Probleme der atmosphärischen Evolution im Präkambrium

Zusammenfassung Infolge des Sauerstoff-Unterschusses im Material von Erdmantel und Erdkruste besitzen deren Entgasungsprodukte generell reduzierenden Charakter und kommen somit als Lieferant von freiem Sauerstoff nicht in Frage. Die Quelle für den Luftsauerstoff muß deshalb in nicht-geologischen Prozessen zu suchen sein, bei denen der Sauerstoff nachträglich aus oxidischen Verbindungen (H₂O, CO₂) freigesetzt wurde. Da als Energiequelle für diese Reaktionen praktisch nur das Sonnenlicht zur Verfügung steht, muß die Anwesenheit von freiem Sauerstoff in der Atmosphäre letztlich auf einem photochemischen Effekt beruhen.Hierbei ist zu unterscheiden zwischen 1. einem anorganischen photochemischen Effekt, der mit dem kurzwelligen (energiereichen) Teil des Sonnenspektrums arbeitet (insbesondere 1500–2100 Å) und 2. einem organischen photochemischen Effekt, der mit dem Spektralbereich des sichtbaren Lichtes arbeitet, aber auf die Mitwirkung eines Katalysators (Chlorophyll) angewiesen ist. Der Anteil des ersteren Prozesses (Photodissoziation von Wasserdampf) am Aufbau der sauerstoffreichen Atmosphäre dürfte bei weitem geringer gewesen sein als der des zweiten (biologische Photosynthese von Kohlehydraten aus CO₂ und H₂O unter Freisetzung von Sauerstoff als Stoffwechselprodukt), so daß der heutige Luftsauerstoff im wesentlichen als biogen gedeutet werden kann. Die geochemische Evolution der Atmosphäre und die Evolution des Lebens sind somit auf das engste miteinander verknüpft. Mit dem Übergang von der primär reduzierenden zur oxidierenden Atmosphäre konnte beim Überschreiten des sog. Pasteur-Punktes (O₂-Partialdruck 10^–2 des heutigen Wertes) der Umschlag vom fermentativen zum oxidativen Energiestoffwechsel erfolgen. Es kann mit guten Gründen angenommen werden, daß die explosive Differenzierung des Lebens an der Wende Präkambrium-Kambrium eine Folge des höheren Energiegewinns bei der Atmung war. Sowohl die Aufrechterhaltung des Lebens als thermodynamisch metastabiler Zustand (mit einer Entropie weit unterhalb des Maximums) als auch seine Differenzierung im Laufe der Evolution bedürfen der ständigen Zufuhr von Energie, sind also nach der bekanntenBoltzmannschen Beziehung im Grunde genommen äußerst unwahrscheinliche Vorgänge. Freier Sauerstoff, der eine vollständige Verbrennung der Kohlehydrate zu Kohlendioxid und Wasser ermöglichte (und damit den Wirkungsgrad des Energiestoffwechsels im Vergleich zur anaeroben Gärung auf etwa das Vierzehnfache erhöhte), spielte bei der Evolution der Metazoen offensichtlich die Rolle Maxwellschen Dämons, der für die Aufrechterhaltung des thermodynamischen Ungleichgewichts (bzw. der Negentropie) in größeren Zellverbänden verantwortlich war.

