DEEP-SEATED ABIOGENIC ORIGIN OF PETROLEUM: FROM GEOLOGICAL ASSESSMENT TO PHYSICAL THEORY

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DEEP-SEATED ABIOGENIC ORIGIN OF PETROLEUM:
FROM GEOLOGICAL ASSESSMENT TO PHYSICAL
THEORY
Vladimir G. Kutcherov1 and Vladilen A. Krayushkin2
Received 28 May 2008; revised 15 April 2009; accepted 29 July 2009; published 12 March 2010.
[1]
The theory of the abyssal abiogenic origin of
petroleum recognizes that natural gas and petroleum are
petroleum is a significant part of the modern scientific
primordial materials of deep origin which have migrated
theories dealing with the formation of hydrocarbons. These
into the Earth's crust. Experimental results and geological
theories include the identification of natural hydrocarbon
investigations presented in this article convincingly confirm
systems, the physical processes leading to their terrestrial
the main postulates of the theory and allow us to reexamine
concentration, and the dynamic processes controlling the
the structure, size, and locality distributions of the world's
migration of that material into geological reservoirs of
hydrocarbon reserves.
petroleum. The theory of the abyssal abiogenic origin of
Citation: Kutcherov, V. G., and V. A. Krayushkin (2010), Deep-seated abiogenic origin of petroleum: From geological assessment to
physical theory, Rev. Geophys., 48, RG1001, doi:10.1029/2008RG000270.
1.
INTRODUCTION
[3] For the historical perspective on the debate surround-
ing the theory, we refer the interested reader to Glasby [2006].
[2] The main goal of this article is to summarize the
Our review aims to support the theory of the abyssal abio-
conclusions of modern petroleum science dealing with the
genic petroleum origin. Opposing arguments are presented
generation, structure, size, and location of the world oil and
by Clark [1934] and American Association of Petroleum
gas potential resources and to provide convincing argu-
Geologists [1971].
ments from both laboratory experiments and geological data
supporting the theory of the abyssal abiogenic origin of
2.
PRINCIPLES OF THE THEORY OF ABYSSAL
petroleum. This paper is organized as follows: Section 2
ABIOGENIC ORIGIN OF PETROLEUM AND ITS
describes the principles of the theory of the abyssal abio-
EXPERIMENTAL CONFIRMATION
genic origin of petroleum, including the possibility of
hydrocarbon generation in mantle conditions as confirmed
2.1. Theory
by distribution characteristic of petroleum and by experi-
[4] The theory of the abyssal abiogenic origin of petro-
mental results obtained. Section 3 provides evidence contra-
leum is an extensive body of scientific knowledge which
dicting the lateral migration of oil and gas at their deposit
covers the subjects as follows: (1) chemical genesis of the
formation. Sections 4 - 14 give geological data (structure,
hydrocarbon molecules, (2) physical processes leading to
size, and location of the world's hydrocarbon reserves)
their terrestrial concentration, (3) dynamic processes placing
which cannot be explained by the biotic hypothesis of
hydrocarbons into geological reservoirs of petroleum, and
petroleum origin but can be explained by the theory of
(4) the location and commercial production of petroleum.
the abyssal abiogenic origin of petroleum. In section 15,
The theory of the abyssal abiogenic origin of petroleum
considerations regarding the petroleum potential of the
recognizes that petroleum is a primordial material of deep
Earth's mantle are presented confirming the inexhaustible
(mantle) origin. This theory, which has been developed in
nature of the hydrocarbon resources of our planet.
the last 50 years in Russia and Ukraine, explains that
hydrocarbon compounds generate in the mantle of the Earth
and migrate through the deep faults into the crust of the
1
Earth. There they form oil and gas deposits in any kind of
Division of Heat and Power Technology, Royal Institute of
rock (crystalline basement, volcanic, and volcanogenic
Technology, Stockholm, Sweden.
2Laboratory of Inorganic Petroleum Origin, Institute of Geological
sedimentary rocks) and in any kind of structural position.
Sciences, National Academy of Sciences, Kiev, Ukraine.
Copyright 2010 by the American Geophysical Union.
Reviews of Geophysics, 48, RG1001 / 2010
1 of 30
8755-1209/10/2008RG000270
Paper number 2008RG000270
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Kutcherov and Krayushkin: NONBIOTIC PETROLEUM ORIGIN
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Figure 1.
A scheme of petroleum deposit formation.
Thus, the accumulation of oil and gas is considered as a part
(MgCO3), and calcite (CaCO3) for carbon and (2) water as
of the natural process of the Earth's outgassing, which was,
supercritical fluid and hydroxyl group in some minerals
in turn, responsible for the creation of its hydrosphere,
(biotite and muscovite) for hydrogen. All the above men-
atmosphere, and biosphere (Figure 1) [Kudryavtsev, 1951;
tioned substances are present in the mantle in sufficient
Kropotkin and Shakhvarstova, 1959; Porfir'ev, 1974;
amounts [Murakami et al., 2002; Isshiki et al., 2004],
Krayushkin, 1984, 1989; Chebanenko et al., 2005].
although quantitative estimates of their abundances vary.
