Thermodynamic data from redox reactions at high temperatures. II. The MnO-0Mn3O4 oxygen buffer,and implications for the thermodynamic properties of MnO and Mn3O4     

Hugh St. C. O'Neill  Mark I. Pownceby 《Contributions to Mineralogy and Petrology》1993,114(3):315-320

The \(\mu _{O_2 } \) defined by the reaction 6 MnO+O₂ =2 Mn₃O₄ has been determined from 917 to 1,433 K using electrochemical cells (with calcia-stabilized zirconta, CSZ) of the type: Steady emfs were achieved rapidly at all temperatures on both increasing and decreasing temperature, indicating that the MnO-Mn₃O₄ oxygen buffer equilibrates relatively easily. It therefore makes a useful alternative choice in experimental petrology to Fe₂O₃-Fe₃O₄ for buffering oxygen potentials at oxidized values. The results are (in J/mol, temperature in K, reference pressure 1 bar); \(\mu _{O_2 } \) (±200)=-563,241+1,761.758T-220.490T inT+0.101819T ² with an uncertainty of ±200 J/mol. Third law analysis of these data, including a correction for the deviations in stoichiometry of MnO, impliesS _298.15 for Mn₃O₄ of 166.6 J/K · mol, which is 2.5 J/K · mol higher than the calorimetric determination of Robie and Hemingway (1985). The low value of the calorimetric entropy may be due to incomplete ordering of the magnetic spins. The third law value of Δ _r H _298.15 ⁰ is-450.09 kJ/mol, which is significantly different from the calorimetric value of-457.5±3.4 kJ/mol, calculated from Δ _f H _298.15 ⁰ of MnO and Mn₃O₄, implying a small error in one or both of these latter.  相似文献   

Mass-radius relationships and constraints on the composition of Pluto,II     

Mark J. Lupo  John S. Lewis 《Icarus》1980,44(1):41-42

A new estimate of Pluto's mass within the range of possible masses considered in an earlier work has enabled us to refine our model of Pluto's interior.  相似文献   

An upper limit on the aperture separation of ion drift meters     

E. A. Bering  K. G. Weber  U. V. Fahleson 《Astrophysics and Space Science》1982,83(1-2):37-49

An upper limit has been calculated on the effective aperture separation or detector thickness of ion drift meters of two fundamental types. The limit applies to meters which compare currents collected by detectors with different view directions at the same retarding potential and to meters which measure the entire thermal ion distribution function. For both types, a single scanned detector may be employed instead of multiple detectors, in which case the limit applies to twice the radius of curvature of the path followed by the detector aperture during a scan, (i.e. the diameter of a spinning payload). The limit was found to be important in two cases. First, in the F region on spacecraft with stringent electrostatic cleanliness requirements, the 10% error limit was found to be 40 cm. Second, in the E region, the limit was found to be 1 cm.Originally submitted to the journalSpace Science Instrumentation.Deceased.  相似文献   

Crustal structure of the Rhenish Massif: results of deep seismic reflection lines Dekorp 2-North and 2-North-Q   总被引：1，自引：1，他引：0  

Prof. Dr. W. Franke  Prof. Dr. R. K. Bortfeld  Dr. M. Brix  Dr. G. Drozdzewski  Prof. Dr. H. J. Dürbaum  Prof. Dr. P. Giese  Dr. W. Janoth  Dr. H. Jödicke  Chr Reichert Dipl.-Geophys.  Dr. A. Scherp  J. Schmoll Dipl.-Geophys.  R. Thomas Dipl.-Geophys.  Dr. M. Thünker  Prof. Dr. K. Weber  Dr. M. G. Wiesner  Prof. Dr. H. K. Wong 《International Journal of Earth Sciences》1990,79(3):523-566

