Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa     

Paolo?A.?SossiEmail author  Julie?Prytulak  Hugh?St.?C.?O’Neill 《Contributions to Mineralogy and Petrology》2018,173(4):27

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities (\({f_{{{\text{O}}_{\text{2}}}}}\)), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V³⁺ and V⁴⁺ in magnetite, and a mixture of IV- and VI-fold V⁵⁺ and V⁴⁺ in the melt. The magnitude of the fractionation factor systematically increases with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\) relative to the Fayalite–Magnetite–Quartz buffer (FMQ), from ?⁵¹V_mag-gl = ? 0.63?±?0.09‰ at FMQ ? 1 to ? 0.92?±?0.11‰ (SD) at ≈?FMQ?+?5, reflecting constant V³⁺/V⁴⁺ in magnetite but increasing V⁵⁺/V⁴⁺ in the melt with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\). These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.  相似文献   

Numerical prediction of an intense convective system associated with the July 1987 montreal flood. part II: A trailing stratiform rainband     

Stéphane Bélair  Da‐Lin Zhang  Jocelyn Mailhot 《大气与海洋》2013,51(3):475-500

Abstract

In this study, the internal circulation structures of the 14 July 1987 intense mesoscale convective system (MCS) are investigated using an improved high‐resolution version of the Canadian regional finite‐element model. It is found that although the MCS is characterized by a leading convective line followed by a trailing stratiform rainband, the associated circulation structures differ substantially from those in the classical midlatitude squall system. These include the rapid propagation and separation of the leading convection from the trailing rainband, the development of a surface‐based instead of an elevated rear‐to‐front descending flow and a shallow front‐to‐rear ascending flow associated with the stratiform precipitation, the generation of low‐ and mid‐level rather than mid‐ to upper‐level stratiform cloudiness and the development of a strong anticyclonic vorticity band at the back edge of the stratiform region. It is shown that the trailing stratiform rainband is dynamically forced by frontogenetical processes, and aided by the release of conditional symmetric instability and local orographical lifting. The intense leading and trailing circulations result from latent heat released by the convective and explicit cloud schemes, respectively. Sensitivity experiments reveal that the proper coupling of these two cloud schemes is instrumental in obtaining a realistic prediction of the above‐mentioned various mesoscale components. Vorticity budget calculations show that tilting of horizontal vorticity contributes the most to the amplification of the anticyclonic vorticity band, particularly during the squall's incipient stage. The sensitivity of the simulated squall system to other model physical parameters is also examined.  相似文献   

Numerical analysis of frost effects in porous media. Benefits and limits of the finite element poroelasticity formulation     

Stéphane Multon  Alain Sellier  Bernard Perrin 《国际地质力学数值与分析法杂志》2012,36(4):438-458

The aim of this paper is to analyse the performance of a finite element formulation usable for predicting the mechanical consequences of frost effects on porous media. It considers the characteristics of porous media and how the frost action can be assessed. The problem is then separated into two parts: thermal and poromechanical calculations. The constitutive equations developed in the framework of poromechanics are presented and the implementation in a usual finite element poroelasticity formulation based on Zuber's method is adopted. An analysis of the time‐step influence on the convergence rate is given and leads us to propose a simple method in order to obtain objectivity of the finite element response and avoid over‐long calculations. Frost effect simulations are carried out on real porous media (two fired clays) as a case study. Although the experimental behaviour of the porous media subjected to frost action is in accordance with some observations, the calculated strains appear to be overestimated compared with measurements. The problem could be largely attributable to the difficulty of assessing permeability evolution during frost development. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

Linking past flood frequencies in Norway to regional atmospheric circulation anomalies     

Eivind N. Støren  Erik W. Kolstad  Øyvind Paasche 《第四纪科学杂志》2012,27(1):71-80

Analysis of two continuous, high‐resolution palaeo‐flood records from southern Norway reveals that the frequency of extreme flood events has changed significantly during the Holocene. During the early and middle Holocene, flood frequency was low; by contrast, it was high over the last 2300 years when the mean flood frequency was about 2.5–3.0 per century. The present regional discharge regime is dominated by spring/summer snowmelt, and our results indicate that the changing flood frequency cannot be explained by local conditions associated with the respective catchments of the two lakes, but rather long‐term variations of solid winter precipitation and related snowmelt. Applying available instrumental winter precipitation data and associated sea‐level pressure re‐analysis data as a modern analogue, we document that atmospheric circulation anomalies, significantly different from the North Atlantic Oscillation (NAO), have some potential in explaining the variability of the two different palaeo‐flood records. Centennial‐scale patterns in shifting flood frequency might be indicative of shifts in atmospheric circulation and shed light on palaeo‐pressure variations in the North Atlantic region, in areas not influenced by the NAO. Major shifts are found at about 2300, 1200 and 200 years ago (cal. a BP). Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