[5] Until recently, the obstacle to accepting the theory of
[7] Thermodynamically favorable reaction environment
the abyssal abiogenic origin of petroleum was the lack of
(reducing conditions) could be created by a presence of
reliable and reproducible experimental results confirming
FeO. The presence of FeO in basic and ultrabasic rocks of
the possibility of the synthesis of complex hydrocarbon
upper mantle is documented [Anderson, 1989].
systems under the conditions of the upper mantle of the
[8] Thus, abiogenic synthesis of hydrocarbons can take
Earth. According to this theory the following conditions are
place in the basic and ultrabasic rocks of the upper mantle in
necessary for the synthesis of hydrocarbons: (1) adequately
the presence of FeO and donors/sources of carbon and
high pressure and temperature, (2) donors/sources of carbon
hydrogen. The possible reaction of synthesis in this case
and hydrogen, and (3) a thermodynamically favorable
could be presented as follows: (1) reduced mantle substance +
reaction environment. Theoretical calculations based on
mantle gases ! oxidized mantle substance + hydrocarbons
methods of modern statistical thermodynamics have estab-
or (2) combination of chemical radicals (methylene (CH2)
lished that (1) polymerization of hydrocarbons takes place
and methyl (CH3)). Different combinations of these radicals
in the temperature range 600C - 1500C and at pressures
define all scales of oil and gas hydrocarbons and also cause
ranging from 20 to 70 kbar [Kenney et al., 2002] and
analogous properties and genetic similarity of oils from dif-
(2) these conditions prevail deep in the Earth at depths of
ferent deposits of the world.
70 - 250 km [Carlson et al., 2005] (Figure 2).
[9] In the theory of the abyssal abiogenic origin of
[6] Donors/sources of carbon and hydrogen are the
petroleum the generation of petroleum accumulations/
following: (1) carbon dioxide (CO2), graphite, magnesite
deposits occurs in four steps as follows: (1) hydrocarbon
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diamonds in kimberlite ejecta in the crust of the Earth.)
The high-pressure chamber that was used in the experi-
ments is described by Nikolaev and Shalimov [1990]. Both
stainless steel and platinum reaction cells with a volume of
0.6 cm3 were used. All were constructed to prevent con-
tamination by air and to provide impermeability during and
after each experimental run. The reaction cell with initial
components was placed into the high-pressure chamber
and was brought from 1 bar to 50 kbar gradually, at a rate
of 2 kbar/min, and from room temperature to the elevated
temperatures of investigation at the rate of 100C/min. The
reaction cell and high-pressure chamber were held for at
least an hour at each temperature for which measure-
ments were taken in order to allow the hydrocarbon system
to come to thermodynamic equilibrium. The samples were
thereafter quenched at the rate of 900C/s to 200C and
from 200C to room temperature over several minutes,
while maintaining the high pressure of investigation. The
pressure was then reduced gradually to 1 bar at the rate of
1 kbar/min. For analyses of reaction products the standard
Figure 2.
Thermobaric conditions in a variety of con-
mass spectrometer and chromatograph with a connected
tinental areas [Ionov et al., 1993; Rudnick and Nyblade,
desorber were used. Chromatographic analyses were carried
1999]. The straight line is the diamond-graphite phase
out simultaneously with two detectors and three chromato-
boundary [Kennedy and Kennedy, 1976], and the short-
graph columns at the temperatures of desorption from
dashed and long-dashed lines show the positions of adiabats
150C to 850C.
for potential temperatures of 1350C and 1400C, respec-
[11] Experiments to demonstrate the high-pressure gene-
tively [Rudnick and Nyblade, 1999]. From Carlson et al.
sis of petroleum hydrocarbons have been conducted using
[2005].
99.9% pure, solid iron oxide, FeO, and marble, CaCO3, wet
with double-distilled water. There were no biotic com-
pounds or hydrocarbons admitted to the reaction chamber.
fluids are generated in the upper mantle; (2) where and
At pressure of 50 kbar with a temperature of 1200C, the
when overlying rocks of the Earth's crust break up/fracture,
synthesis is due to the reaction as follows:
petroliferous fluids rise from the mantle through the deep
faults and their feather joints or fissures; (3) the tremendous
nCaCO3 9
n 3FeO 2
n 1H2O ! nCaOH2
pressure injects the petroliferous fluids from the faults and
3
n 1Fe3O4 CnH2n2:
1
feathers into any rock with porous (sedimentary rocks) or
fractured (basement rocks) pore space; and (4) the petrolif-
Most of the experiments were performed with initial
erous fluids flood the reservoir. (For details, see section 3.)
mixtures for which the reagent abundances had been
These favorable conditions for deep hydrocarbon generation
calculated to provide the maximal output of condensed
are not available everywhere in the mantle. This explains
hydrocarbon phases. All experiments were carried out
the nonuniformity of spatial accommodation of hydrocar-
twice and repeated 6 months later to confirm their reliabil-
bon deposits on the Earth.
ity and reproducibility. Results of chromatographic analyses
[Kutcherov et al., 2002] shown in Table 1 indicate that the
2.2. Laboratory Experiments
mixtures of the initial members of alkanes, alkenes, and
[10] Since petroleum is generated at high pressures and
aromatic hydrocarbons throughout have been obtained as a
high temperatures, a special high-pressure apparatus which
result of chemical reactions in the system CaCO3-H2O-FeO
permits investigations at pressures to 50 kbar and tem-
at pressures of 30 - 50 kbar and at temperatures of 900C -
peratures to 1200C has been designed. The challenge
1200C. (Characteristics for gas-liquid inclusions of
was to establish the above mentioned conditions in high-
granitoid rocks from the White Tiger oil field (Vietnam)
pressure equipment that is capable of preventing contami-
[Areshev et al., 1997] presented in Table 1 show that during
nation by air, is fully sealed for several hours at pressures
high-pressure experiments the system spontaneously
of 50 kbar and temperatures of 1200C, and also allows a
evolved hydrocarbon mixtures in distribution characteristic
rapid drop of temperature while maintaining high pressures.
of natural petroleum.)
