Geologische Rundschau. Organic Geochemistry.
Organic matter alteration and fluid migration in hydrothermal systems
Lewan MD: Laboratory simulation of petroleum formation — hydrous pyrolysis. Edited by: Engle M, Macko S. Lewan MD, Ruble TE: Composition of petroleum generation kinetics by isothermal hydrous and non-isothermal open-system pyrolysis. Erdman M, Horsfield B: Enhanced late gas generation potential of petroleum source rocks via recombination reactions: Evidence from the Norwegian North Sea. Geochimica et Cosmochimica Acta. Connan J, Cassou AM: Properties of gases and petroleum liquids derived from terrestrial kerogen at various maturation levels.
American Association Petroleum Geologists, Bulletin. Stahl WJ: Carbon and nitrogen isotopics in hydrocarbon research and exploration. Chemical Geology. Rowe D, Muhlenbachs A: Low temperature thermal generation of hydrocarbons gases in shallow shales. Ramaswamy GA: Field evidence for mineral-catalyzed formation of gas during coal maturation.
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Mango FD: Transition metal catalysis in the generation of petroleum and natural gas. Mango FD: Carbon isotopic evidence for the catalytic origin of light hydrocarbons. Geochemical Transactions. Mango FD: Methane concentrations in natural gas: the genetic implications.
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Schaefer RG, Weiner B, Leythaeuser D: Determination of sub-nanogram per gram quantities of light hydrocarbons C2-C9 in rock samples by hydrogen stripping in the flow system of a capillary gas chromatograph. Analytical Chemistry. Eiswirth M: Chaos in surface-catalyzed reactions.
Edited by: Field J, Gyorgyi L. Physical Review E. Cirak F, et al: Oscillatory thermomechanical instability of an ultrathin catalyst. Konhauser K: Introduction to Geomicrobiology. Physical Review B. Mango FD: Transition metal catalysis in the generation of natural gas. Mango FD: The origin of light hydrocarbons. Durand B: Kerogen. Download references.
Natural and Laboratory Simulated Thermal Geochemical Processes
We wish to thank Stephen Garcia for his excellent experimental assistance and Eleanor Herriman for her technical assistance and manuscript preparation. Correspondence to Frank D Mango. Reprints and Permissions. Mango, F. Low-temperature gas from marine shales. Geochem Trans 10, 3 doi Download citation.
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Search all BMC articles Search. Abstract Thermal cracking of kerogens and bitumens is widely accepted as the major source of natural gas thermal gas. Background The hydrocarbons in natural gases are believed to come from two sources, one biological 'biogenic gas' , and the other from thermal cracking, 'primary thermal gas' from kerogen cracking, and 'secondary thermal gas' from oil cracking [ 1 , 2 ]. Full size table. Figure 1. Full size image. Figure 2. Figure 3. Experimental Our objective was to analyze the inner anoxic surfaces of marine shales for evidence of natural catalytic activity by LVTM.
Conclusion Marine shales possess natural catalytic activity for converting hydrocarbons kerogens and bitumens to gas at low temperatures. References 1. Google Scholar 4. Google Scholar 5. Google Scholar 6. Others, found in sulfide deposits within the ophiolite area of Cyprus Oudin and Constantinou, and Oman Haymon et al. Banks found in Tynagh, Ireland Myr-old fossils recovered from pyrite chimneys associated with sedimentary-exhalative mineralization. Figure 2, in Martin and Russell , shows iron monosulfide precipitates Fe S , which oxidized to pyrite Fe S 2 , and which hydrothermally formed iron sulfide chimneys.
Some of the chimneys contain sphalerite ZnS which, according to the brilliant hypothesis of Banks et al. The prebiotic broth theory as a modular model of Darwin, Oparin and Haldane Darwin, ; Oparin, ; Haldane, can be considered in modern terms as a heterotrophic origin of life. Miller and colleagues are the modern proponents of that theory Miller, , ; Miller and Bada, The theory of a heterotrophic beginning assumes a slow accumulation of amino acids, bases, sugars, lipids, nucleic acids, and some groups of polypeptides, building more and more complex organic compounds in droplets coacervates concentrated, as it were, in a rich broth in some primitive ocean when the physical conditions of the planet permitted.
The heterotrophic theory considers that such compounds self organized and finally became reproducing entities.
At the outset, this extraordinary theory was very exciting for many biologists. It is typically based on principles of solution chemistry; the reactions have to take place in a water phase. Such prebiotic chemistry is extant organic chemistry writ large. Many experts have criticized its logic and its thermodynamic incompatibility Woese, ; Cairns-Smith, , and also its improbable occurrence, on many grounds Shapiro, , , Since this theory does not appear to offer a bridge between biology, chemistry and biochemistry, most present day theories have preferred other paths Woese, We, like many others nowadays, bet on sufficient concentrations of simple reducing inorganic molecules in iron-sulfide precipitates of crystals in a seepage site with physical compartments isolated from the immediate environment in self-contained redox reactions under a hydrothermal submarine Hadean ocean floor.
Such could have been the beginning of metabolism in status nascendi imprisoned in iron crystals for a long time, before other self-organized chemical and biochemical reactions placed the prisoner in a newer, less rigid cell wall. At the beginning, at the very first stages of evolution, we propose that there was no reproduction, no natural selection, no heredity, and no variability that could serve as units of selection and of evolution.
In such beginnings the conditions for molecules to react under Gibbs conditions of thermodynamics spurred the reactions to proceed undeterred, far from equilibrium. Therefore, there was no origin of life at that time, because the ingredients were absent or incomplete. However, the chemistry for later life was represented in a group of readily made compounds that could respond to each other without catalysis.
Thus, no enzymes, only mineral crystals precipitated as iron sulfide, and others, such as nickel sulfide, which in accordance with the laws of natural chemistry carry on redox reactions catalyzed by iron sulfur centers and by the presence of ferredoxins of simple organic compounds. These were mineral chemistry conditions, distinct from water chemistry, where newly made compounds could be washed away. The organic compounds were then fixed on a pyrite surface, enjoying free electronic energy in a reduced and alkaline condition and relatively high temperature and pressure, under the crust of the Hadean Ocean and in mounds of hydrothermal vents.
Indeed, in all extant organisms, transition metal sulfide clusters play an indispensable role in biological energy conversion systems Spiro, The predominance of mineral sulfides in hydrothermal and volcanic vents Larter et al.