum does not present the composition picture expected from modified biogenic products, and all the arguments from the constituents of ancient oils fit equally well, or better, with the conception of a primordial hydrocarbon mixture to which bio-products have been added.” — Sir Robert Robinson (Nobel Prize in Chemistry, 1947)

Thermodynamics                                                                                                        

   The Second Law of Thermodynamics prohibits the spontaneous formation of hydrocarbons heavier than methane at low pressures. Thermodynamic calculations and various experimental studies performed in Ukraine, Russia and the United States confirmed that n-alkanes (common components in oil) do not evolve spontaneously from methane at pressures typically found in sedimentary basins, so the theory for the origin of abiogenic hydrocarbons suggests deep generation (below 150-200 km, according to studies leading by Dr. J.F. Kenney and Russian colleagues.

Stability of hydrocarbons at temperatures and pressures in the Earth (from Chekaliuk, 1976). Methane (CH4) is the most stable molecule of the hydrocarbons, most of it would survive at all levels down to 300 kilometers, provide the temperature there did not exceed 2000 ^oC. For the other components of natural petroleum-paraffins, aromatics and naphthenes - the percentages in equilibrium are shown, these would be the values most likely to be produced from a mixture of hydrogen and carbon. Methane streaming from great depth could bring up, in solution, significant fractions of these petroleum components.

 
    Molecules of biological origin have low chemical potential and, in accordance with the laws of thermodynamics, could not transform spontaneously into hydrocarbons heavier than methane, which are molecules of high chemical potential. Studies of thermodynamic stabilities and free energies of Hydrogen-Carbon system conducted by Dr. J.F. Kenney clearly demonstrate impossibility of biological organic matter form natural hydrocarbons. Biological molecules in general are oxidized, such as carbohydrates and never could form oil.
   Thinking that, for example, that the jet engines which raise a plane in the air and their strength would be driven by "fossil fuels" is a completely silly notion.
 

“The Hydrogen-Carbon system does not evolve spontaneously at pressures less than 30 Kbar, even in the most favorable environmental conditions. The HC system evolves hydrocarbons under pressures found in Earth's mantle at temperatures consistent with that environment”   —  J. F. Kenney and collaborators, 2002

Biology                                                                                                                         

   Life as we know it is fundamentally based on carbon. The primitive organisms (archaea) derive energy from primordial methane or oil (hydrocarbons) that are deep within the Earth. Many microbes also draw oxygen from reduction of iron oxides and produce magnetite or sulfates forming hydrogen sulfide (H₂S). This deep biosphere as contaminants in oil shares and becomes the so-called biomarkers found in natural petroleum.

   Photosynthesis is a very complicated process that primitive organisms have evolved to assist them in the conquest and survival on the planet surface. This may have occurred when the local source of hydrocarbons may have ceased. The astrophysicist Thomas Gold mentioned, according Deep Hot Biosphere Theory that the primitive kind of bacteria (archaea) invented photosynthesis to conquer the surface to make your own food, i.e. autotrophy.

 Phylogenetic Tree of Life

 

Black smokers on the ocean floor and associated chemosynthetic communities

Serpentinization and chemical synthesis of oil - Fischer-Tropsch Synthesis           

   Another possible formation of inorganic oil is by the Fischer-Tropsch Synthesis. The Fischer-Tropsch catalysis converts carbon monoxide, carbon dioxide and methane in various forms of liquid hydrocarbons. Carbon monoxide and carbon dioxide is generated by the partial oxidation of coal or fuel wood. This process was developed and used extensively in World War II by Germany to produce fuels which had limited access to oil supplies. Is still used today in South Africa by Sasol to produce diesel from coal.

   Serpentinization of ultramafic peridotite reactions involving carbon-rich Fischer-Tropsch and is believed to occur at depth where the mantle peridotite is hydrolyzed becoming serpentinite while there is hydrogen evolution. In presence of transition metal catalysts (Fe, Ni, Co), hydrogen reacts with carbon dioxide from carbonate rocks and result in n-alkane hydrocarbons including linear saturated hydrocarbons, alcohols, aldehydes, ketones, aromatic and cyclic compounds. It is also possible that the methane in the deepest regions of the mantle can be polymerized by the Fischer-Tropsch Synthesis forming n-alkanes and other hydrocarbons.

   Although this type of catalytic reaction can form some hydrocarbons in laboratory and industrial scale with relatively low pressure and temperature, the final products are not exactly natural petroleum. Thus, these reactions, although not all the molecules in the mixture configure feature of natural oil, could contribute to the formation of hydro-polymerization of methane through hydrogen release from serpentinization of upper mantle peridotites, as suggested by Szatmari (1989).