To be able to examine the spontaneous reaction products the
[12] Part of our experimental results were confirmed by
system must be rapidly quenched to ``freeze in'' its high-
experiments conducted by Scott et al. [2004]. The authors
pressure, high-temperature distribution. (Such a mechanism
have presented in situ observations of hydrocarbon forma-
is analogous to that which occurs during eruptive transport
tion via carbonate reduction at upper mantle pressures and
processes responsible for the stability and occurrence of
temperatures. They have shown that methane was formed
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TABLE 1. Content of Synthesized and Natural Hydrocarbon
conditions does not depend substantially on the form in
Mixture
which carbon participates in a reaction. (2) A cooling rate
during high-pressure experiments influences significantly
Content (m3/Mt)
the content of the products of the reactions.
50 kbar,
30 kbar,
White
[14] In the new series of experiments, carbon, iron, and
Hydrocarbon
1473 K
1153 K
Tiger
distillated water were used as initial substances. Experi-
ments were done using the large-volume multianvil press
Methane (CH4)
57.3
89.6
94.0
Ethane (C2H6)
5.9
2.8
0.57
apparatus BARS [Pal'yanov et al., 1990]. A general view of
Ethylen (C2H4)
5.9
2.5
0.55
the apparatus is shown in Figure 3. Chepurov et al.'s [1999]
Propane (C3H8)
3.6
0.9
1.77
method of high-pressure experiments was similar to the
Propylen (C3H6)
8.7
3.2
0.13
Isobuthane (iso-C4H10)
0.2
0.1
0.9
method which we used for the ring anvil (CONAC)-type
Butane (n-C4H10)
2.1
0.3
0.9
chamber. The cell and reaction chamber were held for
Isopenthane (iso-C5H12)
0.4
0.15
0.4
30 min at pressure of 50 kbar and temperature of 1200C.
Pentane (n-C5H12)
1.2
0.25
0.3
Isohexane (iso-C6H14)
0.12
0.01
0.26
The samples were then cooled at different rates (several
Hexane (n-C6H14)
0.6
0.1
0.27
seconds, 2 h, and 4 h) to room temperature, while main-
Other
13.98
0.09
0
taining the high pressure of investigation. The pressure was
then reduced gradually to 1 bar. The reaction cell was then
from FeO, CaCO
gently placed in the chromatograph for analysis. The
3-calcite, and water at pressures between
50 and 110 kbar and temperatures ranging from 500C to
chromatographic analysis was carried out at temperature
1500C.
of 150C. Besides hydrocarbons, a content of H2O, CO2,
[
and CO was determined. The results of chromatographic
13] In our new experiments the following suggestions
were checked: (1) The hydrocarbon synthesis under mantle
analysis of the products of reactions for three experiments
Figure 3.
General view of BARS apparatus.
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TABLE 2. Results of Gas Chromatograph Analyses at 150C for Two Series of Experiments
Concentration (mg/kg)
Experiment Details
CH4
C2H6/C2H4
C3H8/C3H6
C4H10/C4H8
H2
O2
CO2
Previous experiment, CaCO3 + FeO + H2O,
155
4.9
0
0
0.1
0
0
p = 30 kbar, T = 1500 K, quenching (900C/s)
New experiment 1, C + Fe + H2O, p = 50 kbar,
40
3
0
0
7
0
0
T = 1500 K, quenching (900C/s)
New experiment 2, C + Fe + H2O, p = 50 kbar,
30
5
3
0
60
0
0
T = 1500 K, sample was cooled during 2 h at 50 kbar
New experiment 3, C + Fe + H2O, p = 50 kbar,
640
80
8
4
530
0
0
T = 1500 K, sample was cooled during 4 h at 50 kbar
made at different cooling rates are shown in Table 2. The
tion of oil and gas accumulations formed this way depends
new results presented confirm that hydrocarbon synthesis
on the cooling rate of the fluids during their injection into
does not depend on the type of carbon donor. A drop of the
the rocks of the Earth's crust. When and where the further
cooling rate leads to formation of heavier hydrocarbons and
supply of injected hydrocarbons from the mantle stops, the
increases the amount of saturated hydrocarbons detected in
fluids do not move further into any forms of the Earth's
the reaction products. The experimental results obtained by
crust (anticline, syncline, and horizontal and tilted beds)
independent groups of researchers in the different laborato-
without the restart of the injection of the abyssal petrolif-
ries discussed above confirm one of the main postulates of
erous fluids.
the theory of the abyssal abiogenic origin of petroleum:
[16] The most convincing evidence of the above men-
complex hydrocarbon systems could be spontaneously
tioned mechanism of oil and gas deposit formations is the
generated deeply in the Earth under the upper mantle
existence of such giant gas fields as Deep Basin (Figure 4),
conditions.
