- "The claims which have traditionally been put forward
to argue a connection between natural petroleum and biological matter have
been subjected to scientific scrutiny and have been established to be baseless.
The outcome of such scrutiny comes hardly as a surprise, given recognition
of the constraints of thermodynamics upon the genesis of hydrocarbons.
-
- If liquid hydrocarbons might evolve from biological detritus
in the thermodynamic regime of the crust of the Earth, we could all expect
to go to bed at night in our dotage, with white hair (or, at least, whatever
might remain of same), a spreading waistline, and all the undesirable decrepitude
of age, and to awake in the morning, clear eyed, with our hair returned
of the color of our youth, with a slim waistline, a strong, flexible body,
and with our sexual vigor restored. Alas, such is not to be. The merciless
laws of thermodynamics do not accommodate folklore fables. Natural petroleum
has no connection with biological matter."
-
- _____
-
-
- Dismissal of the Claims of a Biological Connection for
Natural Petroleum
-
- (Scientific Paper Published In 'Energia')
-
- J. F. Kenney
- Joint Institute of The Physics of the Earth - Russian
Academy of Sciences
- Gas Resources Corporation, 11811 North Freeway, Houston,
TX 77060, U.S.A.
-
- Ac. Ye. F. Shnyukov
- National Academy of Sciences of Ukraine
- Vladimirskaya Street 56, 252.601 Kiev, Ukraine
-
- V. A. Krayushkin
- Institute of Geological Sciences
- O. Gonchara Street 55-B, 01054 Kiev, Ukraine
-
- I. K. Karpov
- Institute of Geochemistry - Russian Academy of Sciences
- Favorskii Street 1a, 664.033 Irkutsk, RUSSIA
-
- V. G. Kutcherov
- Russian State University of Oil and Gas
- Leninskii Prospect 65, 117.917 Moscow, Russia
-
- I. N. Plotnikova
- National Petroleum Company of Tatarstan (TatNeft S.A.)
- Butlerov Street 45-54, 423.020 Kazan, Tatarstan, RUSSIA
-
-
- 1. Introduction.
-
- With recognition that the laws of thermodynamics prohibit
spontaneous evolution of liquid hydrocarbons in the regime of temperature
and pressure characteristic of the crust of the Earth, one should not expect
there to exist legitimate scientific evidence that might suggest that such
could occur. Indeed, and correctly, there exists no such evidence.
-
- Nonetheless, and surprisingly, there continue
to be often promulgated diverse claims purporting to constitute "evidence"
that natural petroleum somehow evolves (miraculously) from biological matter.
In this short article, such claims are briefly subjected to scientific
scrutiny, demonstrated to be without merit, and dismissed.
-
- The claims which purport to argue for some connection
between natural petroleum and biological matter fall into roughly two classes:
the "look-like/come-from" claims; and the "similar(recondite)-properties/come-from"
claims.
-
- The "look-like/come-from" claims apply
a line of unreason exactly as designated: Such argue that, because certain
molecules found in natural petroleum "look like" certain other
molecules found in biological systems, then the former must "come-from"
the latter. Such notion is, of course, equivalent to asserting that elephant
tusks evolve because those animals must eat piano keys.
-
- In some instances, the "look-like/come-from"
claims assert that certain molecules found in natural petroleum actually
are biological molecules, and evolve only in biological systems. These
molecules have often been given the spurious name "biomarkers."
-
- The scientific correction must be stated unequivocally:
There have never been observed any specifically biological molecules in
natural petroleum, except as contaminants. Petroleum is an excellent solvent
for carbon compounds; and, in the sedimentary strata from which petroleum
is often produced, natural petroleum takes into solution much carbon material,
including biological detritus. However, such contaminants are unrelated
to the petroleum solvent.
-
- The claims about "biomarkers" have
been thoroughly discredited by observations of those molecules in the interiors
of ancient, abiotic meteorites, and also in many cases by laboratory synthesis
under imposed conditions mimicking the natural environment. In the discussion
below, the claims put forth about porphyrin and isoprenoid molecules are
addressed particularly, because many "look-like/come-from" claims
have been put forth for those compounds.
