Dismissal of the Claims of a Biological Connection for Natural Petroleum
Summary of the Article
By J. F. Kenney
Joint Institute of The Physics of the Earth - Russian Academy of Sciences
By Ac. Ye. F. Shnyukov
National Academy of Sciences of Ukraine
By V. A. Krayushkin
Institute of Geological Sciences
By I. K. Karpov
Institute of Geochemistry - Russian Academy of Sciences
By V. G. Kutcherov
Russian State University of Oil and Gas
By I. N. Plotnikova
National Petroleum Company of Tatarstan (TatNeft S.A.)
Diverse claims purport to constitute "evidence" that natural petroleum evolves from biological matter. In this article, such claims are briefly subjected to scientific scrutiny enabling scientists to dismiss them. The claims fall into two classes: the "look-like/come-from" claims; and the "similar (recondite)-properties/come-from" claims.
The "look-like/come-from" claims argue that certain molecules found in natural petroleum "look like" certain other molecules found in biological systems, then the former must "come-from" the latter, or that certain molecules found in natural petroleum are biological molecules and evolve only in biological systems, being given the spurious name 'biomarkers." This is as though they're saying that elephant tusks evolve because these animals eat piano keys.
Nothing has ever been observed as specifically biological molecules in natural petroleum except 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.
"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 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 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 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 were thoroughly discredited decades ago by observation of optical activity in the petroleum material extracted from the interiors of carbonaceous meteorites. Moreover, and 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.
Two subjects which are particularly relevant for destroying the diverse and 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. They are important.
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 (not from a life form). 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. 
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 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. Hydrocarbons evolve from the native materials of the Earth.
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 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, C 27 H48 , 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.
Editor's note: It wouldn't be "almost every textbook," it would be every textbook. The Rockefeller Foundation would have seen to that since it controls education. The authors also state this fact regarding every textbook below in this article, without, however, stating who is responsible for this fact.
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]
These observations of such molecules in meteorites mentioned above 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 B 12; 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, [C 738 H1166 O208 N203 S2Fe] 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.
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]
No intelligent teenage student at, for example, a Russian, German, Dutch, or Swiss gymnasium (school), would accept the claims concerning the imbalance of linear molecules containing odd and even numbers, respectively, of carbon atoms having the same properties as the constituents of biological systems. Nonetheless, such claims are commonly put forth in English-language textbooks purporting to deal with petroleum geology.
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. The imbalance of abundances and slight excess of chain molecules with odd numbers of carbon atoms are quoted. 
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] ."
The "odd-even abundance-imbalance" claim, as "evidence" of a biological origin of hydrocarbon molecules, was rejected by 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.
There is evidence of an abiotic high-pressure genesis in petroleum. 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 - aminoisobutyric acid, isovaline, pseudoleucine, which had been considered biotic. [22-24] The ages of the carbonaceous meteorites were determined to be 3-4.5 billion years old, 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 do not have 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. 
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 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 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.  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.
The claims which have been forwarded 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.
The merciless laws of thermodynamics do not accommodate folklore fables. Natural petroleum has no connection with biological matter.
Recognition of such fact still leaves unanswered the conundrums which have 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.
Editor's note: The article which is referred to just above, follows next in summary. To read both articles in their entirety, log on to http://www.gasresources.net
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