Milk River, and San Juan. They are located in Alberta,
Canada, and Colorado, United States. The formation of
these giant gas fields questions the existence of any lateral
3.
FORMATION OF OIL AND GAS FIELDS IN LIGHT
migration of oil and gas during the oil and gas accumulation
OF ABIOGENIC ORIGIN OF PETROLEUM
process. Those giant gas fields occur in synclines where gas
must be generated but not accumulated, according to the
[15] The theory of the abyssal abiogenic origin of petro-
hypothesis of biotic petroleum origin and hydrodynamically
leum denies the lateral migration of oil and gas in their
controlled migration. The giant gas volumes (12.5 A 1012 m3
reservoirs unless a hydrodynamic (hydraulic) fluid move-
in Deep Basin, 935 A 109 m3 in San Juan, and 255 A 109 m3
ment exists. Capillary forces which are related to the pore
in Milk River) are concentrated in the very fine grained,
radius and to the surface tension across the oil-water (or gas-
tight, impermeable argillites, clays, and shales and in tight
water) interface (the process is described by Laplace's
sandstones and siltstones. These rocks are usually accepted
equation) are, generally, 12 - 16 thousand times stronger
as source rocks and caprocks/seal rocks in petroleum
than the buoyancy forces of oil and gas (according to the
geology but by no means are universally recognized reser-
Navier-Stokes equation) in the natural porous, permeable
voir rocks of oil and natural gas. All the gas-saturated tight
media of the subsurface. This was confirmed by the respec-
rocks here are graded updip into coarse-grained, highly
tive modeling experiments [Krayushkin, 1967, 1989]. In
porous, and highly permeable aquifers with no visible
these experiments, natural gas was injected in the bottom
tectonic, lithological, and stratigraphic barriers to prevent
part of water-saturated sands placed in a transparent tank,
updip gas migration. Therefore, the tremendous gas vol-
a model of a gas bed. In all experiments, injected gas
umes of the above mentioned gas fields have tremendous
remained in the bottom part of the tank. Updip gas migra-
buoyancy, but it never overcomes capillary resistance in
tion was never observed. Change of sand porosity in a wide
pores of the water-saturated reservoir rocks.
range did not influence the results of the experiments. This
[17] Existence of the above mentioned giant gas fields
was also supported by the practice of subsurface gas store
indicates the following:
building in the tilted or horizontal water-saturated sands and
[18] 1. The models of lateral migration of oil and gas at
sandstones. Natural gas that was injected in the gas store
their deposit formation are not consistent with the stand-
remained around an injected well. Updip gas migration was
point of the classic physics laws describing the relation
never observed in this case also. According to the theory of
between capillary and buoyancy forces of oil and gas in the
the abyssal abiogenic origin of petroleum, oil and gas fields
natural porous media. A mechanism of the separation of the
are born as follows. Rising from subcrust zones through the
phases and undeniable presence of fluid contacts is caused
deep faults and their feather joints or fissures, the petrolif-
by the capillary phenomena. This is a subject of petroleum
erous fluid of the mantle is injected under high pressure into
engineering, which is why we did not consider this mech-
any rock and distributed there. The hydrocarbon composi-
anism in detail in our paper.
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Figure 4.
Cross section of Alberta showing gas-saturated sands of Deep Basin [from Masters, 1979].
Gas is concentrated in the tight impermeable sand, which is transformed progressively and continuously
updip into the coarse-grained, highly porous, and highly permeable sand saturated by water.
[19] 2. These fields were formed as a result of the migra-
methane have been discovered every 20 - 40 km between
tion of the mantle petroliferous fluid from the depths to the
12N and 37N along the Mid-Atlantic Ridge (MAR) over a
surface of the Earth.
distance of 1200 km. MAR's sites, trans-Atlantic geotraverse
(TAG) (26N), Snake Pit (23N), Logatchev (14450N),
Broken Spur (29N), Rainbow (37170N), and Menez Gwen
4.
NATURAL GAS AND OIL IN THE RECENT
(37500N), are the most interesting.
SEAFLOOR SPREADING CENTERS
[22] 2. At the Rainbow site, where the bottom outcrops
are represented by ultramafic rocks of mantle origin, the
[20] Petroleum of abyssal abiogenic origin and its em-
presence of the following substances was demonstrated (by
placement into the crust of the Earth can occur in the recent
chromatography/mass spectrometry): CH4, C2H6, C3H8,
seafloor spreading centers in the oceans. Igneous rocks
CO, CO2, H2, H2S, and N2 as well as petroleum consisting
occupy 99% of the total length (55,000 km) of them, while
of n-C16 - n-C29 alkanes together with branched alkanes and
the thickness of sedimentary cover over the spreading
diaromatics [Charlou and Donval, 1993; Charlou et al.,
centers does not exceed 450 - 500 m [Rona, 1988]. Addi-
2002]. Contemporary science does not yet know any microbe
tionally, subbottom convectional hydrothermal systems dis-
which really generates n-C11 - n-C22 alkanes, phytan, pri-
charge hot (170C - 430C) water through the sea bottom's
stan, and aromatic hydrocarbons.
black and white ``smokers.'' Up to now, more than 100 hydro-
[23] 3. At the TAG site, there were no bottom sediments,
thermal systems of this kind have been identified and studied
sedimentary rocks [Simoneit, 1988; Thompson et al., 1988],
in scientific expeditions using submarines such as Alvin,
buried organic matter, or any source rocks. The hydrother-
Mir, Nautile, and Nautilus in the Atlantic, Pacific, and Indian
mal fluid is too hot (290C - 321C) for any microbes. There
oceans. Their observations pertaining to the deep abiogenic
are the Beggiatoa mats, but they were only found at some
origin of petroleum are as follows:
distances from smokers.
