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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    European biophysics journal 6 (1980), S. 119-119 
    ISSN: 1432-1017
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1437-3262
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Description / Table of Contents: Abstract The recent discovery that atomic carbon occurs plentiful in olivines from mantle-derived rocks opens new aspects for the chemical evolution of the early atmosphere and the origin of life. It has been shown conclusively that atomic carbon which is dissolved in the model oxide MgO is capable of reacting in an O2-free atmosphere with the lattice oxygen to give CO2 and with the lattice hydrogen, derived from OH−, to give a profuse variety of hydrocarbons. The diffusional processes and low temperature gas/solid interface reactions involved in these processes are expected to introduce, purely abiotically, isotope fractionation resulting in a13C enrichment of the CO2 fraction and in a13C depletion of the hydrocarbon fraction which may be confused with the12C/13C isotope fractionation along biological pathways. Atomic carbon dissolved in olivines and in basalts shows a similar behaviour and yields similar quantities as C in MgO: 1–2 mg/g CO2 and 25–100μg/g hydrocarbons degassing between 400 and 1000 °C. On a geological scale this means that each cubic kilometer of basaltic magma degassing in an O2-free atmosphere has the capacity of sending off about 3–6·109 kg (2·109 m3) of CO2 and about 1–3·108 kg (2·108 m3) of hydrocarbons. The presence of water modifies the composition to give, among others, alcohols and organic acids. On the basis of these results we are led to the conclusion that the early atmosphere of the earth may have contained a very high concentration of abiotically formed “organic” compounds of great chemical complexity.
    Abstract: Résumé La découverte du carbone atomique dans les olivines du manteau entraîne de nouvelles idées sur la composition de l'atmosphère originelle et sur les conditions du développement de la vie. Comme l'est le cas pour le MgO, le carbone atomique dans les olivines est capable de réagir, dans une atmosphère exempte de O2, avec l'oxygène du réseau cristallin en formant du CO2, et avec l'hydrogène provenant des groupements OH− du réseau, pour former une grande variété de composés organiques. Les processus de diffusion et d'échange gas-solide liés à ces réactions provoquent, d'après les premiers résultats, un enrichissement en13C dans le CO2 et un appauvrissement en13C dans les hydrocarbures formés. Ceci ressemble au fractionnement dû à des réactions biologiques. Le comportement du carbone atomique et sa réactivité se retrouvent dans les basaltes et les olivines. La gamme des produits de réaction et leur quantité ressemble à celle du MgO: 1–2 mg/g CO2 et 25–100μg/g composés organiques. A l'échelle géologique ceci implique que chaque km3 de magma basaltique dégazé en contact avec une atmosphère exempte d'oxygène pouvait émettre 3–6·109 kg, soit 2·109 m3 de CO2 et 1–3·108 kg, soit 2·108 m3 d'hydrocarbures abiotiques. La présence d'eau entraîne la formation d'alcools et d'acides organiques. La conclusion tirée de ce travail indique que l'atmosphère originelle et la»soupe primordiale» étaient plus riches qu'on ne l'a admis jusqu'à présent en composés organiques dûs à des processus purement thermiques, et donc abiotiques.