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Because of the oxygen deficiency within the material of the earth's crust and mantle, degassing of the lithosphere does not furnish free oxygen, but gases possessing a strongly reducing character. Therefore, other than geological sources must have provided the free oxygen forming a major constituent of the present atmosphere. It is reasonable to conclude that this oxygen has been liberated from gaseous oxides such as water vapour and carbon dioxide. Since a large-scale dissociation of these compounds can only be brought about by solar radiation, photochemical activity must be responsible for the presence of molecular oxygen in the earth's atmosphere.In this context, we have to distinguish between 1. an inorganic photochemical process working with the energy-rich short wave-lengths of the solar spectrum (2 between 1500 and 2100 Å) and 2. an organic or biologic photochemical process which utilizes the spectral range of the visible light. In addition, the biologic process requires a porphyrin body (chlorophyll) to be present as a catalyst. The oxygen-producing capacity of the inorganic process, i. e., photodissociation of water vapour, is considerably smaller (about 10^–3) than that of the organic process (photosynthesis of carbohydrates from CO₂ and H₂O, releasing oxygen as a metabolic by-product). Accordingly, the bulk of the oxygen now present in the atmosphere may safely be regarded as being biologic in origin.Thus, the geochemical evolution of the atmosphere and the evolution of life are closely related and interdependent. The rise of the oxygen pressure of the ancient atmosphere to about 10^–2 P.A.L. (Present Atmospheric Level) enabled life to pass thePasteur point and change from fermentative (anaerobic) to respiratory (aerobic) metabolism. There is reason to believe that the appearance of the first metazoan faunas in the Late Precambrian, about 0.7×10⁹ years ago (Nama-Ediacara fauna), was a direct result of the enormous rise in metabolic energies derived from the more efficient aerobic metabolism.Life as a nonequilibrium steady state, being characterized by an entropy far below the level of its surroundings, requires a constant supply with free energy for its maintenance. As may be concluded from the impact of respiration on the diversification of life at the dawn of the Phanerozoic, this diversification was also dependent on an increased supply in free energy. Evolution thus being— just as life itself — an energy-absorbing (endergonic) process, it must be regarded as highly improbable in terms of theBoltzmann theory of thermodynamics. The mechanism of respiration, using oxygen as a final hydrogen acceptor in energyreleasing biologic redox processes (thereby increasing metabolic energies by the factor of fourteen), obviously played the role of the Maxwellian demon which caused the process of evolution to go into the direction of more order (or diversification) and less entropy.

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Résumé Le présent travail donne un aperçu de l'état actuel de nos connaissances concernant l'évolution de l'atmosphère terrestre depuis le Précambrien ancien. La transformation de l'atmosphère primitive réductrice en l'atmosphère actuelle oxydante paraît, pour la plus grande part, être due à des facteurs biologiques. En raison du parallélisme frappant entre l'évolution organique et l'évolution atmosphérique, la Paléontologie revêt une importance particulière pour l'histoire de l'atmosphère terrestre.

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Green clinopyroxenes and associated phases in a potassium-rich lava from the Leucite Hills,Wyoming

Green, salitic pyroxenes occur as megacrysts and as cores in diopsidic pyroxene phenocrysts and microphenocrysts in a wyomingite lava from Hatcher Mesa, Leucite Hills, Wyoming. Al-rich phlogopite (16–21% Al₂O₃), apatite, Fe-Ti-oxide, Mg-rich olivine (Fo₉₃) and orthopyroxene (En₆₁) also occur as megacrysts or as inclusions in diopside phenocrysts. All of these phases are found in ultramafic xenoliths in the host lava, and petrographic and chemical evidence is presented that the megacrysts originate by the disaggregation of the xenoliths. It is concluded that the latter are accidental fragments of the wall rocks traversed by the wyomingite magma and it is suggested that the clinopyroxene-rich xenoliths, from which the green pyroxenes are derived, formed in the upper mantle as a result of local metasomatism or by crystallization from magmas of unknown composition during an earlier igneous event. The precise role of the clinopyroxene-rich xenoliths (which also contain apatite, Fe-Ti-oxide and amphibole) in the genesis of the Leucite Hills magmas cannot be elucidated on the basis of the available data, but it is unlikely that they represent the source material from which these magmas are derived.     

Geochemical trends across an arc-continent collision zone: magma sources and slab-wedge transfer processes below the Pantar Strait volcanoes, Indonesia