[21] 1. The bottom smokers of deepwater rift valleys vent
[24] 4. Active submarine hydrothermal systems produce
hot water, methane, some other gases, and petroleum fluids.
the sulfide metal ore deposits along the whole length of the
Active ``plumes'' with heights of 800 - 1000 m venting
East Pacific Rise (EPR). At 13N the axis of EPR is free of
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any sediment, but here aliphatic hydrocarbons are present in
sions of hydrocarbon gas were registered in only one of the
hot hydrothermal fluids of black smokers. In the sulfide
mines mentioned above. The total quantity of methane
metal ores here the methane and alkanes higher than n-C25
produced through the ventilation system of these mines
with prevalence of the odd number of carbon atoms have
exceeds 5 A 108 m3/yr [Hugo, 1963]. In 2004 - 2006 the oil
been identified [Simoneit, 1988].
fields Kingfisher, Mputa, and Waraga were discovered on
[25] 5. Oil accumulations have been studied by the Alvin
the eastern coast of Lake Albert in Uganda (Figure 5).
submarine and by the deep marine drilling in the Gulf of
``In-place'' oil resources of these oil fields are 210 A 106 t
California (the Guaymas Basin) and in the Escanaba Trough
[Patton et al., 1995]. There are only Precambrian crystalline
in the Gorda Ridge [Gieskes et al., 1988; Koski et al., 1988;
rocks and Quaternary clays surrounding Lake Albert.
Kvenvolden and Simoneit, 1987; Lonsdale, 1985; Peter and
5.2. Baltic Region
Scott, 1988; Simoneit, 1988; Simoneit and Lonsdale, 1982;
Thompson et al., 1988] of the Pacific Ocean. These sites are
[30] In the Baltic Shield, 240 km northwest of Stockholm,
covered by sediments. However, petroleum fluids identified
oil was discovered at the depth of 2883 m in the 1 Stenberg
there are of hydrothermal origin according to Simoneit and
well and at the depth of $6800 m in the 1 Gravberg well.
Lonsdale [1982], and no source rocks have yet been
Both of these wells were drilled in the Precambrian granites
identified there.
only [Aldhous, 1991; Brown, 1991]. All Precambrian igne-
[
ous rocks in the Kola segment of the Baltic Shield contain
26] 6. As for other sites around the globe, scientific
investigations with submarines have established that meth-
from 90 to 110 g/t of Vaseline-like bitumen consisting of
ane plumes occur over sea bottom smokers or other hydro-
n-C27-n-C31 alkanes (32% of mass) as well as cyclo-
thermal systems in the Red Sea, near the Galapagos Isles, in
alkanes and arenes [Petersilje et al., 1967]. The 3-SG-Kola
the Mariana and Tonga deepwater trenches, in the Gulf of
ultradeep well penetrating Precambrian rocks discovered the
California, etc. [Baker et al., 1987; Blanc et al., 1990; Craig
same oil-saturated igneous rocks at the depth range of
et al., 1987; Evans et al., 1988; Horibe et al., 1986; Ramboz
7004-8004 m [Oil and Gas Journal, 1991, 1992a; Krayushkin,
et al., 1988]. Nonbiogenic methane (105 - 106 m3/yr)
2000].
released from a submarine rift off Jamaica [Brooks, 1979]
5.3. Canada
has been also known. A recent investigation along the Mid-
[31] The pulse influx of methane along with chloride-
Atlantic Ridge 2300 miles east of Florida confirms that the
saturated solution under the abnormally high pressure
hydrogen-rich fluids venting at the bottom of the Atlantic
(8.1 MPa at the depth of 510 m) was met in the Precambrian
Ocean in the Lost City Hydrothermal Field were produced
shield crystalline rocks during the work to increase the
by an abiotic synthesis of hydrocarbons in the mantle of the
depth of the Underseal Mine. This mine is very rich in
Earth [Proskurowski et al., 2008]. Quantitatively speaking,
native copper which occurs in the voids, interstices, and
the seafloor spreading centers may vent 1.3 A 109 m3 of
fractures of the Precambrian crystalline rocks near Lake
hydrogen and 16 A 107 m3 methane annually [Welhan and
Superior, Ontario, Canada. In the adjacent Central Patricia
Craig, 1979].
Mine, which is also rich in commercial copper ores, the
[27] Data discussed in this section confirm the following:
methane emissions from the Archean crystalline rocks were
(1) source rocks accounting for the volume of the petroleum
very abundant: 135 flashes and explosions of methane were
venting described are not available and (2) the natural gas
registered in both mines during 1940 - 1950 [Tigert, 1951].
and petroleum fluids in the recent seafloor spreading centers
In the White Pine mining district that is situated on the
can be explained as a result of the vertical migration of
Michigan shore of Lake Superior, Precambrian crystalline
mantle fluids.
rocks comprising copper ores in commercial grade and
quantity are impregnated with liquid crude oil. This crude
5.
