Glass formation in silicates: Insights from composition     

《Chemical Geology》2006,225(3-4):388-401

The composition dependence of glass formation is examined in a variety of silicate systems that include alkali and alkaline earth alumino-, titano-, ferro- and ferrisilicates. Empirically, there is a clear correlation between wide extent of glass formation, possible crystallization from the melt of numerous compounds, and moderate liquidus temperatures. Vitrification with usual cooling rates is in contrast impossible when binary and ternary compounds are scarce and liquidus temperatures are high. These correlations imply that vitrification is favored by moderately negative enthalpies of mixing in the melt but made difficult by high configurational heat capacities. The close connection between glass formation and viscosity is reviewed in the light of these melt properties. That bulk viscosity is in general not directly relevant to the kinetics of crystal nucleation in particular indicates that vitrification theories cannot be considered as by-products of crystallization theories.  相似文献   

Determination of phospholipid fatty acid structures and stable carbon isotope compositions of deep-sea sediments of the Northwest Pacific, ODP site 1179   总被引：1，自引：0，他引：1  

Christopher T. Mills  Robert F. Dias  Dennis Graham  Kevin W. Mandernack   《Marine Chemistry》2006,98(2-4):197-209

Sediment samples ranging from 0.05 to 278 m below sea floor (mbsf) at a Northwest Pacific deep-water (5564 mbsl) site (ODP Leg 191, Site 1179) were analyzed for phospholipid fatty acids (PLFAs). Total PLFA concentrations decreased by a factor of three over the first meter of sediment and then decreased at a slower rate to approximately 30 mbsf. The sharp decrease over the first meter corresponds to the depth of nitrate and Mn(IV) reduction as indicated by pore water chemistry. PLFA-based cell numbers at site 1179 had a similar depth profile as that for Acridine orange direct cell counts previously made on ODP site 1149 sediments which have a similar water depth and lithology. The mole percentage of straight chain saturated PLFAs increases with depth, with a large shift between the 0.95 and 3.95 mbsf samples. PLFA stable carbon isotope ratios were determined for sediments from 0.05 to 4.53 mbsf and showed a general trend toward more depleted δ¹³C values with depth. Both of these observations may indicate a shift in the bacterial community with depth across the different redox zones inferred from pore water chemistry data. The PLFA 10me16:0, which has been attributed to the bacterial genera Desulfobacter in many marine sediments, showed the greatest isotopic depletion, decreasing from − 20 to − 35‰ over the first meter of sediment. Pore water chemistry suggested that sulfate reduction was absent or minimal over this same sediment interval. However, 10me16:0 has been shown to be produced by recently discovered anaerobic ammonium oxidizing (anammox) bacteria which are known chemoautotrophs. The increasing depletion in δ¹³C of 10me16:0 with the unusually lower concentration of ammonium and linear decrease of nitrate concentration is consistent with a scenario of anammox bacteria mediating the oxidation of ammonium via nitrite, an intermediate of nitrate reduction.  相似文献   

The “Zero-order Model” revisited: Paul Schindler's influence on the development of trace metal scavenging models     

Santschi  Peter H.  Honeyman  Bruce D.  Quigley  Matthew S. 《Aquatic Sciences - Research Across Boundaries》1993,55(4):230-239

In 1975 Paul Schindler produced the first oceanic trace metal scavenging model to explicitly include the role of surface chemistry as a control on trace metal water column residence times. The eighteen years that have elapsed since the publication of Schindler's seminal paper have seen the development of a variety of oceanic scavenging models; yet, the fundamental insight of his Zero-order Model remains the benchmark. This paper describes the role of Paul Schindler's work on surface chemistry in providing a framework for the current generation of trace element scavenging models.  相似文献   