-
- The "similar(recondite)-properties/come-from"
claims involve diverse, odd phenomena with which persons not working directly
in a scientific profession would be unfamiliar. These include the "odd-even
abundance imbalance" claims, the "carbon isotope" claims,
and the "optical-activity" claims. The first, the "odd-even
abundance imbalance" claims, are demonstrated to be utterly unrelated
to any biological property. The second, "carbon isotope" claims,
are shown to depend upon measurement of an obscure property of carbon fluids
which cannot reliably be considered a measure of origin. The third, the
"optical-activity" claims, deserve particular note; for the
observations of optical activity in natural petroleum have been trumpeted
loudly for years as a "proof" of some "biological origin"
of petroleum. Those claims have been thoroughly discredited decades ago
by observation of optical activity in the petroleum material extracted
from the interiors of carbonaceous meteorites.
- More significantly, recent analysis, which has resolved
the previously-outstanding problem of the genesis of optical activity in
abiotic fluids, has established that the phenomenon of optical activity
is an inevitable thermodynamic consequence of the phase stability of multicomponent
fluids at high pressures. Thereby, the observation of optical activity
in natural petroleum is entirely consistent with the results of the thermodynamic
analysis of the stability of the hydrogen-carbon [H-C] system, which establish
that hydrocarbon molecules heavier than methane, and particularly liquid
hydrocarbons, evolve spontaneously only at high pressures, comparable to
those necessary for diamond formation.
-
- There are two subjects which are particularly
relevant for destroying the diverse, spurious claims concerning a putative
connection of petroleum and biological matter: the investigations of the
carbon material from carbonaceous meteorites; and the reaction products
of the Fischer-Tropsch process. Because of their importance, a brief discussion
of both is in order.
-
-
- 1.1 The carbonaceous meteorites.
-
- The carbonaceous meteorites, including particularly
the carbonaceous chondrites, are meteorites whose chemical composition
includes carbon in quantities ranging from a few tenths of a percent to
approximately six percent, by mass.1-5 The age of the carbonaceous meteorites
is typically 3-4.5 billion years; and their origins clearly abiotic.
The mineral structures in these rocks establish that the carbonaceous meteorites
have existed at very low temperatures, much below the freezing point of
water, effectively since the time of their original formation. Such thermal
history of the carbonaceous meteorites eliminates any probability that
there ever existed on them life, or biological matter.6 The evidence obtained
from scientific investigations of the carbon material in carbonaceous meteorites
has destroyed many claims which assert a biological connection between
natural petroleum and biological matter.
-
- Significantly, much of the carbon material of
the carbonaceous meteorites consists of hydrocarbons, as both solids and
in liquid form.1, 5, 7, 8 However, the petroleum material contained in
carbonaceous meteorites cannot be considered to be the origin of the natural
petroleum found in the near-surface crust of the Earth. The heating which
inevitably accompanied the impact process during the accretion of meteorites
into the Earth at the time of its formation would almost certainly have
caused decomposition of most of their contained hydrocarbon molecules.
The carbonaceous meteorites provided the Earth with its carbon (albeit
much of it delivered in the form of hydrocarbons) but not its hydrocarbons
or natural petroleum. (The processes by which hydrocarbons evolve from
the native materials of the Earth are described, and demonstrated, in the
following article.)
-
-
- 1.2 The Fischer-Tropsch process.
-
- The Fischer-Tropsch process is the best-known
industrial technique for the synthesis of hydrocarbons, and has been used
for more than seventy-five years. The Fischer-Tropsch process reacts carbon
monoxide and hydrogen at synthesis conditions of approximately 150 bar
and 700 K, in the presence of ThO2, MgO, Al2O3, MnO, clays, and the catalysts
Ni, Co, and Fe. The reactions are as follow:
-
- When a Ni-Co catalyst is used, the Fischer-Tropsch synthesis
proceeds according to the reaction:
-
- When a Fe catalyst is used, the Fischer-Tropsch synthesis
proceeds according to the reaction:
-
- The yield of the Fischer-Tropsch process is approximately
200 g of hydrocarbons from 1 m3 of CO and H2 mixture. During World War
II, the production of liquid fuels by the Fischer-Tropsch process was used
extensively in Germany; approximately 600,000 t of synthetic gasoline
were synthesized in 1943.
-
- The reaction products of the Fischer-Tropsch
process are only metastable in the thermodynamic conditions of their synthesis;
at pressures of approximately only 150 bar and 700 K, the destruction
of liquid hydrocarbons is inevitable. During the industrial Fischer-Tropsch
process, the reaction products are promptly cooled and moved to conditions
of lower pressure. The natural environment does not mimic the highly-controlled,
and highly-regulated, industrial, Fischer-Tropsch process. The Fischer-Tropsch
process cannot be considered for the generation of natural petroleum.