    Notes: Zusammenfassung Die Entdeckung des atomar gelösten Kohlenstoffs in Olivinen aus Mantelgesteinen führt zu neuen Vorstellungen über die Zusammensetzung der Uratmosphäre und Entwicklungsbedingungen des Lebens. Atomarer Kohlenstoff im MgO ist in der Lage, in einer O2-freien Atmosphäre mit dem Gittersauerstoff zu CO2 zu reagieren und mit dem aus OH− stammenden Gitterwasserstoff eine große Vielfalt von organischen Verbindungen zu bilden. Diffusionsprozesse und Gas-Festkörper-Austauschreaktionen, die an diesen Reaktionen beteiligt sind, führen nach ersten Untersuchungen zu einer13C-Anreicherung im CO2 und einer13C-Abreicherung bei den Kohlenwasserstoffen. Diese12C/13C-Fraktionierung ist gleichsinnig mit der biologischen12C/13C-Fraktionierung. Atomarer Kohlenstoff in Olivinen und Basalten zeigt ein sehr ähnliches Reaktionsverhalten wie im MgO und führt zu ähnlichen Reaktionsprodukten: 1–2 mg/g CO2 und 25–100μg/g Kohlenwasserstoffe zwischen 400–1000 °C. Übertragen auf geologische Verhältnisse bedeutet dies, daß jeder km3 eines entgasenden basaltischen Magmas 3–6·109 kg (2·109 m3) CO2 und 1–3·108 kg (2·108 m3) abwüschen Kohlenwasserstoff abgeben kann. Die Anwesenheit von Wasser führt zur Bildung von Alkoholen und organischen Säuren. Diese Ergebnisse deuten darauf hin, daß die Uratmosphäre und die „Ursuppe“ viel reicher waren als bisher angenommen an komplexen organischen Verbindungen, die rein thermisch entstanden sind.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Contributions to mineralogy and petrology 76 (1981), S. 474-482 
    ISSN: 1432-0967
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract The dissolution of water does not stop at the OH− stage but may proceed further towards H2 plus O− formation. The discovery of atomic carbon dissolved in minerals suggests that, if CO2 enters oxides and silicates at high pressures and temperatures, not only [CO3]2− ions but also [CO 4 . ]4− complexes are formed via a charge transfer which produces O− and essentially zero-valent, atomic carbon. Under P —T-conditions of the mantle, where the solubility for water and CO2 is high, the silicate phases formed may therefore consist to a large volume fraction of O− ions which are much smaller than O2−ions and strongly cova-lently bonding. The implications for the crystal chemistry of high pressure phases, for the petrology of mantle rocks are outlined.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] The presence of krypton and nitrogen as well as isotopically anomalous xenon ('CCFXe', or 'Xe-HL') in the C8 residue5'6 has been interpreted to mean that the diamond is interstellar in origin1'2. Several low-pressure1'7'8 as well as high-pressure4 mechanisms of formation for interstellar diamond ...
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  • 5
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 11 (1984), S. 113-124 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Any oxide and silicate mineral which is nominally anhydrous but crystallized in the presence of H2O incorporates traces of H2O in solid solution. In the case of MgO it can be shown that OH− pairs convert into H2+O 2 2− . If the H2 molecules are lost, the O 2 2− remain in the lattice as excess oxygen stabilized by excess cation vacancies. When the O 2 2− anions decay either thermally or by decompression unbound O− states (positive holes) are generated which lead to surface charges and subsurface space charge layers. Calculated space charge profiles are presented. O− concentrations as small as 10–20 ppm suffice to create electric surface fields of the order of 4·107 V·m−1. The diffusion mechanism which derives from these premises incorporates novel features: the cation diffusion is coupled to the counterdiffusion of unbound and vacancy-bound O− states. The cation diffusion is predicted to be very fast because first, it is field-enhanced (electrochemically driven) and second, it is not rate-limited by the intrinsic cation vacancy concentration nor by the counter-diffusion of other cations. The model may apply to cases of inverse zoning and diffusion rim formation in minerals under certain P-T conditions.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 15 (1987), S. 1-18 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The dissolution of H2O and CO2 in structurally dense, nominally anhydrous and non-carbonate oxide matrices such as MgO and CaO is reviewed. H2O and CO2 are treated as gaseous oxide components which enter into solid solution with the refractory oxide hosts. They form anion complexes associated with cation vacancy sites. Evidence is presented that OH− pairs which derive from the dissolution of H2O are subject to a charge transfer (CT) conversion into peroxy moieties and molecular hydrogen, O 2 2− ... H2. Because the O 2 2− moiety is small (O−-O− distance ≈ 1.5 Å) high pressure probably favors the CT conversion. Mass spectroscopic studies show that molecular H2 may be lost from the solid which retains excess oxygen in the form of O 2 2− , leading to the release of atomic O. The dissociation of O 2 2− moieties into a vacancy-bound O− state and an unbound O− state can be followed by measuring the internal redox reactions involving transition metal