The reflection seismic line DEKORP 2-N reveals an almost complete cross section through the Rhenohercynian Zone, the most external part of the Variscan orogen in Europe.The northern part of DEKORP 2-N and a NE-directed branch (2-N-Q) reveal the Cretaceous of the Münsterland basin and the underlying folded Palaeozoic rocks. The northward decreasing intensity of folding is depicted in great detail by the highly reflective Late Carboniferous coal-measures and deeper reflections down to the level of the Givetian/Frasnian shallow-water carbonates.In the Devonian and older rocks of the Rhenish Massif, bedding is only represented by relatively weak, short and irregular reflections. These are truncated by stronger, southward dipping reflections, which exhibit the listric curvature and flat/ramp geometry characteristic of faults. In the northern part of the section, the thrusts appear to be blind. From the Ebbe Anticline southwards, prominent reflections can be correlated with important thrust faults known from the surface, such as the Ebbe-, Siegen-, Müsen- and Sackpfeife- Thrusts, as well as further important thrust faults in the Lahn- and Dill Synclines. The basal thrust of the extremely thin-skinned Giessen Nappe is only recognizable for a very short distance.At depth, the thrusts flatten out in a relatively transparent zone between 3–5 s TWT, with strongly reflective bands at its bottom and top. The transparent zone might correlate with a high-conductivity layer detected in a magnetotelluric survey; it represents either graphitic metapelites or a zone with an interconnected, brine-filled pore space. The seismic record relates either to lithological differences, or to rheological boundaries.The lower crust in the north is characterized by a relatively transparent zone, which wedges out towards south under the northern margin of the Siegen Anticline. Comparisons with a similar feature in the ECORS profile »Nord de la France« suggest that the transparent zones in both sections correspond to a pre-Palaeozoic basement, such as it underlies the Brabant Massif. Further south, the lower crust is increasingly reflective.The curvilinear, thrust-related reflections are cut by a conjugate set of much weaker, N- and S-dipping reflectors indicating a later deformation with pure shear. Displacement of some marker reflections suggests late- or post-Variscan compression.In an alternative interpretation, these straight and weak reflections represent the only thrust faults, while the curvilinear elements might relate to bedding.A southward rise of the Moho from approx. 11 to 8.5 s TWT is probably due to Tertiary rifting.

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Zusammenfassung Das reflexionsseismische Profil DEKORP 2-N stellt einen fast vollständigen Querschnitt durch das Rhenohercynikum dar.Der nördliche Teil des Profiles 2-N sowie ein SW/NE-verlaufender Abzweig (2-N-Q) zeigen die Transgression der Münsterländer Kreide und das unterlagernde gefaltete Paläozoikum. Schichtgebundene Reflektoren (flözführendes Karbon, devonischer Massenkalk) bilden das Ausklingen der variscischen Faltung nach NW detailliert ab.In den devonischen und vordevonischen Sedimenten des rechtsrheinischen Schiefergebirges erzeugt die Schichtung nur relativ schwache, kurze und unregelmäßige Reflexionen. Diese werden von stärkeren, südfallenden Reflektoren abgeschnitten, die aufgrund ihrer listrischen Krümmung und flat/ramp-Geometrie wahrscheinlich als Überschiebungen zu interpretieren sind. Im Nordteil des Schiefergebirges sind diese Überschiebungen offenbar blind, werden also nahe der Oberfläche durch Faltung kompensiert. Im Ebbe-Sattel und weiter südlich lassen sich die meisten der starken, südfallenden Reflektoren zweifelsfrei mit bekannten Großüberschiebungen korrelieren (Ebbe-, Siegen-, Müsen-, Sackpfeife-Ü, sowie weitere Überschiebungen in der Lahn- u. Dill-Mulde). Die Basisüberschiebung der Giessen-Decke wird nur teilweise abgebildet.Zur Tiefe hin zeigen die Überschiebungen ein zunehmend flacheres Einfallen, und verschwinden in einer relativ transparenten Zone zwischen 3 und 5 s TWT, die im Hangenden und Liegenden durch dünne, stark reflektive Zonen begrenzt ist. Diese transparente Zone entspricht möglicherweise einer Zone hoher integrierter Leitfähigkeit, die in einem begleitenden magnetotellurischen Experiment nachgewiesen worden ist; es handelt sich entweder um einen Graphit-führenden Phyllit-Horizont oder eine mächtigere permeable Zone mit Elektrolyt-gefülltem Porenraum. Die hochreflektiven Bänder über und unter der transparenten Zone entsprechen entweder lithologischen Kontrasten oder rheologischen Grenzen, die vermutlich von einer scherenden Verformung überprägt worden sind.Die Unterkruste im N-Teil des Profiles enthält einen relativ transparenten Bereich, der nach Süden hin unter dem Nordteil des Siegener Sattels keilförmig ausläuft. Ein ähnliches Bild zeigt der Nordteil des ECORS-Profiles »Nord de la France«. Die transparenten Bereiche beider Profile entsprechen wahrscheinlich einem prä-paläozoischen kristallinen Basement, das das Brabanter Massif unterlagert und sich rechtsrheinisch fortsetzt. Südlich des transparenten Keiles wird die Unterkruste zunehmend reflexionsreicher. Die listrisch gekrümmten, an Überschiebungen gebundenen Reflektoren werden von einem konjugierten System schwächerer, N- u. S-fallender Reflektoren abgeschnitten, die auf eine jüngere, bruchhafte Verformung durch reine Scherung hindeuten. Der Versatz einiger älterer Reflektoren deutet auf spät- oder postvariscische Kompression hin.In einer alternativen Interpretation werden nur diese jüngeren Reflektoren als Überschiebungen gedeutet; die älteren, gekrümmten Elemente müßten dann primären lithologischen Grenzen entsprechen.Die Moho steigt von ca. 11 s TWT im N auf 8.5 s TWT unter dem Taunus an. Die Krustenverdünnung im Süden geht wahrscheinlich auf Dehnung im Tertiär zurück.