-
-
- 2. The specious "biomarker" claims: The
irrelevancy of the presence in petroleum of porphyrins, - and similarly
of isoprenoids, pristane, phytane, clorins, terpines, cholestane, etc.
-
- One may read, in almost every textbook published
in the English language purporting to deal with the subject of petroleum
geology, diverse claims made that the presence of certain molecules found
in natural petroleum constitute "evidence," or even "proof,"
that the petroleum evolved from biological matter. Such molecules, claimed
as evidence of a biological connection, include such as porphyrins, isoprenoids,
pristane, phytane, cholestane, terpines, and clorins. Closer investigations
have proven such claims to be groundless. Pristane and phytane are simply
branched alkanes of the isoprenoid class. Cholestane, C27H48, is a true,
highly-reduced hydrocarbon, but is not to be confused with the oxidized,
biotic, molecule cholesterol. Cholestane and cholesterol have similar
geometric structures, and share similar carbon skeletons; there the similarity
ends. Cholestane is a constituent of natural petroleum; cholesterol is
not. Significantly, the Fischer-Tropsch synthesis produces isoprenoids,
including phytane and pristine.
-
- Material of truly biogenic origin, such as fossil spores
or pollen, is indeed often observed in petroleum, - and too often mislabeled
as "biomarkers," supposedly indicating a connection between the
natural petroleum and biological material. Careful investigation has established
that such material has been leached into solution by the crude oil from
buried organic matter in the (typically sedimentary) reservoir rocks from
which the oil has been taken.9, 10
-
- Contrarily, the indisputably biological material, such
as spores and pollen, found in petroleum can be considered as "abiomarkers"
of petroleum origin. For examples, crude oil found in reservoir rocks
of the Permian age always contain not only spores and pollen of the Permian
age but also spores and pollen of older ages, such as, for example, the
Carboniferous, Devonian and Precambrian in petroleum investigated in Tatarstan,
Russia. In the same region and in other portions of the Volga-Urals geological
province, crude oils in the Carbonaceous sediments are characterized with
concentrations of spores of Carbonaceous-through-Precambrian ages, and
crudes in the Devonian sandstones with spores of Devonian-through-Precambrian
ages.9, 11
- The types of porphyrins, isoprenoids, terpines, and
clorins found in natural petroleum have been observed in material extracted
from the interiors of no fewer than fifty-four meteorites, including amphoteric
meteorites (Chainpur, Ngavi, Semarkona), bronze chondrites (Charis, Ghubara,
Kulp, Tieschitz), carbonaceous chondrites of all four petrological classes
(Alais, Bali, Bells, Cold Bockeveld, Eracot, Felix, Groznaia, Haripura,
Ivuna, Kaba, Kainsaz, Karoonda, Lance, Mighei, Mokoia, Murchison, Murrey,
Orgueil, Ornans, Pseudo, Renazzo, Santa Cruz, St.Capraix, Staroye Boriskino,
Tonk, Vigarano, Warrenton), enstatite meteorites (Abee, Hvittis, Indarkh),
hypersthene chondrites (Bishunpur, Bruderheim, Gallingebirge, Holbrook,
Homestead, Krymka), iron meteorites (Arus (Yardymli), Burgavli, Canyon
Diabolo, Odessa, Toluca), aubrite meteorites (Norton County), and ureilite
meteorites (Dyalpur, Goalpara, Novo Urei).9, 12, 13
-
- The observations of such molecules in meteorites
thoroughly discredited the claims that their presence in natural petroleum
might somehow constitute evidence of a biological connection. Because
especially strenuous (and especially erroneous) claims are often made particularly
about the porphyrins observed in natural petroleum, those molecules will
be discussed in modest detail.
-
- Porphyrins comprise a class of molecules designated
cyclic ionopheres, a special class of polydentate ligands for metals.
Porphyrins are heavy, approximately planar, chelating molecules, found
in both biotic and abiotic systems. Several porphyrin molecules are of
special biological significance: vitamin B12; chlorophyll, the porphyrin
which is the agent of the photosynthesis process in plants; and the heme
molecule, the porphyrin component of the protein hemoglobin which is responsible
for the transport of oxygen in mammalian blood. As an example of the high
molecular weight of porphyrins, hemoglobin has the empirical chemical formula,
[C738H1166O208N203S2Fe]4. Neither vitamin B12, nor chlorophyll, nor heme
(nor hemoglobin), nor any biotic porphyrin has ever been observed as a
component of natural petroleum.