Precious metals in massive base metal sulfide deposits     

R. W. Hutchinson 《International Journal of Earth Sciences》1990,79(2):241-263

Gold and silver are ubiquitous, sometimes minor but economically important metals in massive base metal sulfide ores. Their content, proportions and distribution in the ores depend on complex, interrelated factors of their source, mobilization, transport and deposition.Different types of these deposits are formed by similar seafloor hydrothermal systems operating, however, in widely differing tectono-stratigraphic environments which span a spectrum from ensimatic-oceanic, through continent-margin to ensialic-continental ones. Like those of the base metals, the proportions and distribution of the precious metals in the ores vary regionally with these changing depositional environments. This suggests that precious metal content of the sub-seafloor rocks in which the generative fluids circulate is one factor that governs the amounts and distribution in the ores. The lithology of these source-rocks is also important. Pillowed, tholeiitic basalts have high permeability, golddepleted crystalline pillow interiors and relatively gold-rich palagonitic rims, and are consequently particularly favorable sources.Mobilization of gold from the sub-seafloor rocks may require basalt-water, and/or carbonaceous sediment-water reactions to produce strongly reduced bisulfide, carbonyl or cyanide complexes that promote gold transport. Chloride complexing and transport are less important for gold but more so for silver and the base metals.Seafloor hydrothermal discharge at shallow depth is commonly accompanied by boiling, steamblast explosions in the vent and resulting deep penetration and mixing of cool, oxygenated seawater with rising hot, reduced metalliferous fluid. This results in deposition of both chloride- and isulfide-complexed gold at depth and centrally in the footwall stockwork or in copper ore in the base of the massive body. Chloride-complexed silver, stable to lower temperatures, is carried farther and deposited with higher-level and more distal, massive zinc-lead ores. Boiling in deep water, however, although possible, is rare. This fact minimizes deep fluid mixing and allows transport of lower temperaturestable, bisulfide-complexed gold to the seafloor and outward from the vent. Gold too, is then deposited with the shallower, distal, massive zinc-lead-silver ore. Late-stage changes in fluid Eh, salinity and activity of sulfur during evolution of the generative hydrothermal system, and by discharge through previously deposited, early stage sulfides around the vent also cause diagenetic remobilization of gold, moving it to shallower, more distal locations in the system. In combination, these relationships explain the three associations of gold in primary, in-situ massive sulfide deposits; in central, deep footwall stockwork mineralization with or without copper, in central copper ore in the base of the massive body and in shallow, peripheral pyritic zinclead-silver ore.Primary, in-situ ore near the vent is sometimes reworked by seafloor density flows which transport clasts of the primary sulfides down-slope, mix them with rock and sedimentary detritus and redeposit them to form secondary, transported ore. Gold, like iron and the base metals, is diluted during this clastic transport. But silver and barite may be enriched indicating transport in the density flows not only as clasts of primary ore but partly also m solution in the hydrothermal fluids that, in this case, must have lubricated the density flows.