Activity-composition relations in FeTiO3-MnTiO3 ilmenite solid solutions from EMF measurements at 1050–1300 K     

Hugh St. C. O'Neill  Mark I. Pownceby  Victor J. Wall 《Contributions to Mineralogy and Petrology》1989,103(2):216-222

The activity of FeTiO₃ in the binary ilmenitepyrophanite (FeTiO₃-MnTiO₃) solid solution has been determined for the temperature range 1050–1300 K by displacement of the reaction: 2 FeTiO₃=2 Fe+2 TiO₂+O₂ in T-O₂ space, using an electrochemical technique with calcia- and yttria-stabilized zirconia solid electrolytes. The activities show small positive deviations from ideality, which, although the data are unusually precise, may be perfectly described by the simple regular solution model, with an interaction parameter, W _Fe-Mn ^ilm , of 2.2±0.3 kJ g-atom^–1, which is independent of temperature. This value, together with the experimental data on the partitioning of Fe and Mn between ilmenite and garnet (Pownceby et al. 1987), gives W _Fe-Mn ^gt =1.2±0.5 kJ g-atom^–1 for the almandine-spessartine (Fe₃Al₂Si₃O₁₂-Mn₃Al₂Si₃O₁₂) solid solution.  相似文献   

Temperature and precipitation trends in Europe and their possible link with greenhouse-induced climatic change     

C. -D. Schönwiese  U. Stähler  W. Birrong 《Theoretical and Applied Climatology》1990,41(3):173-175

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Preface     

B. Stöckhert  K. H. Wedepohl 《International Journal of Earth Sciences》1991,80(2):I-I

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Temperature dependence of the cation distribution in nickel aluminate (NiAl2O4) spinel: a powder XRD study     

H. St. C. O'Neill  W. A. Dollase  C. R. Ross II 《Physics and Chemistry of Minerals》1991,18(5):302-319

NiAl₂O₄ is a largely inverse spinel, which in detail shows increasing randomisation with temperature of Ni and Al between the octahedral and tetrahedral cation sites of the spinel structure. We have used powder XRD to determine this cation distribution in various samples of NiAl₂O₄ quenched after annealing between 700 and 1400° C. The inversion parameter (x) can be measured with a precision of ± 0.004 (one standard deviation), and a comparison of different methods of synthesis, X-ray diffraction and refinement techniques, suggests a probable accuracy of better than 0.01. The results are supported by some preliminary single crystal refinements on flux-grown samples.Below 800° C the rate of cation ordering becomes very slow, and, despite reaching an apparently steady state, it is doubtful if our samples attained complete internal equilibrium. Above 1250° C the cation redistribution becomes so fast that the quenching method becomes unreliable. Between 800 and 1250° C inclusive, the degree of inversion changes smoothly from 0.87 at 800° C to 0.79 at 1250° C, and is accompanied by linear changes in u, the oxygen parameter, from 0.2555 to 0.2563 (±0.0002), and a₀, the lattice parameter, from 8.0462 to 8.0522 Å (±0.0002 Å).  相似文献   

Biochemische Abbaubarkeit ausgewählter alicyclischer Verbindungen     

J. Wotzka  B. Giest  St. Pfitzner 《洁净——土壤、空气、水》1985,13(5):583-590

Thirteen alicyclic compounds (C₅… C₇) are examined for their biochemical degradability in a laboratory activating tank and in two respirometers (Warburg, Sapromat). The tests were performed with adapted and nonadapted activated sludge. In addition, the COD was determined by three different methods. With the exception of cycloheptane (BOD < 25% of the BOD_theor.), six compounds prove to be easily degradable (BOD > 45% of the BOD_theor.) and six compounds prove to be degradable (BOD 45… 25% of the BOD_theor.).  相似文献   

Thermodynamics of Co3O4: a possible electron spin unpairing transition in Co3+     

H.St. C. O'Neill 《Physics and Chemistry of Minerals》1985,12(3):149-154

The free energy of the reaction: $$Co_3 O_4 \rightleftarrows 3C_O O + \tfrac{1}{2}O_2$$ has been studied between 890 and 1,240 K using an e.m.f. technique. There is a phase transition in Co₃O₄ at 1,120±20 K which is accompanied by a large change in entropy (～47 JK^?1 mol^?1 of Co₃O₄), and a rapid increase in unit cell volume and in electical conductivity. This is interpreted to be due to a partial change in electronic spin states in Co^{3 +} from the spin-paired (low spin) configuration observed at room temperature to the spin-unpaired (high spin) state. The transition is probably not first order.  相似文献