-
- The porphyrin molecules found in natural petroleum
possess different side-groups than do those of chlorophyll or heme. The
central chelated metal element in chlorophyll is always magnesium; in heme,
it is iron. In porphyrin molecules found in natural petroleum, the central
chelated metal element is typically vanadium or nickel.
-
- As stated, porphyrin molecules evolve both biologically
and abiologically. During the 1960's and 1970's, porphyrin molecules,
which are the same as those found in terrestrial natural petroleum, were
observed in the hydrocarbon fluids extracted from the interiors of carbonaceous
meteorites.
- The observations of petroleum-type porphyrins
in the hydrocarbon fluids extracted from the interiors of carbonaceous
meteorites destroyed, a fortiori, the claims that such molecules constitute
"evidence" for a connection of petroleum with biological matter.
Additionally, after the observations of porphyrins in carbonaceous meteorites,
those petroleum-type porphyrins were synthesized abiologically in the laboratory
under chemical and thermodynamic conditions specially set to mimic the
abiotic conditions in meteorites.8, 14
-
- The "porphyrin evidence" claims were
destroyed by the investigations of carbonaceous meteorites approximately
thirty years ago, and are well known throughout the community of scientists
working in the field of petroleum. Every compound designated as a "biomarker,"
and not otherwise identified as a contaminant, has been either observed
in the fluids extracted from the interiors of meteorites, or synthesized
in laboratories under conditions comparable to the crust of the Earth,
- or both.
- Such scientific facts, and the general knowledge
of same, not withstanding, every textbook published in the English language
purportedly dealing with the subject of petroleum geology, including the
ones cited above, continues to repeat the old discredited claims that the
presence of (abiotic) porphyrins in natural petroleum provide evidence
for its origin from biological matter.15-17 Such assertions, thirty years
after having been demonstrated scientifically insupportable, must be acknowledged
to be intellectual fraud, pure and simple.
-
-
- 3. The "odd-even" abundance claims, -
involving the small imbalance of the relative abundances of linear hydrocarbon
molecules containing an odd number of carbon atoms, compared to homologous
ones containing an even number.
-
- The claims concerning the imbalance of linear
molecules containing odd and even numbers, respectively, of carbon atoms
is another of the genre of "the constituents of natural petroleum
'have the same properties as' the constituents of biological systems, in
such-or-so a way, and therefore petroleum must have evolved from biological
matter." No intelligent teenage student at, for examples, a Russian,
German, Dutch, or Swiss gymnasium, would accept such reasoning. Nonetheless,
such claims are commonly put forth in English-language textbooks purporting
to deal with petroleum geology. Such claims are herewith shown to be without
merit and insupportable.
-
-
- Fig. 1 Symbolic representation of a molecule of normal
octane, n-C8H18.
- (see http://www.gasresources.net/DisposalBioClaims.htm)
-
- Natural petroleum is a mixture of hydrocarbon
molecules of several classes. The most common class of molecules in petroleum
is that of the normal alkanes, or n-alkanes, which have the chemical formula
CnH2n+2 and a chain-like structure (as noted in the first article). For
example, n-octane, C8H18, has the structure shown schematically in Fig.
1. Correctly, the carbon atoms do not lie exactly along a straight line;
a picture of n-octane which more accurately represents its geometric properties
is shown in Fig. 2, where n-C8H18 is drawn as a "stick-&-ball"
model. Nonetheless, in both figures, the linear chain-like aspect of the
n-alkane molecule is shown clearly.
-
- Similarly as for cyclohexane as described in the first
article, the hydrocarbon n-C8H18 is geometrically related to one or more
biological molecules by substitution of some of the hydrogen atoms by OH
radicals. Specifically, if one of the hydrogen atoms on each carbon atom
in n-C8H18 were replaced by an OH radical, the resulting molecule, n-C8H18O8,
would be a carbohydrate, as shown in Fig. 3, a simple sugar related to
fructose (and whose chemical potential is approximately 2,500 cal lower
than that of n-octane).
-
- Fig. 2 Stick & ball representation of a molecule
of normal octane, n-C8H18.
- (see http://www.gasresources.net/DisposalBioClaims.htm)
-
- In a distribution of linear hydrocarbon molecules
which comprise natural petroleum, the chain-like n-alkanes manifest a slight
imbalance of abundances which favors molecules possessing an odd number
of carbon atoms, as compared to those with an even number. Similarly,
a distribution of linear biological molecules, such as the chain-like carbohydrates,
manifests also a similar slight imbalance of molecules possessing an odd
number of carbon atoms, again as compared to those with an even number.