NATURAL GAS AND PETROLEUM FLUIDS IN
seeps from fractures, fissures, and caverns in the face, top,
THE PRECAMBRIAN CRYSTALLINE SHIELDS
and walls of the copper mine and consists of the full and
typical petroleum spectrum hydrocarbons including the
[28] Additional evidence confirming the abyssal abiogenic
optically active alkanes, porphyrins, phytane, and pristane
petroleum origin is an abundant presence of natural gas and
[Barghoorn et al., 1965; Kelly and Nishioka, 1985].
petroleum fluids in the Precambrian crystalline shields
5.4. Greenland
(African, Baltic, Canadian, Greenlandian, Sino-Korean,
and Ukrainian shields) with no source rocks around as
[32] In western Greenland near Peninsula Nuussuaq the
follows.
Precambrian crystalline rocks of the Greenlandian shield are
dissected with numerous faults and intruded with the
5.1. Africa
Tertiary age plateau basalts. Having a total thickness of
[29] An abundant presence of natural gas in the Precam-
more than 6500 m they overlap regionally in the shield's
brian igneous and crystalline metamorphic rocks of the
rocks. In 1993 one exploration well was drilled to a total
Caapvaal Craton, South Africa, has been observed. In many
depth (TD) of 448 m. This well penetrated to a series of
gold mines of the Witwatersrand mining district, natural gas
porous zones in basalt and indicated the presence of liquid
is abundantly detected to occur in Archean crystalline rocks
petroleum down to the depth of 90 m in basalt. In eastern
filling an ancient graben. Till 1958, more than 190 explo-
Greenland, where the Paleocene plateau basalts overlap the
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Figure 5.
(a) Geological map of the Albert Graben and its commercial petroleum fields. Data are from
Oil and Gas Journal [2006l]. (b) Generalized structural section, Alberta Graben. Data are from Patton et
al. [1995]. Patterns are as follows: 1, gneisses and granite gneisses; 2, crystalline schist; 3, granites;
4, volcanic; 5, sand; 6, fault.
Precambrian crystalline rock mass of the shield, the liquid
talline limestones, dolomites, and marbles. Their total
bitumen was found in 1992 as an active natural seepage of
thickness exceeds 9000 m. The isotopic age of carbonates
heavy viscous oil/bitumen. It seeps from the Tertiary plateau
varies from 800 to 1850 Ma. Here 65 native liquid oil and
basalts exposed near a base of the Paleocene lava pillow. All
solid bitumen shows have been mapped in outcrops of Tilin
the interstices, voids, and vugs of lava and basalt are filled
and Vumishan crystalline carbonates, whereas the Lontang-
fully with bitumen in the area of $1 km along the strike
chou lenticular bituminous basal quartzite (the isotopic age
and of several hundred meters capwise [Schiener and
is 1000 Ma) occurs on the more ancient crystalline rocks of
Leythaeuser, 1978; Requejo et al., 1989; Oil and Gas Journal,
the aulacogen. In this quartzite the concentration of bitumen
1993a].
varies from 8% to 15% of mass. The host rock of the
bituminous quartzite (Zyamalyang Formation) was intruded
5.5. Sino-Korean Region
with the gabbro-diabase sills (the isotopic age is $763 Ma).
[33] In northern China the Yanshan aulacogen is filled
The bitumen of the above mentioned quartzite is considered
predominantly with the Middle and Later Proterozoic crys-
to be a residue or remnant of an ancient oil accumulation
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Kutcherov and Krayushkin: NONBIOTIC PETROLEUM ORIGIN
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which has undergone a thermodestruction during the early
which was reported at the level of 3 g/kg (V. S. Zubkov,
Riphean time [Wang, 1991].
Heavy hydrocarbons in mantlean fluid of the Earth, synop-
sis of thesis prepared by Dr. Ph., A. P. Vinogradov Institute
5.6. Ukraine
of Geochemistry, Russian Academy of Sciences, Irkutsk,
[34] Covered predominantly with the Tertiary and Qua-
2005). C1-C6 alkanes with concentrations from 4.09 to
ternary beds and being exposed in the deep entrenched river
63.35 L/t were found in primary fluid inclusions of albite,
valleys and ravines, the Ukrainian Precambrian shield with
apatite, nepheline, sphene (titanite), aegirine, and eudialite
its surface area of 200,000 km2 is an uplifted geologically
from the olivine-titanium-augite gabbro and urtites in east
complex crystalline basement of the East European Platform.