Four volcanoes in the Pantar Strait, the westernmost part of the extinct sector of the east Sunda arc, show remarkable across-arc variation in elemental abundances (K₂O: 1.2 to 4.3%), trace element ratios (Pb/Ce: 0.4 to 0.18; Ce/Yb: 20 to 55) and isotope ratios (¹⁴³Nd/¹⁴⁴Nd: 0.51263 to 0.51245; ⁸⁷Sr/⁸⁶Sr: 0.7053 to 0.7068; ²⁰⁶Pb/²⁰⁴Pb: 19.29 to 19.15). Pb isotopes are decoupled from Sr and Nd isotopes, with the frontal volcanoes showing the higher Nd and Pb and lower Sr isotopic ratios. The isotopic and trace element ratios of the volcanic samples are best explained by modification of a MORB-type source (with Indian Ocean island basalt-type Pb isotopic characteristics) by a fluid and a partial melt of subducted continental material (SCM). The frontal volcano contains the highest proportion of the fluid component, with a small contribution of partial melt. The source of the rear-arc volcano is strongly influenced by a partial melt of SCM that had undergone a previous dehydration event, by which it lost most of its fluid-mobile elements such as Pb. The SCM partial melt was in equilibrium with both rutile and garnet, whereas mantle melting took place in the presence of residual mica. The relatively large across-arc increase in incompatible elements can be explained by a combination of increasing addition of SCM partial melt, changing mantle wedge fertility and smaller degrees of partial melting toward the rear of the arc. Comparison with a more westerly across-arc transect shows that the relatively low ¹⁴³Nd/¹⁴⁴Nd ratios of the frontal volcano, and the decoupling of Pb from Sr and Nd isotopes are unique to the Pantar Strait volcanoes. This is likely to reflect magma generation in a collisional environment, where the leading edge of the Australian continent, rather than subducted sediment, contributes to the magma source.     

Surface-rupturing history of the Bree fault scarp, Roer Valley graben: Evidence for six events since the late Pleistocene

Since 1996 paleoseismological investigations have been used to develop the surface- rupturing history of the Bree fault scarp, the morphologically best-defined segment of the southwestern border fault of the Roer Valley graben in northeastern Belgium. The first studies determined that the escarpment is associated with a surface fault, and they exposed evidence for three surface displacements since about 40 ka BP. The most recent eventprobably occurred between 1000 and 1350 yr cal BP. Geophysical and trenching studies at a new site near the southeastern end of the fault scarp reconfirmed the coincidence of the frontal escarpment with a shallow normal fault, which displaces the Middle Pleistocene `Main Terrace' of the Maas River, as well as overlying coversands of Saalian to late Weichselian age. Different amounts of displacement shown by the two youngest coversand units indicate two discrete faulting events, but primary evidence for the coseismic nature of these events is sparse. Radiocarbon and optically stimulated luminescence dating constrainthe age of these events to the Holocene and between 14.0 ± 2.3 ka BP and 15.8 ± 2.9 ka BP, respectively. In addition, four older surface-rupturing events are inferred from the presence of four wedge-shaped units of reworked Main Terrace deposits that are interbedded with coversand units in the hanging wall of the trench and in shallow boreholes. These wedges are interpreted as colluvial wedges, produced by accelerated slope processes in response torejuvenation of the fault scarp, most probably in a periglacial environment. Luminescence dating indicates that five out of a total of six identified faulting events are younger than 136.6 ± 17.6 ka. The antepenultimate event was the largest faulting event, associated with a total fault displacement in excess of 1 m. Thus, the newly investigated trench site represents the longest and most complete record of surface rupturing recovered so far along the Bree fault scarp. This study also demonstrates the viability of the paleoseismological approach to identify past large earthquakes in areas of present-day moderate to low seismic activity.     

Geochemical characterisation of organic matter in Keg River Formation (Elk point group, Middle Devonian), La Crete Basin, Western Canada