From this modest, and somewhat arcane, similarity of odd-to-even abundances,
assertions have been made that hydrocarbons evolve from biological matter.
Of course, the second law of thermodynamics prohibits such, which fact
should obviate any such assertion.
-
- Simple investigation of hydrocarbons generated
from abiotic matter manifest also such odd-to-even imbalance of molecular
abundances for the linear molecules. The reaction products of the Fischer-Tropsch
process manifest the same odd-to-even abundance imbalances of linear molecules
as do both natural petroleum, as well as biological molecules.
-
- A specific example of the inevitable genesis
of hydrocarbon molecules which manifest such odd-to-even abundance imbalances
of linear molecules was demonstrated by Zemanian, Streett, and Zollweg
more than fifteen years ago. Zemanian et al. demonstrated the genesis
of heavy and liquid hydrocarbons at high pressures and temperatures from
a mixture of methane and propane. Particularly, Zemanian et al. measured
the relative abundances of the linear chain hydrocarbon molecules. Their
observations, of the imbalance of abundances, and slight excess, of chain
molecules with odd numbers of carbon atoms are quoted here (pp. 63-64):18
- Fig. 3 The simple carbohydrate, n-C8H18O8.
- (see http://www.gasresources.net/DisposalBioClaims.htm)
- "These results are also notable when one
considers the even-to-odd carbon number ratio of petroleum.
- One of the arguments for a biological origin
of petroleum has been that these fluids generally show a small marked prevalence
of odd numbered hydrocarbons. It is also well known that living organisms
produce primarily odd numbered carbon [or carbohydrate] chains. Abiological
processes have been presumed to produce even and odd numbered hydrocarbons
in roughly equal concentrations. The results of this work demonstrate
that presumption to be false. Both biological and abiological hydrocarbon
chemistries favor reactions involving two carbons over single carbon reactions
[leading to preferred reactants of odd-numbered chain molecules]."
-
- It deserves note that the "odd-even abundance-imbalance"
claim, as "evidence"[sic] of a biological origin of hydrocarbon
molecules, was rejected by competent physicists and statistical mechanicians,
almost immediately when it was introduced. The odd-even abundance imbalance
is simply a result of the directional property of the covalent bond together
with the geometry of linear molecules.
-
-
- 4. The phenomenon of optical activity in natural
petroleum: Evidence of an abiotic, high-pressure genesis.
-
- Perhaps for reason of its historical provenance
in fermented wine, the phenomenon of optical activity in fluids was for
some time believed to have some intrinsic connection with biological processes
or materials.20, 21 Such error persisted until the phenomenon of optical
activity was observed in material extracted from the interiors of meteorites;
some of which material had been believed previously to be uniquely of
biotic origin.
-
- From the interiors of carbonaceous meteorites
have been extracted the common amino-acid molecules alanine, aspartic acid,
glutamic acid, glycine, leusine, proline, serine, threonine, as well as
the unusual ones a-aminoisobutyric acid, isovaline, pseudoleucine.22-24
At one time, all had been considered to be solely of biotic origin. The
ages of the carbonaceous meteorites were determined to be 3-4.5 billion
years, and their origins clearly abiotic. Therefore, those amino acids
had to be recognized as compounds of both biological and abiological genesis.
Furthermore, solutions of amino acid molecules from carbonaceous meteorites
were observed to manifest optical activity. Thus was thoroughly discredited
the notion that the phenomenon of optical activity in fluids (particularly
those of carbon compounds) might have any intrinsic connection with biotic
matter. Significantly, the optical activity observed in the amino acids
extracted from carbonaceous meteorites has not the characteristics of such
of common biotic origin, with only one enantiomer present; instead, it
manifests the characteristics observed in natural petroleum, with unbalanced,
so-called scalemic, abundances of chiral molecules.25
-
- The optical activity commonly observed in natural
petroleum has been for years speciously claimed as "proof" of
some connection with biological detritus, - albeit one requiring both a
willing disregard of the considerable differences between the optical activity
observed in natural petroleum and that in materials of truly biotic origin,
such as wine, as well as desuetude of the dictates of the laws of thermodynamics.
-
- Optical activity is observed in minerals such
as quartz or Iceland spar, as well as in oil, and among biological molecules.