Siberia [Petersilje et al., 1967]. In the Pamir Mountains
The Archean rock mass of that shield consists of amphib-
bitumen was found in the mantle xenoliths embedded in
olites, apoporphyrites, calciphyres, crystalline schists, dio-
igneous rocks. Here also primary fluid inclusions occur in
rites, ferriferous quartzites, gneisses and graphitic gneisses,
xenoliths of the garnet pyroxenites (the mantle rocks),
granites, marbles, metaconglomerates, metasandstones, and
explosion pipe rocks and dykes of fergusite-porphyres or
quartzites intruded with the Proterozoic igneous rock bodies
tinguaites (derivatives of mantle magma), amphibolites,
such as the Korosten, Korsun-Shevchenko, near - Azov Sea,
granites, hyperbasites, charnockites, basic granulites, and
and Novomirgorod plutons. The Proterozoic crystalline
eclogites (granulite-basite layer). The average petroleum
complex of the shield is distributed broadly and comprises
fluid concentration of the primary fluid inclusions varies
amphibolites, gabbro, gabbro-norites, labradorites, norites,
in the range of 6 - 8 g/t, decreasing regularly in the direction
gneisses and graphitic gneisses, granites, diabases, carbo-
from the Earth's mantle to the granite/gneiss layer. This is
natites, calciphyres, crystalline schists, ferriferous quartz-
evidence of the abyssal nonbiogenic origin of bitumen
ites, felsites, leptites, marbles, metasandstones, tuffs, and
[Mogarovski et al., 1980]. In Ukraine, primary fluid inclu-
alkali ultrabasites. Both the Archean and the Proterozoic
sions of pegmatite quartz comprise n-C1 - n-C4 alkanes in
rocks here do have petroleum fluid indications over large
the Proterozoic age Korosten, Korsun-Shevchenkovo, and
areas. Liquid crude oil was observed in fissures and
Novomirgorod plutons of the Ukrainian shield (Z. I. Kova-
fractures of amphibolites and granite core samples recov-
lishin, Geochemical investigations of the abyssal origin
ered from several boreholes at the depth of 380 - 900 m in
gases on inclusions in minerals, synopsis of thesis prepared
the northeast area of the Ukrainian shield [Porfir'ev et
by Dr. Ph., Institute of Geology and Geochemistry of
al., 1977]. As indicated by gas chromatography of gas
Combustible Minerals, Lvov, Ukraine, 1986).
mixture samples from pulverized Precambrian rocks of the
Ukrainian shield, they contain 0.001 - 0.204 cm3/g of
6.3. Antarctica
methane [Semenenko et al., 1985].
[38] The Shackleton Ridge of eastern Antarctica is rich in
Precambrian supracrustal volcanogenic sedimentary rocks
5.7. Conclusions
and their zonal metamorphic forms (kyanite-sillimanite
[35] Examples discussed in sections 5.1 - 5.6 indicate that
facial series). Primary fluid inclusions of 13 garnet crystals
(1) petroleum shows/deposits have been found in Precam-
samples from parametamorphites of the Shackleton Ridge
brian crystalline shields all over the world, (2) presence of
comprise methane and heavy hydrocarbons [Prasolov et al.,
oil and gas deposits in the Precambrian crystalline shields
1986]. Mantle xenoliths found in the Quaternary lavas of
without sedimentary rocks cannot be explained from the
Mount Erebus Volcano [Sugisaki and Mimura, 1994] (Ross
traditional biotic petroleum origin point of view, and (3) pet-
Island, East Antarctica) are dunites, garzburgites, and
roliferous fluid of the mantle could be the only possible
pyroxenites. Gas content of their primary fluid hydrocarbon
source of petroleum deposits in the Precambrian crystalline
fluid inclusions is 0.2 - 1.0 g/t.
shields.
6.4. Africa
[39] Primary petroleum fluid inclusions (PFI) are fre-
6.
PETROLEUM FLUID INCLUSIONS IN MINERALS
quently reported in the Precambrian shield rocks of south-
OF IGNEOUS AND OTHER CRYSTALLINE ROCKS
west Africa. PFI of quartz contain CH4, C2H6, C3H8, CO,
CO2, H2O, H2, N2, and Vaseline-like heavy crude oil
6.1. Victoria, SE Australia
[Kvenvolden and Roedder, 1971; Walter et al., 1996]. This
[36] The Pleistocene alkali basalts of Victoria (SE Aus-
oil is geochemically prominent because it has an extraordi-
tralia) are found at the southern termination of the Mesozoic-
narily high concentration of isoprenoidic hydrocarbons.
Recent basaltoid belt. They contain mantle xenoliths. These
Primary fluid inclusions of this oil comprise identical
are the spinel lherzolites with numerous primary fluid
quantities of hydrocarbon molecules with their odd and
inclusions which contain up to 6 g/t of aliphatic hydro-
even carbon atom numbers as well as the noncyclic iso-
carbons with measured d13C values of A28.9% [Sugisaki
prenoids, pristane, phytane, and pharnesane.
and Mimura, 1994].
6.5. Brazilian Shield and Baltic Shield
6.2. Russia and Ukraine
[40] Mesozoic age basalts breaking through the Precam-
[37] Lherzolites from the recent Baikal Rift belt are rich
brian crystalline rocks of the Brazilian shield (Santa Cata-
in primary fluid inclusions, the methane concentration of
rina) are unweathered; poor in fractures; and rich in geodes,
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TABLE 3. Results of Investigation of Gas Mixtures From
hydrocarbons in mantle rocks confirms that abiogenic
Native Diamonds, Carbonado, and Kimberlites
abyssal origin of hydrocarbons is a reality. (3) The content
of CO, CH4, and other hydrocarbons in the amphibole-
Region
Gas Mixture Concentration (vol %)
bearing xenoliths indicates that in certain parts of the upper
Africa, diamonds
CH4, C2H4, C3H6, solid hydrocarbons,
mantle, favorable reduction conditions necessary for nona-
C2H5OH, Ar, CO, CO2, H2, O2, H2O,
biotic synthesis of hydrocarbons could take place [Matson
and N2.
and Muenow, 1984].
Congo, Brazil, and Zaire,
5.8 of CH4, 0.4 of C2H4, 2.0 of C3H6,
diamonds
traces of C4H8, C4H10, and solid
hydrocarbons.