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Zusammenfassung Gold- und Silbervorkommen in massiven Metallsulfid-Lagerstätten sind stets ökonomisch wichtige Metalle, auch wenn sie nur in geringen Konzentrationen vorliegen. Der Gehalt an diesen Metallen und ihre Verteilung innerhalb der Lagerstätte hängt von komplexen, sich gegenseitig beeinflussenden Faktoren wie Metallquelle, Art der Mobilisation, Transport und Fällung ab.Unterschiedliche Lagerstättentypen werden von ähnlichen hydrothermalen Systemen auf den Ozeanböden gebildet. Die tektonostratigraphischen Environments unterscheiden sich dabei allerdings beträchtlich; sie befinden sich in ensimatisch-ozeanischen, kontinentalrandlichen und ensialischkontinentalen Bereichen. Innerhalb dieser regional wechselnden Ablagerungsbedingungen variiert Konzentration und Verteilung der Edelmetalle in den Lagerstätten wie bei den einfachen Metallen. Dies bedeutet, daß der Gehalt an Edelmetallen der Gesteine, die den Meeresboden unterlagern und durch die die metallhaltigen Lösungen zirkulieren, ein Faktor ist, der Menge und Verteilung der Metalle in der Lagerstätte steuert. Ebenso ist die Lithologie dieser Gesteine von Bedeutung. Als besonders gut geeignete Quellen gelten kissenartige tholeitische Basalte mit hoher Permeabilität, goldarmen Kisseninneren und relativ goldreichem palagonitischem Rand.Um das Gold aus diesen Gesteinen mobilisieren zu können, bedarf es einer Reaktion zwischen Basalt und Wasser und/oder eines karbonatischen Sediments mit Wasser, um stark reduziertes Bisulfid, Carbonyl-oder Cyanidkomplexe zu bilden, die den Goldtransport ermöglichen. Chlorid-Komplexbildung und -Transport sind zwar wichtig für Silber und einfache Metalle, für Gold spielen sie nur eine untergeordnete Rolle.Der Austritt hydrothermaler Lösungen an Ozeanböden in geringer Tiefe wird in der Regel von Sieden und explosionsartigem Dampfaustritt begleitet und führt deshalb zu einem tiefen Eindringen und Durchmischen von kaltem, sauerstoffreichen Meereswasser mit den aufsteigenden heißen, reduzierten metallischen Lösungen. Daher kommt es zur Fällung von sowohl an Chloridkomplexe als auch an Bisulfidkomplexe gebundenem Gold. Diese Ausfällung findet in größerer Tiefe statt und zwar hauptsächlich im liegenden Stockwerk oder mit Kupfer zusammen an der Basis der massiven Lagerstätte. An Chloridkomplexe gebundenes Silber ist auch bei niedrigeren Temperaturen stabil, wird also weiter transportiert und in einem höheren Niveau in distal gelegenen Blei-Zink-Lagerstätten gefällt. In größeren Wassertiefen kommt es seltener zu dem beobachteten Sieden der austretenden Lösungen. Diese Tatsache reduziert das Durchmischen der Lösungen in größeren Tiefen und ermöglicht den Transport von Gold, das an Bisulfidkomplexe gebunden ist. In diesem Fall ist die Verbindung auch bei niedrigeren Temperaturen noch stabil also transportfähig und kann bis zum Meeresboden oder außerhalb des Schlotes in Lösung bleiben. Dabei kann das Gold zusammen mit Blei, Zink und Silber in mehr distalen Lagerstätten angereichert werden. Späte Änderungen in Eh, Salinität und Schwefelaktivität der Lösungen während der Entwicklung des hydrothermalen Systems, sowie der Austritt durch früher abgelagerte den Schlot umgebende Sulfide, können eine diagenetische Gold-Remobilisation auslösen. Auch dabei kann das Metall zu in geringer Tiefe liegenden, distalen Ablagerungsorten transportiert werden. Berücksichtigt man alle Faktoren, so erklären diese Verhältnisse die drei möglichen Goldvorkommen in primären, in-situ vorliegenden Sulfid-Lagerstätten: Mit Kupfer vergesellschaftet, allerdings nicht unbedingt, zentral im liegenden Stockwerk; an der Basis der Kupferlagerstätte und in geringer Tiefe in Verbindung mit peripheren Blei-Zink-Silber-Vorkommen.Primäre, in-situ neben Schloten vorkommende Lagerstätten werden in einigen Fällen von meeresbodennahen Masseströmen aufgearbeitet. Diese transportieren Sulfidkomponenten, die während des Transports mit Sediment und Gesteinsbruchstücken vermischt und schließlich als sekundäre sedimentäre Lagerstätte abgelagert werden. Durch diesen Transport und die Mischung der Klastika wird die Goldkonzentration in der späteren Lagerstätte stark reduziert. Silber und Barit können dagegen in Ausnahmefällen während des Transports angereichert werden, da diese Komponenten nicht nur als Sulfidbruchstücke transportiert werden, sondern auch in Lösung in den hydrothermalen Lösungen vorhanden sein können. Diese Lösungen dienen in solchen Fällen den Masseströmen als Gleithorizont.

