A group of petrochemical engineers produced propane, butane, hexane, octane and other petroleum hydrocarbons from pure marble and iron oxide and distilled water, under 50kbar of pressure and 1500o C temperature. These conditions correspond to areas deep within the earth’s mantle. Their experiment was the capstone of an article in the Proceedings of the National Academy of Sciences online preprints (Aug 12) about the thermodynamics of oil production, and the constraints on chemical evolution by the second law of thermodynamics. They describe how the only naturally-occurring hydrocarbon at atmospheric pressure is methane, CH4, the simplest; all the other hydrocarbon chains require tremendous pressure and heat, more than can exist in earth’s crust. Accordingly, they dispute that oil can be produced from any biological material: “applying the dictates of thermodynamic-stability theory, disposes of any hypothesis of an origin for hydrocarbon molecules from biological matter, excepting only the lightest, methane.” They dispute that microorganisms or decaying biological material can produce oil, or that its formation depends on the properties of certain geological strata; instead, it must form below the crust, in the mantle, where temperatures and pressures are adequate to overcome the high chemical potentials of complex hydrocarbons. In passing, they note that a few biological compounds have similarly high chemical potentials: “Although there exist biotic molecules of unusually high chemical potential such as beta-carotene (C40H56), vitamin D (C38H44O), and some of the pheromone hormones, such compounds are relatively rare by abundance. They are produced by biological systems only when the producing entity is alive (and at formidable metabolic cost to the producing entity), and the production ceases with the death of the entity.”

If oil is not a “fossil fuel” but is produced in the mantle, perhaps it will not prove to be such a depletable resource. This raises questions about where oil is likely to be found, and how long it takes to form. It should be acknowledged that this paper represents a minority view. Nature Science Update disputes the claim, saying that most geochemists believe the bulk of earth’s oil is of biological origin and that the high temperatures and pressures are not required. We’ll leave those questions to the specialists to debate, but it should be noticed that thermodynamics must be taken into account in questions of chemical evolution. The oxygenated (organic) hydrocarbons in living things do not have such high chemical potentials as octane gasoline, but many still require special conditions for their formation. Notice the unusual nature of beta-carotene and vitamin D which would never form spontaneously by natural processes, but can only be formed by highly-specific enzymes; and when the organism dies, they decay rapidly.

Speaking of methane, the authors throw in a little humor about the “bean-eater’s” reaction: “no biochemical investigation has ever observed a molecule of any hydrocarbon heavier than methane resulting from the decomposition of biological detritus. After a meal of, e.g., Boston baked beans, one does experience biogenic methane, but not biogenic octane.” Scientific papers don’t have to be totally deadpan...

I believe this study will disconfirm several anti-YEC claims.

J. F. Kenney , Vladimir A. Kutcherov ¶, Nikolai A. Bendeliani ||, and Vladimir A. Alekseev ||
Gas Resources Corporation, 11811 North Parkway, Floor 5, Houston, TX 77060; Russian Academy of Sciences, Joint Institute of Earth Physics, Bolshaya Gruzinskaya 10, 123810 Moscow, Russia; ¶Russian State University of Oil and Gas, Leninski Prospect 65, 117917 Moscow, Russia; and ||Russian Academy of Sciences, Institute for High Pressure Physics, 142092 Troitsk, Moscow Region, Russia



Communicated by Howard Reiss, University of California, Los Angeles, CA, June 24, 2002 (received for review April 3, 2002)

The spontaneous genesis of hydrocarbons that comprise natural petroleum have been analyzed by chemical thermodynamic-stability theory. The constraints imposed on chemical evolution by the second law of thermodynamics are briefly reviewed, and the effective prohibition of transformation, in the regime of temperatures and pressures characteristic of the near-surface crust of the Earth, of biological molecules into hydrocarbon molecules heavier than methane is recognized. For the theoretical analysis of this phenomenon, a general, first-principles equation of state has been developed by extending scaled particle theory and by using the technique of the factored partition function of the simplified perturbed hard-chain theory. The chemical potentials and the respective thermodynamic Affinity have been calculated for typical components of the HC system over a range of pressures between 1 and 100 kbar (1 kbar = 100 MPa) and at temperatures consistent with those of the depths of the Earth at such pressures. The theoretical analyses establish that the normal alkanes, the homologous hydrocarbon group of lowest chemical potential, evolve only at pressures greater than 30 kbar, excepting only the lightest, methane. The pressure of 30 kbar corresponds to depths of 100 km. For experimental verification of the predictions of the theoretical analysis, a special high-pressure apparatus has been designed that permits investigations at pressures to 50 kbar and temperatures to 1,500°C and also allows rapid cooling while maintaining high pressures. The high-pressure genesis of petroleum hydrocarbons has been demonstrated using only the reagents solid iron oxide, FeO, and marble, CaCO3, 99.9% pure and wet with triple-distilled water.

I just had an evil thought.

Hey, Sal, your quoted abstract says that oil can be made from marble. OK, where does marble come from?

Actually, I'll save you the trouble of going to Wikipedia. Limestone is a sedimentary rock that forms from the calcified remains of ancient marine creatures. Marble is the recrystalization of limestone. So, you see Sal old buddy, even if you could squeeze oil out of marble, which you can't by the way, it would still be a fossil fuel.

Thanks for the diversion. It was fun. .

Remarkably, earth’s limestone holds a thousand times more calcium and carbon than today’s atmosphere, oceans, coal, oil, and living matter combined. A simple, visual examination of limestone grains shows that few are ground-up sea shells or corals, as some believe.

I believe this study will disconfirm several anti-YEC claims.