Arkansas, United States,
0.9 - 5.8 of CH4, 0.0 - 5.2 of CH3OH,
7.
BITUMEN AND HYDROCARBONS IN NATIVE
diamonds
0.0 - 3.2 of C2H5OH, 1.2 - 9.4
DIAMONDS, CARBONADO, AND KIMBERLITES
of CO, 5.3 - 29.6 of CO2, 1.5 - 38.9
of H2, 2.9 - 76.9 of H2O, 0.0 - 87.1
of N2, and 0.0 - 0.2 of Ar.
[44] A presence of bitumen and hydrocarbons in native
Brazil, carbonado
The homologies of naphthalene (C10H8),
diamonds, carbonado, and kimberlites could be taken into
phenanthrene (C14H10), and pyrene
consideration as evidence confirming the abyssal petroleum
(C16H10). Total concentration varies
from 20 to 38.75 g/t.
origin. Studying the native diamonds, carbonado, and kimber-
East Siberia, Russia,
C6H6, C12H10, C20H12, C16H10, and other
lites under the microscope, many scientists from several
diamonds and kimberlites
polynuclear aromatic hydrocarbons.
countries have found numerous primary fluid inclusions
Total concentration is $0.136 g/t.
which have been opened due to the specific methods. Fluid
contents of primary fluid inclusions have been recovered with-
out any contamination and studied by mass spectrometry/gas
voids, and interstices filled with liquid crude oil [Powers,
chromatography. Results of such investigations carried out on
1932]. Something similar was also found in the Baltic
the samples from Africa, Asia, Europe, and North and South
Shield, Sweden. Although there are no sedimentary rocks
America can be summarized as follows.
in or around the Arendal area, the dolerite (crystallization
[45] The well-known diamond-producing mines such as
temperature is more than 1000C - 1200C) dykes intersect-
the Dan Carl, Finsh, Kimberley, and Roberts Victor mines
ing the Archean gneisses have many interstices and amyg-
are located in the kimberlite pipes of South Africa. There
daloidal voids filled with liquid petroleum of n-C10 - n-C22
the African shield is characterized by the remarkable
alkanes with some admixture of isoprenoid hydrocarbons.
disjunctive dislocations and nonorogenic magmatism which
Evans et al. [1964] have concluded that this petroleum
has produced a great number of the carbonatite and kim-
doubtlessly is of nonbiogenic origin.
berlite intrusions and explosion pipes in the area around
Lake Tanganyika, Lake Malawi, and Lake Victoria between
6.6. United States
70 and 3000 Ma [Irvine, 1989]. These lakes are in the Great
[41] Matson and Muenow [1984] studied the volatiles in
East African Rift Valley. The valley's margins and disjunc-
amphiboles from the mantle xenoliths, Vulcan's Throne,
tive edges consist of the African shield crystalline rocks.
Grand Canyon, Arizona, United States. The amphiboles
Two hundred and fifty-eight samples of diamonds from this
there contain CH4, C2H4, C3H8, and the heavier hydro-
area have been investigated under the microscope [Deines et
carbons. Methane concentrations vary from 200 to 500 g/t.
al., 1989]. The investigation has shown the presence of
The above mentioned hydrocarbons have d13C equal to
primary fluid inclusions in all samples investigated. These
A26.0% 0.5% that is typical for the noncarbonate carbon
samples have been disintegrated into small particles in a
in ultramafic igneous rocks where d13C varies from A22.2%
vacuum of $1.3 A 10A6 Pa and 200C. The gas mixture
to A27.1%. According to experiments, amphibole-bearing
from each sample was received. Mass spectrometric/gas
xenoliths crystallize at the depth of 65 km.
chromatographic studies of the mixtures are shown in
[42] Sugisaki and Mimura [1994] carried out the most
Table 3. The same hydrocarbons and gas mixtures were
extensive study of petroleum presence in pores, vugs, voids,
detected in natural diamonds from Congo, Brazil [Melton
interstices, caverns, fractures, fissures, and primary fluid
and Giardini, 1974], and Zaire [Giardini et al., 1982]
inclusions which occur within basalts, gabbro, granites,
(Table 3).
peridotites, and their mantle xenoliths. A collection of those
[46] The composition of the primary fluid inclusion
rocks consisted of 227 samples from all over the world. All
composition has been studied by mass spectrometry in
samples contain CH4, while ultramafics also contain n-C14-
seven native Arkansas diamonds. The result of the investi-
n-C33 alkanes with total concentrations of 0.1 -2.3 g/t and
gation has confirmed the presence of different kinds of
d13C = A23% to A28.9%.
hydrocarbon in all samples (Table 3) [Melton and Giardini,
1974].
6.7. Conclusions
[47] In a Brazil, carbonado primary fluid inclusions
[43] The examples shown in sections 6.1 - 6.6 show the
comprise a set of heavy hydrocarbons (Table 3). Pyrope
following: (1) The petroleum fluid content of mantle rocks
(Mg3Al2(SiO4)3) and olivine, which were recovered from
including primary inclusions was formed in the conditions
diamond crystals and kimberlites of the Mir, Ruslovoye,
of the mantle of the Earth. (2) The presence of complex
and Udatchnoye Eastern diamond-bearing pipes, east Siberia,
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