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Résumé Le profil sismique par réflexion DEKORP-2-N représente une transversale quasiment complète à travers la zone rhénohercynienne. La partie septentrionale du DEKORP-2-N ainsi qu'une branche de direction SW-NE (2-N-Q) mettent en évidence la transgression du Crétacé du Münsterland sur le Paléozoïque sous-jacent plissé. Des réflecteurs liés à la stratification (à savoir: le Houiller et les calcaires de plate-forme dévoniens) illustrent de façon détaillée la diminution vers le nord de l'intensité du plissement varisque.Dans les sédiments dévoniens et pré-dévoniens du Massif Rhénan à l'est du Rhin, la stratification ne fournit que que des réflexions relativement faibles, courtes et irrégulières. Elles sont tronquées par des réflecteurs plus intenses, à pendage sud qui, en raison de leur courbure listrique et de leur géométrie en «flat/ramp», doivent être interprétés comme des chevauchements. Dans la partie septentrionale du Massif, ces chevauchements sont apparemment aveugles, c'est-à-dire qu'ils sont compensés, près de la surface, par le plissement. Dans l'anticlinal d'Ebbe, ainsi que plus au sud, la plupart des réflecteurs intenses à plongement sud peuvent être corrélés avec des chevauchements majeurs connus, tels ceux de Ebbe, Siegen, Müsen, Sackpfeife et d'autres encore dans les synclinaux de la Lahn et de la Dill. Le chevauchement basai de la nappe de Giessen n'est que partiellement représenté.Les chevauchements deviennent de plus en plus plats en profondeur pour disparaître dans une zone relativement transparente qui se situe entre 3–5 sec TWT. Celle-ci est prise en sandwich par des zones minces à forte réflectivité. La zone transparente correspond probablement à une zone de conductivité intégrée élevée dont l'existence a par ailleurs été démontrée dans un essai magnétotellurique mené parallèlement. Il s'agit soit d'un horizon phyllitique graphiteux, soit d'une zone perméable plus épaisse dont les pores sont remplis d'électrolyte. Les bandes à haute réflectivité au-dessus et en-dessous de la zone transparente correspondent soit à des contrastes lithologiques, soit à des limites rhéologiques probablement accentuées par la déformation cisaillante.La croûte inférieure dans la partie septentrionale du profil comporte un domaine relativement transparent qui s'amincit vers le S et se termine, en dessous de la partie nord de l'anticlinal de Siegen, en forme de coin. La partie nord du profil ECORS «Nord de la France» montre une image semblable.Les domaines transparents des deux profils correspondent vraisemblablement à un soubassement cristallin pré-paléozoïque qui est sousjacent au Paléozoïque du Massif du Brabant et se prolonge vers l'est au-delà du Rhin. Au sud du coin transparent, la réflectivité de la croûte inférieure va en augmentant. Les réflecteurs listriques liés à des chevauchements sont recoupés par un système conjugué de réflecteurs plus faibles à plongement nord et sud qui indiquent des failles plus récentes. Le déplacement de quelques réflecteurs plus anciens suggère l'effet d'une compression tardiou post-varisque.Dans une interprétation alternative, seuls ces réflecteurs plus récents sont considérés comme correspondant à des chevauchements. Dans ce cas, les éléments courbes plus anciens devraient représenter des limites lithologiques primaires.Le Moho s'élève à partir de 11 sec TWT environ au nord jusqu'à 8.5 sec TWT en-dessous du Taunus. L'amincissement crustal au sud résulterait du régime de distension survenu au Tertiaire.