Petroleum synthesis in collision zones. Water and CO₂, expelled from underthrust shelf carbonates, cause serpentinization and carbonatization in basal peridotites of overriding oceanic lithosphere (Ophiolite suite), with attendant hydrogen and hydrocarbon formation. (Szatmari, 1989)

Association of oil with deep structures                                                                      

   Oil and gas fields are mainly found on the deep structures present in the basement, related to lithospheric plate boundaries, structures of meteorite impact (impact craters). This association may be observed according to distribution of oil fields along the arcs, such as Indonesia, Persian Gulf, the Apennines (Italy), Alaska,  Barbados Arch and its continuity to Trinidad and Tobago and Venezuela among others. Divergent margin basins or even aborted rifts, petroleum occurrences are associated with faults of great magnitude that communicate the crust and upper mantle in elevation. Reactivation of important geological structures along the fill of sedimentary basins facilitates migration of hydrocarbons to structural highs where these accumulations can form when they find reservoir rocks and impermeable rocks (seals) above, forming traps.

Why oil is often found in sedimentary basins?                                                          

   Sedimentary basins fill depression areas where there were deeply faulted, associated with plate boundaries (rifts, convergence compression or collision between two continental lithospheric plates).
   The sedimentary strata form excellent reservoirs (pore spaces) and sealing rocks which when combined can form traps for hydrocarbons. These traps are connected with deep sources, related to very deep faults also, having interactions with the upper mantle during the evolution and reactivation of the basin.
   Oil also occurs commercially in basement rocks, although the accumulations are more rare, it because due ignorance of the geology of this kind of terrane, and there is little effort to exploratory drilling and surveys in this context. The success of the discoveries of the oil and natural gas accumulations in sedimentary basins is due to the remarkable development of seismic reflection methods, which allow better identification of structures (traps) and prediction of reservoirs and anomalies.
   Hydrocarbons (oil, gas) migrating through faults from deep to the host sedimentary rocks are mainly in the reservoirs (rock porosity), however it is fairly common interaction between allocthonous hydrocarbon and fine interstratified argillaceous rocks such as shales and/or alternating thin shales and carbonate rocks, leading to erroneous interpretation that these lithotypes are the so-called "source rocks" of oil (sic).

Examples of oil trends in areas of compressional regimes

 

Oilfields in the Middle East. The Arabian Plate has relatively small size and suffered several tectonic events and recurrences - These are the main reasons why the region is plenty of oil. There, oil fields are related to deep structures in which the hydrocarbons migrate to excellent reservoirs in sedimentary basins, from Precambrian to the Cenozoic time, due reactivation of old deep structures

Structure of the Arc of Indonesia. The occurrences of oil and coal are related to seismogenic zones, mud and lava volcanism on the plate boundary. Deep structures promote hydrocarbon upwelling and migration besides decompression and partial melting forming lava volcanoes

 

Structure of the Caribbean Plate. The occurrence of oil in Venezuela and neighbors countries follow the plate boundary, where there are deep faults that allow for the rise of the hydrocarbon to sedimentary basins above

Tectonic sketch of Italy and distribution of oil and gas occurrences. This is a remarkable example to show that hydrocarbons (oil and natural gas) merely follow the deep structures and fit perfectly to the major deep thrust faults present in the structural framework of the Apennines chain, the Bradanic trench and  Calabrian Arc  which permit  migration of hydrocarbons from mantle below to shallower reservoirs above in sedimentary basins, during reactivation of those deep structures.

Conceptual models of extensional regimes which show interaction between mantle and oil trends that follow megastructures

  

Model of ocean opening and extensional basin formation of divergent margins. Reactivation of old rift structures that formed the sedimentary basins will rise hydrocarbon from Earth's mantle to the crust, where rocks of sedimentary basins form the best reservoirs and sealing systems in favorable structural situation for the hydrocarbons accumulations

Model for the Viking Graben in the North Sea. Large hydrocarbon accumulations of this area clearly follow the extensional trend of the rift where there is interaction with deep mantle through deep faults that allow the rise of primordial oil to the sedimentary basins and their consequent accumulation

“Geology is the prisoner of several dogmas that have had widespread influence on the development of scientific thought.” — William R. Corliss, 1975

“It is a singular and notable fact that, while most other branches of science have emancipated themselves from the trammels of metaphysical reasoning, the science of geology still remains imprisoned in ‘a priori’ theories.” — Sir Henry H. Howorth, 1895