Carbonates from the Keg River Formation, La Crete Basin, Alberta, western Canada were examined in order to define: (a) oil source rock potential; (b) bulk maceral composition; (c) extract yield; and finally (d) facies variations using PY-GC-MS. Thirty samples from 6 different wells were examined from the lower Keg River member and 4 from the upper Keg River member using conventional geochemical methods. As maturity differences are absent within the sample set, variations in TOC, T_max, hydrogen index, organic petrography and extract yields are caused by variability in organic matter input, which is revealed by molecular characterisation using PY-GC-MS. Lower Keg River member bituminous wackestones are excellent potential source rocks containing Types I–II and Type II organic matter. Types I–II organic matter contains large well preserved (up to 200μm in diameter) thick-walled Tasmanites (10–15% of sample) and akinete algal cells indicative of algal blooms within an amorphous bituminite. Type II organic matter contains a higher proportion of degraded alginites/bituminite relative to well-preserved alginites. Extract yields (mg/g TOC) were seen to increase from Types I–II to Type II organic matter. PY-GC-MS revealed that 1,2,3,4-tetramethylbenzene was a major peak in most samples. This is a pyrolysis product arising from β-cleavage of C₄₀ diaromatic carotenoids incorporated within the kerogen during diagenesis. The source of this compound is thought to be from an unknown diaromatic compound with a 2,3,6-/3,4,5-trimethyl substitution pattern and isorenieratene, which is specific to photosynthetic green sulphur bacteria (Chlorobiaceae) suggesting that the photic zone was at least partially anoxic during deposition of these samples. The relative abundance of this compound/n-C11-alkene and organic sulphur (calculated from the thiophene ratio) both increase from Types I–II to Type II organic matter. This trend was grossly similar to the trend seen in the variability of extract yield with hydrogen index. A similar trend for HI and T_max indicates samples containing a higher proportion of degraded alginites/bituminite relative to well-preserved alginite are more labile than Type I–II organic matter. Upper Keg River member marls contain Type II organic matter, which is characterised by heavily degraded algal material within a bituminous groundmass. Pyrolysates of two of the marl samples contain only low amounts of 1,2,3,4-tetramethylbenzene, in contrast to the bituminous wackestones, indicating that the depositional environment/source input was different during deposition of the marl samples. Although both marls contain similar organic matter, their pyrolysates were significantly different. One marl (1141.9 m) was highly paraffinic containing dominantly short-chain alkene/alkane doublets, while the other marl (1137.6 m) contained a bimodal n-alkane/alkene distribution and high amounts of alkylphenols, which may be derived from preservation of resistant algal polyphenolic molecules or suggest a terrestrial input.     

Distribution and Migrations of two Cerithid Snails on a Sand Flat in Bermuda

Abstract. Two species of cerithid prosobranchs live on a sand flat in Bermuda. At low tide during day light Batillaria minima is found on the surface whereas Cerithium lutosum remains buried in the sediment. This correlates with much higher lethal and coma temperatures, as well as much greater resistance to desiccation, of the former species. However, at other diurnal or tidal stages the two species co-occur in the same layer of sand. Despite greater resistance to physical factors the population of B. minima seems to be declining since in 1980 juveniles of this species were rare on Tuckers Town Flat whereas the population of C. lutosum was thriving.     

Measurements of positive ion conversion and removal reactions relating to the Jovian ionosphere

Measured rates are presented for the reaction of He⁺ ions with H₂ (and D₂) molecules to form H⁺, H₂⁺, and HeH⁺ ions, as well as for the subsequent reactions of H⁺ and HeH⁺ ions with H₂ to form H₃⁺. The neutralization of H₃⁺ (and H₅⁺) ions by dissociative recombination with electrons is shown to be fast. The reaction He⁺ + H₂ is slow (k = 1.1 × 10^?13 cm³/sec at300°K) and produces principally H⁺ by the dissociative charge transfer branch. It is concluded that there may be a serious bottleneck in the conversion of two of the primary ions of the upper Jovian ionosphere, H⁺ and He⁺ (which recombine slowly), to the rapidly recombining H₃⁺ ion (α[H₃⁺]?3.4 × 10^?7 cm³/sec at 150°K).     

Analysis of processes leading to localized electron enhancements in the outer radiation belt

New information obtained about >500 keV electron intensity enhancements, which have been observed intermittently close to the outer edge of the electron radiation belt, is used in conjunction with an earlier statistical study by Brown and Stone (1972) to investigate processes which could lead to such structures. The enhancements are typically of ～20 sec duration and occur in a very narrow invariant latitude band, maximally 2° wide. The intensity increase relative to the “normal” background level is up to a factor 10, and the “spike” frequency of occurrence is strongly local time dependent, with more spikes observed in the night and dusk-noon sectors than in the noon-dawn sector. The processes investigated quantitatively are distortions of the magnetospheric topology in the equatorial region, wave-particle interactions and the effects of ionospheric currents. It is shown that the various processes which contribute to equatorial field disturbances can explain the observations.