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DEKORP 2 Nord. x-t- ray-tracing'a. 6,0 6,6 /, — 7,0 8,2 /. 6,25 /. 28 30 . , .

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Abbreviations MORB Mid-Ocean Ridge Basalt - TWT two-way travel time, seconds (s) - CMP common mid-point - VP vibration point - SNR signal to noise ratio  相似文献   

Does reactive surface area depend on grain size? Results from pH 3, 25 °C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite     

Mark E. Hodson 《Geochimica et cosmochimica acta》2006,70(7):1655-1667

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 μm were dissolved in pH 3, HCl at 25 °C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol_feldspar g⁻¹ s⁻¹. For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 × 10⁻¹² mol_biotite m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 × 10⁻¹² mol_biotite g⁻¹ s⁻¹. For all normalising terms rates varied significantly (p ? 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over which they would change significantly.  相似文献   

Search for nucleosynthetic and radiogenic tellurium isotope anomalies in carbonaceous chondrites     

Manuela A. Fehr  Mark Rehkämper  Alex N. Halliday  Maria Schönbächler  Bodo Hattendorf 《Geochimica et cosmochimica acta》2006,70(13):3436-3448

Tellurium isotope data acquired by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) are presented for sequential acid leachates of the carbonaceous chondrites Orgueil, Murchison, and Allende. Tellurium isotopes are produced by a broad range of nucleosynthetic pathways and they are therefore of particular interest given the isotopic anomalies previously identified for other elements in these meteorites. In addition, the data provide new constraints on the initial solar system abundance of the r-process nuclide ¹²⁶Sn, which decays to ¹²⁶Te with a half-life of 234,500 years. The ¹²⁶Te/¹²⁸Te ratios of all leachates were found to be identical, within uncertainty, despite variations in ¹²⁴Sn/¹²⁸Te of between about 0.002 and 1.4. The data define a ¹²⁶Sn/¹²⁴Sn ratio of <7.7 × 10⁻⁵ at the time of last isotopic closure, consistent with the value of <18 × 10⁻⁵ previously reported for bulk carbonaceous chondrites. How close this is to the initial ¹²⁶Sn/¹²⁴Sn ratio of the solar system depends on when the investigated samples last experienced redistribution of Sn and Te. No clear evidence is found for nucleosynthetic anomalies in the abundances of p-, s-, and r-process nuclides. The largest effect detected in this study is a small excess of the r-process nuclide ¹³⁰Te in a nitric acid leachate of Murchison. This fraction displays an anomalous ε¹³⁰Te of +3.5 ± 2.5. Although barely resolvable given the analytical uncertainties, this is consistent with the presence of a small excess r-process component or an s-process deficit. The general absence of anomalies contrasts with previous results obtained for K, Cr, Zr, Mo, and Ba isotopes in similar leachates, which display nucleosynthetic anomalies of up to 3.8%. The reason for this discrepancy is unclear but it may reflect volatility and more efficient mixing of Te in the solar nebula.  相似文献   

Holocene record of productivity in the NW Iberian continental shelf     

V. Alves Martins  C. Patinha  E. Ferreira da Silva  J.-M. Jouanneau  O. Weber  F. Rocha   《Journal of Geochemical Exploration》2006,88(1-3):408

A multiproxy approach (textural characteristics, heavy metal concentrations and benthic foraminifera data) was adopted to study the OMEX core KSGX 40, collected at the Galicia Mud Deposit (NW Iberian outer continental shelf) and recording the last ca. 4.8 ka cal BP. Geochemical profiles of Fe, Mn, Zn, Co, Cr, Cu, Ni, Pb, Al and Ca show significant temporal variations. Benthic foraminifera productivity proxy suggests that the recorded muddy events were contemporaneous of a higher C_org flux to the marine benthic environment. The higher flux of organic matter, following a long-term intensification of the upwelling and coinciding with a finer sedimentation, led to depressed levels of oxygen beneath the water-sediments interface and to early diagenetic processes of several redox-sensitive elements.  相似文献   

Experimental evaluation of biases associated with sampling estuarine fishes with seines     

Mark A. Steele  Stephen C. Schroeter  Henry M. Pace 《Estuaries and Coasts》2006,29(6):1172-1184