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Résumé Dans les gisements de sulfures métalliques massifs, l'or et l'argent sont des métaux ubiquistes, parfois mineurs, mais toujours d'importance économique. Leur teneur et leur distribution dans les corps minéralisés dépendent de facteurs complexes, en relation les uns avec les autres, tels que: leur source, leur mobilité, leurs modalités de transport et de dépôt.A partir des mêmes systèmes hydrothermaux en action sur le fond de la mer, divers types de gisements peuvent être engendrés, selon leur environnement tectono-stratigraphique: océanique ensimatique, de marge continentale ou continental ensialique. Les teneurs et la répartition des métaux précieux, comme celle des autres métaux varient régionalement selon ces divers milieux. Ceci suggère que le contenu en métaux précieux dans les roches sous-jacentes au fond marin à travers lesquelles circulent les solutions minéralisantes est un facteur qui détermine leurs teneurs et leurs répartitions dans les minerais. La lithologie de ces roches-sources est également importante. Une source particulièrement significative est représentée par les coussins des basaltes tholéiitiques, très perméables, avec leur coeur pauvre en or et leur couronne palagonitique relativement riche.Le lessivage de l'or dans les roches situées sous le fond marin peut impliquer des réactions eau-basalte et/ou eausédiments carbonatés, réactions susceptibles d'engendrer les bisulfures très réduits et les complexes carbonés ou cyanurés qui permettent le transport de l'or. Le transport par complexes chlorurés joue un rôle subordoné dans le cas de l'or, mais important dans le cas de l'argent et des autres métaux.L'arrivée de solutions hydrothermales sur les fonds marins peu profonds est d'ordinaire accompagnée d'ébullitons et d'émissions explosives de vapeur, ce qui provoque la pénétration profonde d'eau de mer froide et oxygénée et son mélange avec les fluides métallifères chauds et réducteurs ascendants. Il en résulte le dépôt de complexes aurifères bisulfurés et chlorurés. Cette précipitation s'opère en profondeur, particulièrement dans les roches sous-jacentes ou dans le minerai de cuivre, à la base des corps minéralisés massifs. L'argent des complexes chlorurés, stables à plus basse température, est transporté plus loin et se dépose, en situation plus distale, dans les minerals massifs de Pb-Zn. Dans les mers profondes, l'ébullition, sans être impossible, est néanmoins un phénomène rare; cette circonstance minimise le mélange des fluides en profondeur et permet le transport de l'or jusqu'à la surface du fond et même loin des évents sous la forme de complexes bisulfurés stables à basse température. L'or est alors déposé en situation distale peu profonde avec les minerals massifs de Zn-Pb-Ag. Des modifications tardives d'Eh, de salinité et d'activité du soufre dans les solutions au cours de l'évolution du système hydrothermal, de même que le lessivage des sulfures déjà accumulés autour des évents entraînent une remobilisation diagénétique de l'or vers des situations distales d'eau peu profonde. La combinaison de ces divers facteurs permet d'expliquer les trois occurrences de l'or dans les dépôts in situ de sulfures massifs primaires: dans les parties centrales des masses sous-jacentes en association ou non avec le Cu, à la base des corps minéralisés en Cu, et à faible profondeur, en liaison avec les gisements périphériques de Pb-Zn-Ag.Les gisements primaires, formés in situ près des évents sont parfois remaniés par des courants de densité, qui emportent des clastes de sulfures, les mélangent aux débris sédimentaires et les redéposent sous forme de minerais secondaires. De tels transports provoquent la dilution de l'or, en même temps que celle du fer et des autres métaux. Par contre, l'argent et la barite peuvent subir un enrichissement car leur transport dans les courants de densité ne s'effectue pas seulement sous forme de clastes, mais également en solution dans des fludies hydrothermaux, lesquels, dans ce cas, contribuent à lubrifier le courant de densité.

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Mathematical models for petroleum-forming processes: carbon isotope fractionation     

Douglas W Waples  Leonard Tornheim 《Geochimica et cosmochimica acta》1978,42(5):467-472

A mathematical model has been developed in which carbon isotope fractionation during thermal cracking of n-paraffins can be simulated. The model has been calibrated based on data from laboratory cracking experiments carried out on n-octadecane. Relative rate constants for cleavage of C¹²-C¹², C¹²-C¹³ and C¹³-C¹³ bonds agree with the experimental values obtained by other workers.Application of this model to the process of petroleum formation gives good agreement with some existing experimental data, but suggests that a review of our understanding of isotope fractionation during thermal cracking may be necessary. The relative importance of the degree to which the organic material has been cracked and of the type of the organic material in influencing δC¹³ values is discussed.The present model predicts that cracking of n-paraffin distributions having initial odd or even carbon number predominances can induce isotopic inhomogeneity among the homologs of the resulting distribution. The model exhibits some deficiencies in explaining or predicting the δC¹³ values of ethane and propane in relation to methane in gases and of oils and associated methane. Explanations for these discrepancies may lie in the simplicity of our mathematical model, in our assumption of initial isotopic homogeneity within molecules and in our use of only n-paraffins as the source molecules for the cracking reactions.  相似文献   