impurities, the transient paramagnetism of the O− and their effect on the d.c. conductivity. Evidence is presented that CO2 molecules dissolve dissociatively in the structurally dense oxide matrix, as if they were first to dissociate into CO+O and then to form separate solute moieties CO 2 2− and O 2 2− , both associated with cation vacancy sites. In the CO 2 2− moiety (C-O− distance 1.2–1.3 Å, OCO angle ≈ 130°) the C atom probably sits off center. The transition of the C atom into interstitial sites is accompanied by dissociation of the CO 2 2− moiety into CO− and O−. This transition can be followed by infrared spectroscopy, using OH− as local probes. Further support derives from magnetic susceptibility, thermal expansion, low frequency dielectric loss and low temperature deformation measurements. The recently observed emission of O and Mg atoms besides a variety of molecules such as CO, CO2, CH4, HCN and other hydrocarbons during impact fracture of MgO single crystals is presented and discussed in the light of the other experimental data.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 13 (1986), S. 262-276 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract If carbon is to be analyzed by secondary ion mass spectroscopy (SIMS) in an oxide such as MgO, one has to know how the carbon is incorporated in the oxide host structure, before a successful experiment can be planned. If the carbon impurities derive from dissolved CO2 component which form a solid solution while the crystal grew from a melt in equilibrium with CO2, upon cooling, the solid solution becomes supersaturated with respect to the volatile CO2 component. This creates a thermodynamic driving force for exsolution leading to carbon segregation towards the surface. At the surface rapid degassing occurs in vacuum, enhanced by ion bombardment and electron irradiation. Using freshly cleaved synthetic MgO single crystals it can be shown by SIMS (i) that contamination during short exposure to air and during evacuation remains slight, (ii) that rapid surface/subsurface segregation of solute carbon seems to compete with rapid degassing so that, while no extended segregation profile builds up, the carbon concentration in the bulk beneath the surface decreases to a constant level, (iii) that electron irradiation speeds up degassing, (iv) that heating speeds up carbon diffusion, hence its segregation from the bulk, and (v) that Ar+ ion sputtering for the purpose of removing possible contaminants reduces the driving force for carbon surface segregation to the point that no segregation profile can be observed. By placing freshly cleaved MgO crystals under isotopically 99 percent pure 13CO2 for various periods of time subsequent SIMS analysis reveals extended 12C profiles, probably about 1 μm wide, which can only have formed by 12C segregation from the bulk. These results confirm earlier reports that solute carbon exists as mobile impurity in synthetic MgO and natural olivine, probably due to dissolved CO2 component.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Naturwissenschaften 57 (1970), S. 493-493 
    ISSN: 1432-1904
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Natural Sciences in General
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 29 (1999), S. 489-509 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Carboxylic and dicarboxylic acids (glycolic, oxalic, malonic and succinic) have been extracted with tetrahydrofuran (THF) and H2O from large synthetic MgO crystals, crushed to a medium fine powder. The extracts were characterized by infrared spectroscopy and 1H-NMR. The THF extracts were derivatized with tert-butyldimethylsilyl (t-BDMS) for GC-MS analysis. A single crystal separated from the extract was used for an x-ray structure analysis, giving the monoclinic unit cell, space group P21/c with ao = 5.543 Å, bo = 8.845 Å, co = 5.086 Å, and β = 91.9°, consistent with β-succinic acid, HOOC(CH2)COOH. The amount of extracted acids is estimated to be of the order of 0.1 to 0.5 mg g-1 MgO. The MgO crystals from which these organic acids were extracted grew from the 2860 °C hot melt, saturated with CO/CO2 and H2O, thereby incorporating small amounts of the gaseous components to form a solid solution (ss) with MgO. Upon cooling, the ss becomes supersaturated, causing solute carbon and other solute species to segregate not only to the surface but also internally, to dislocations and subgrain boundaries. The organic acids extracted from the MgO crystals after crushing appear to derive from these segregated solutes that formed C–C, C–H and C–O bonds along dislocations and other defects in the MgO structure, leading to entities that can generically be described as (HxCyOz)n-. The processes underlying the formation of these precursors are fundamental in nature and expected to be operational in any minerals, preferentially those with dense structures, that crystallized in H2O–CO2-laden environments. This opens the possibility that common magmatic and metamorphic rocks when weathering at the surface of a tectonically active planet like Earth may be an important source of abiogenically formed complex organic compounds.
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