Beach seines are widely used to estimate the density and species richness of fishes in estuaries. We evaluated the causes and extent of bias in estimates from seines using a series of field experiments in small estuaries in southern California, USA. Seining in spatially paired areas that were either enclosed by block nets or not, revealed that seines used without block nets und erestimated density by more than 4-fold and species richness by more than 2-fold relative to blocked areas. Seining in paired blocked areas with seines of two lengths revealed that net length affected estimates of density, but not species richness; a 7.6-m long seine produced 1.6-fold higher estimates of total density than did a 15.2-m long seine due to increased catches of demersal fishes, but not midwater species. Paired sampling in blocked areas also revealed that many fishes initially evaded capture by the seine. Estimates of density but not species richness were significantly higher in areas through which a seine was swept 5 times compared to once. This was due to higher catches of demersal fishes but not midwater fishes in areas seined 5 times. Repeated seining through blocked areas revealed that the vast majority (90% or more) of species and individuals of midwater fishes were captured within the first 5 sweeps, compared to only about 50% of the individuals of demersal species. A mark-recapture study in blocked areas revealed lower probabilities of capture for demersal species relative to midwater species.  相似文献   

Sampling characteristics and biases of enclosure traps for sampling fishes in estuaries     

Mark A. Steele  Stephen C. Schroeter  Henry M. Page 《Estuaries and Coasts》2006,29(4):630-638

We evaluated the sampling characteristics of enclosure traps in estuaries in southern California, USA. Using enclosure traps that sampled 0.25, 0.5, and 1-m² footprints, we found that enclosure trap size significantly affected estimates of fish density and the precision of these estimates. The highest estimates were produced by the 0.5-m² trap and the lowest by the 0.25-m² trap. Precision of the density estimates improved with increasing trap size, while the proportion of zero values in the data sets decreased and estimates of species richness increased. The largest trap was difficult to use in the field and often did not function properly; thus we concluded that intermediate enclosure trap sizes offered the best compromise between statistical and logistical considerations. By examination of burrows in sediment cores taken in fished out enclosure traps, we found no evidence to support the widely held view that burrow-dwelling fishes evaded capture by hiding in burrows. We also used mark-recapture techniques to estimate recovery efficiency in 0.43-m² enclosure traps. Recovery efficiency averaged 91% and did not differ significantly among estuaries or sampling stations within estuaries. Based on extensive netting within enclosure traps, we determined that in areas with dense fish populations (>90 fish 0.43-m⁻²), netting could be ceased after the first sweep that captured no fish with only a trivial effect on the estimate of density. In more sparsely populated areas, netting had to continue until 2–3 sweeps had captured no fish in order to obtain estimates of density that were within 90% of the actual values present. Overall, we found enclosure traps to be effective tools for sampling small, abundant fishes in shallow estuaries in southern California, but we recommend that care be taken when choosing trap size and sampling (netting) effort within traps in order to optimize their sampling characteristics.  相似文献   

Relative effects of physical and biological processes on nutrient and phytoplankton dynamics in a shallow estuary after a storm event     

Stephanie K. Moore  Mark E. Baird  Iain M. Suthers 《Estuaries and Coasts》2006,29(1):81-95

The effects of advection, dispersion, and biological processes on nitrogen and phytoplankton dynamics after a storm event in December 2002 are investigated in an estuary located on the northern New South Wales coast, Australia. Salinity observations for 16 d after the storm are used to estimate hydrodynamic transports for a one-dimensional box model. A biological model with nitrogen limited phytoplankton growth, mussel grazing, and a phytoplankton mortality term is forced by the calculated transports. The model captured important aspects of the temporal and spatial dynamics of the bloom. A quantitative analysis of hydrodynamic and biological processes shows that increased phytoplankton biomass due to elevated nitrogen loads after the storm was not primarily regulated by advection or dispersion in spite of an increase in river flow from <1 to 928×10³ m³ d⁻¹. Of the dissolved nitrogen that entered the surface layer of the estuary in the 16 d following the storm event, the model estimated that 28% was lost through exchange with the ocean or bottom layers, while 15% was removed by the grazing of just one mussel species,Xenostrobus securis, on phytoplankton, and 50% was lost through other biological phytoplankton loss processes.X. securis grazing remained an important loss process even when the estimated biological parameters in the model were varied by factors of ± 2. The intertidal mangrove pneumatophore habitat ofX. securis allows filtering of the upper water column from the lateral boundaries when the water column is vertically stratified, exerting top-down control on phytoplankton biomass.  相似文献