The optical activity observed in petroleum is more characteristic of the
same in abiotic minerals, such as naturally occurring quartz, which are
polycrystalline minerals, with a scalemic distribution of domains of left-
and right-rotational properties. The chiral molecules in petroleum manifest
scalemic distributions, and significantly lack the homochiral distribution
which characterize biotic optically active matter. The optical activity
in natural petroleum is characterized by either a right (positive, or dextrorotary)
or left (negative, or levorotary) rotation of the plane of polarization.
By contrast, in biological material left (levorotary) rotation dominates.
-
- The observation of optical activity in hydrocarbon
material extracted from the interiors of carbonaceous meteorites, and typical
of such in natural petroleum, discredited those claims.2, 26 Nonetheless,
the scientific conundrum as to why the hydrocarbons manifest optical activity,
in both carbonaceous meteorites and terrestrial crude oil remained unresolved
until recently.
-
- The chiral molecules in natural petroleum originate
from three distinct sources: contamination by biological detritus in the
near-surface strata from which the oil has been taken; the biological
alteration and degradation of the original oil by microbes which consume
and metabolize oil; and the chiral hydrocarbon molecules which are intrinsic
to the petroleum and generated with it. Only the last concerns the origin
of petroleum.
-
- The genesis of the scalemic distribution of chiral
molecules of natural petroleum has recently been shown to be a direct consequence
of the chiral geometry of the system particles acting according to the
laws of classical thermodynamics. The resolution of the problem of the
origin of the scalemic distributions of chiral molecules in natural petroleum
has been shown to be an inevitable consequence of their high-pressure genesis.19
Thus, the phenomenon of optical activity in natural petroleum, contrary
to supporting any assertion of a biological connection, strongly confirms
the high-pressure genesis of natural petroleum, and thereby the modern
Russian-Ukrainian theory of deep, abiotic petroleum origins.
-
-
- 5. The carbon isotope ratios, and their inadequacy
as indicators of origin.
-
- The claims made concerning the carbon isotope
ratios, and specifically such as purport to identify the origin of the
material, particularly the hydrocarbons, are especially recondite and outside
the experience of most persons not knowledgeable in the physics of hydrogen-carbon
[H-C] systems. Furthermore, the claims concerning the carbon isotope ratios
most often involve methane, the only hydrocarbon which is thermodynamically
stable in the regime of temperatures and pressures of the Earth's crust,
and the only one which spontaneously evolves there.
-
- The carbon nucleus has two stable isotopes,
12C and 13C. The overwhelmingly most abundance stable isotope of carbon
is 12C, which possesses six protons and six neutrons; 13C possesses an
extra neutron. (There is another, unstable isotope, 14C, which possesses
two extra neutrons; 14C results from a high-energy reaction of the nitrogen
nucleus, 14N, with a high-energy cosmic ray particle. The isotope 14C
is not involved in the claims about the isotope ratios of carbon.) The
carbon isotope ratio, designated d13C, is simply the ratio of the abundance
of carbon isotopes 13C/12C, normalized to the standard of the marine carbonate
named Pee Dee Belemnite. The values of the measured d13C ratio is expressed
as a percentage (compared to the standard).
-
- During the 1950's, increasingly numerous measurements
of the carbon isotope ratios of hydrocarbon gases were taken, particularly
of methane; and too often assertions were made that such ratios could unambiguously
determine the origin of the hydrocarbons. The validity of such assertions
were tested, independently by Colombo, Gazzarini, and Gonfiantini in Italy
and by Galimov in Russia. Both sets of workers established that the carbon
isotope ratios cannot be used reliably to determine the origin of the carbon
compound tested.
-
- Colombo, Gazzarini, and Gonfiantini demonstrated
conclusively, by a simple experiment the results of which admitted no ambiguity,
that the carbon isotope ratios of methane change continuously along its
transport path, becoming progressively lighter with distance traveled.
Colombo et al. took a sample of natural gas and passed it through a column
of crushed rock, chosen to resemble as closely as possible the terrestrial
environment.27 Their results were definitive: The greater the distance
of rock through which the sample of methane passes, the lighter becomes
its carbon isotope ratio.
-
- The reason for the result observed by Colombo
et al. is straightforward: there is a slight preference for the heavier
isotope of carbon to react chemically with the rock through which the gas
passes. Therefore, the greater the transit distance through the rock,
the lighter becomes the carbon isotope ratio, as the heavier is preferentially
removed by chemical reaction along the transport path. This result is
not surprising; contrarily, such is entirely consistent with the fundamental
requirements of quantum mechanics and kinetic theory.