Mathematical models for petroleum-forming processes: n-paraffins and isoprenoid hydrocarbons     

Douglas W Waples  Leonard Tornheim 《Geochimica et cosmochimica acta》1978,42(5):457-465

Mathematical models have been developed which simulate both random and nonrandom thermal cracking of branched and straight-chain hydrocarbons. Application of these models to n-paraffins suggests that thermal cracking alone cannot be the dominant mechanism in formation of the n-paraffin distributions present in crude oils. Application to isoprenoid hydrocarbons indicates that nonrandom cracking could be important in producing the isoprenoid distributions found in oils.Results of the mathematical modeling show that methane formation should, as predicted from energy considerations, be kinetically disfavored. It therefore is likely that substantial quantities of methane are produced from saturated hydrocarbons only under thermal conditions more severe than those under which oil is produced.The mathematical models employed are adaptable for other geochemical applications, such as isotope fractionation.  相似文献   

Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians     

M.D. Lewan  M.J. Kotarba  D. Wi?c?aw 《Geochimica et cosmochimica acta》2006,70(13):3351-3368

The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S₂ generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S₂ generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S₂ generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen.  相似文献   

P‐wave stacking‐velocity tomography for VTI media     

Vladimir Grechka  res Pech  Ilya Tsvankin 《Geophysical Prospecting》2002,50(2):151-168

A major complication caused by anisotropy in velocity analysis and imaging is the uncertainty in estimating the vertical velocity and depth scale of the model from surface data. For laterally homogeneous VTI (transversely isotropic with a vertical symmetry axis) media above the target reflector, P‐wave moveout has to be combined with other information (e.g. borehole data or converted waves) to build velocity models for depth imaging. The presence of lateral heterogeneity in the overburden creates the dependence of P‐wave reflection data on all three relevant parameters (the vertical velocity V_P0 and the Thomsen coefficients ε and δ) and, therefore, may help to determine the depth scale of the velocity field. Here, we propose a tomographic algorithm designed to invert NMO ellipses (obtained from azimuthally varying stacking velocities) and zero‐offset traveltimes of P‐waves for the parameters of homogeneous VTI layers separated by either plane dipping or curved interfaces. For plane non‐intersecting layer boundaries, the interval parameters cannot be recovered from P‐wave moveout in a unique way. Nonetheless, if the reflectors have sufficiently different azimuths, a priori knowledge of any single interval parameter makes it possible to reconstruct the whole model in depth. For example, the parameter estimation becomes unique if the subsurface layer is known to be isotropic. In the case of 2D inversion on the dip line of co‐orientated reflectors, it is necessary to specify one parameter (e.g. the vertical velocity) per layer. Despite the higher complexity of models with curved interfaces, the increased angle coverage of reflected rays helps to resolve the trade‐offs between the medium parameters. Singular value decomposition (SVD) shows that in the presence of sufficient interface curvature all parameters needed for anisotropic depth processing can be obtained solely from conventional‐spread P‐wave moveout. By performing tests on noise‐contaminated data we demonstrate that the tomographic inversion procedure reconstructs both the interfaces and the VTI parameters with high accuracy. Both SVD analysis and moveout inversion are implemented using an efficient modelling technique based on the theory of NMO‐velocity surfaces generalized for wave propagation through curved interfaces.  相似文献   

Data and model uncertainty estimation for linear inversion   总被引：1，自引：0，他引：1  

Kasper van Wijk  John A. Scales  William Navidi  Luis Tenorio 《Geophysical Journal International》2002,149(3):625-632

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Water wars in the Middle East: a looming threat     

Hussein A. Amery 《The Geographical journal》2002,168(4):313-323

This paper explains how hydropolitical dynamics and spatial variables almost triggered a water war between Israel and Lebanon because the latter was building a pump on the Wazzani Spring, a tributary of the Jordan River. The convergence of a regional drought, history of violent confrontations between the two riparians, distrust, varying development needs and territorial disputes almost culminated in a war between these east Mediterranean neighbours. While most international water disputes in the Middle East will be resolved peacefully, some are likely to trigger violent confrontations threatening political stability in the Middle East in the next few decades.  相似文献