-
- Pertinent to the matter of any claim that a
light carbon isotope ratio might be indicative of a biological origin,
the results demonstrated by Colombo et al. establish that such a claim
is insupportable. Methane which might have originated from carbon material
from the remains of a carbonaceous meteorite in the mantle of the Earth,
and possessing initially a heavy carbon isotope ratio, could easily have
that ratio diminished, along the path of its transit into the crust of
the Earth, to a value comparable to common biological material.
-
- Galimov demonstrated that the carbon isotope
ratio of methane can become progressively heavier while at rest in a reservoir
in the crust of the Earth, through the action of methane-consuming microbes.28
The city of Moscow stores methane in water-wet reservoirs on the outskirts
of that city, into which natural gas is injected throughout the year.
During summers, the quantity of methane in the reservoirs increases because
of less use (primarily by heating), and during winters the quantity is
drawn down. By calibrating the reservoir volumes and the distance from
the injection facilities, the residency time of the methane in the reservoir
is determined. Galimov established that the longer the methane remains
in the reservoir, the heavier becomes its carbon isotope ratio.
-
- The reason for the result observed by Galimov
is also straightforward: In the water of the reservoir, there live microbes
of the common, methane-metabolizing type. There is a slight preference
for the lighter isotope of carbon to enter the microbe cell and to be metabolized.
The longer the methane remains in the reservoir, the more of it is consumed
by the methane-metabolizing microbes, with the molecules possessing lighter
isotope being consumed more. Therefore, the longer its residency time
in the reservoir, the heavier becomes the carbon isotope ratio, as the
lighter is preferentially removed by methane-metabolizing microbes. This
result is entirely consistent with the fundamental requirements of kinetic
theory.
-
- Furthermore, the carbon isotope ratios in hydrocarbon
systems are also strongly influenced by the temperature of reaction. For
hydrocarbons produced by the Fischer-Tropsch process, the d13C varies from
-65% at 127 C to -20% at 177 C.29, 30 No material parameter, the measurement
of which varies by almost 70% with a variation of temperature of only approximately
10%, can be used as a reliable determinant of any property of that material.
-
- The d13C carbon isotope ratio cannot be considered
to determine reliably the origin of a sample of methane, - or any other
compound.
-
-
- 6. Conclusion.
-
- The claims which have traditionally been put
forward to argue a connection between natural petroleum and biological
matter have been subjected to scientific scrutiny and have been established
to be baseless. The outcome of such scrutiny comes hardly as a surprise,
given recognition of the constraints of thermodynamics upon the genesis
of hydrocarbons.
-
- If liquid hydrocarbons might evolve from biological
detritus in the thermodynamic regime of the crust of the Earth, we could
all expect to go to bed at night in our dotage, with white hair (or, at
least, whatever might remain of same), a spreading waistline, and all the
undesirable decrepitude of age, and to awake in the morning, clear eyed,
with our hair returned of the color of our youth, with a slim waistline,
a strong, flexible body, and with our sexual vigor restored. Alas, such
is not to be. The merciless laws of thermodynamics do not accommodate
folklore fables. Natural petroleum has no connection with biological matter.
-
- However, recognition of such fact leaves unanswered
the conundrums which eluded the scientific community for more than a century:
How does natural petroleum evolve ? And from where does natural petroleum
come ?
-
- The theoretical resolution of these questions
had to await development of the most modern techniques of quantum statistical
mechanics. The experimental demonstration of the required equipment has
been only recently available. The following article substantially answers
these questions.
-
- 1 M. H. Studier, R. Hayatsu and E. Anders, "Organic
compounds in carbonaceous chondrites", Science, 1965, 149, 1455-1459.
- 2 B. Nagy, Carbonaceous Meteorites, Elsevier,
Amsterdam, 1975.
- 3 G. P. Vdovykin, Carbonaceous Matter of Meteorites
(Organic Compounds, Diamonds, Graphite), Nauka Press, Moscow, 1976.
- 4 B. Mason, "The carbonaceous chondrites",
Space Science Review, 1963, 1, 621-640.
- 5 C. A. Ponnamperuma, "The carbonaceous meteorites",
in Carbonaceous Meteorites, ed. B. Nagy, Elsevier, Amsterdam, 1975, 747.
- 6 J. D. Bernal, "Significance of carbonaceous
meteorites in theories on the origin of life", Nature, 1961, 190,
129-131.
- 7 E. Gelphi and J. Oro, "Organic compounds
in meteorites - IV. Gas chromatographic - mass spectrometric studies of
isoprenoids and other isomeric alkanes in carbonaceous chordrites",
Geochim. Cosmochim. Acta, 1970, 34, 981-994.
- 8 G. W. Hodgson and B. L. Baker, "Evidence
for porphyrins in the Orgueil meteorite", Nature, 1964, 202, 125-131.
- 9 V. A. Krayushkin, The Abiotic, Mantle Origin
of Petroleum, Naukova Dumka, Kiev, 1984.
- 10 V. B. Porfir'yev, "Inorganic origin of petroleum",
American Association of Petroleum Geologists Bulletin, 1974, 58, 3-33.
- 11 P. N. Kropotkin, Y. I. Pikovskii, B. M. Valyaev,
K. B. Serebrovskaya, A. P. Rudenko, A. L. Lapidus, E. B. Chekaliuk and
G. N. Dolenko, Journal of D. I. Mendeleev, All-Union Chem. Soc., Moscow,
1986.
- 12 M. H. Studier, R. Hayatsu and E. Anders, "Origin
of organic matter in the early solar system: I. Hydrocarbons", Geochim.
Cosmochim. Acta, 1968, 32, 151-173.
- 13 G. P. Vdovykin, Meteorites, Nauka, Moscow, 1968.
- 14 G. W. Hodgson and B. L. Baker, "Porphyrin
abiogenesis from pyrole and formaldehyde under simulated geochemical conditions",
Nature, 1967, 216, 29-32.
- 15 F. K. North, Petroleum Geology, Allen & Unwin,
Boston, 1985.
- 16 B. Tissot and D. H. Welte, Petroleum Formation
and Occurrence, Springer, Berlin, 1981.
- 17 R. C. Selley, Elements of Petroleum Geology,
W. H. Freeman, New York, 1995.
- 18 T. S. Zemanian, Chemical Kinetics and Equilibria
of Hydrocarbon Mixtures at Advanced Temperatures and Pressures, Cornell,
Ithaca, 1985.
- 19 J. F. Kenney and U. K. Deiters, "The evolution
of multicomponent systems at high pressures: IV. The genesis of optical
activity in high-density, abiotic fluids", Phys. Chem. Chem. Phys.,
2000, 2, 3163-3174.
- 20 L. Pasteur, "Sur la dissymétrie moleculaire",
C.R. Hebd. Séanc, 1848, 26, 535.
- 21 L. Pasteur, "Sur la dissymétrie moleculaire",
in Leçons de chimie professées en 1860 par M. M. Pasteur,
Cahours, Wurtz, Berthelot, Sante-claire Deville, Barral, et Dumas, Paris
1861, Hachette, Paris, 1886.
- 22 M. H. Engel and B. Nagy, "Distribution and
enantiomeric composition of amino acids in the Murchison meteorite",
Nature, 1982, 296, 837-840.
- 23 M. H. Engel, S. A. Macko and J. A. Silfer, "Carbon
isotope composition of individual amino acids in the Murchison meteorite",
Nature, 1990, 348, 47-49.
- 24 M. H. Engel and S. A. Macko, "Isotopic evidence
for extraterrestrial non-racemic amino acids in the Murchison meteorite",
Nature, 1997, 389, 265-268.
- 25 S. Pizzarello and J. R. Cronin, "Non-racemic
amino acids in the Murray and Murchison meteorites", Geochim. Cosmochim.
Acta, 2000, 64, 329-338.
- 26 B. Nagy, "Optical Activity in the Orgueil
meteorite", Science, 1965, 150, 1846.
- 27 U. Colombo, F. Gazzarini and R. Gonfiantini,
"Die Variationen in der chemischen und isotopen Zusammensetzung von
Erdgas aus Suditalien", Leipzig, 1967, vol. Vortrag ASTI-67.
- 28 E. M. Galimov, Isotope Zusammensetzung des Kohlenstoffe
aus Gassen der Erdrinde, Leipzig, 1967.
- 29 V. A. Krayushkin, "Origins, patterns, dimensions,
and distributions of the world petroleum potential", Georesursy, 2000,
3, 14-18.
- 30 P. Szatmari, "Petroleum formation by Fischer-Tropsch
synthesis in plate tectonics", Bull. A.A.P.G., 1989, 73, 989-996.
-
- Published in Energia, 2001, 22/3, 26-34.
- http://www.gasresources.net/DisposalBioClaims.htm
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