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1.
Distribution of Ferric Iron in some Upper-Mantle Assemblages   总被引:16,自引:5,他引:11  
The distribution of ferric iron among the phases of upper-mantlerocks, as a function of pressure (P), temperature (T) and bulkcomposition, has been studied using 57Fe Mssbauer spectroscopyto determine the Fe3+/Fe ratios of mineral separates from 35peridotite and pyroxenite samples. The whole-rock Fe3+ complementof a peridotite is typically shared approximately evenly amongthe major anhydrous phases (spinel and/or garnet, orthopyroxeneand clinopyroxene), with the important exception of olivine,which contains negligible Fe3+. Whole-rock Fe3+ contents areindependent of the T and P of equilibration of the rock, butshow a well-defined simple inverse correlation with the degreeof depletion in a basaltic component. Fe3+ in spinel and inboth pyroxenes from the spinel Iherzolite facies shows a positivecorrelation with temperature, presumably owing to the decreasein the modal abundance of spinel. In garnet peridotites, theFe3+ in garnet increases markedly with increasing T and P, whereasthat in clinopyroxene remains approximately constant. The complexnature of the partitioning of Fe3+ between mantle phases resultsin complicated patterns of the activities of the Fe3+ -bearingcomponents, and thus in calculated equilibrium fO2, which showlittle correlation with whole-rock Fe3+ or degree of depletion.Whether Fe3+ is taken into account or ignored in calculatingmineral formulae for geothermobarometry can have major effectson the resulting calculated T and P. For Fe-Mg exchange geothermometers,large errors must occur when applied to samples more oxidizedor reduced than the experimental calibrations, whose fO2 conditionsare largely unknown. Two-pyroxene thermometry is more immuneto this problem, and probably provides the most reliable P—Testimates. Accordingly, the convergence of P—T valuesderived for a given garnet peridotite assemblage may not necessarilybe indicative of mineral equilibrium. The prospects for thecalculation of accurate Fe3+ contents from electron microprobeanalyses by assuming stoichiometry are good for spinel, uncertainfor garnet, and distinctly poor for pyroxenes. KEY WORDS: mantle; oxidation; partitioning; peridotite; thermobarometry *Corresponding author. Present address: School of Earth and Ocean Sciences, University of Victoria, P.O. Box 1700, Victoria, B.C., V8W 2Y2, Canada  相似文献   
2.
The solubility of sulfur as S2– has been experimentallydetermined for 19 silicate melt compositions in the system CaO–MgO–Al2O3–SiO2(CMAS)± TiO2 ± FeO, at 1400°C and 1 bar, using CO–CO2–SO2gas mixtures to vary oxygen fugacity (fO2) and sulfur fugacity(fS2). For all compositions, the S solubility is confirmed tobe proportional to (fS2/fO2)1/2, allowing the definition ofthe sulfide capacity (CS) of a silicate melt as CS = [S](fO2/fS2)1/2.Additional experiments covering over 150 melt compositions,including some with Na and K, were then used to determine CSas a function of melt composition at 1400°C. The resultswere fitted to the equation  相似文献   
3.
Hydrogen solubility and hydroxyl substitution mechanism in olivineat upper-mantle conditions are not only a function of pressure,temperature, water fugacity and hydrogen fugacity, but are alsoinfluenced by silica activity. Olivine synthesized in equilibriumwith magnesiowüstite displays hydroxyl stretching bandsin the wavenumber range from 3640 to 3430 cm–1. In contrast,olivine in equilibrium with orthopyroxene shows absorption bandsin a narrower wavenumber range from 3380 to 3285 cm–1.The two fundamentally different spectra are assigned to hydroxylin tetrahedral and octahedral sublattices, respectively. Olivinein equilibrium with orthopyroxene is also less capable of incorporatinghydroxyl, relative to olivines in equilibrium with magnesiowüstite,by about a factor of ten. A comparison of spectra obtained aspart of this study with hydroxyl spectra of natural mantle olivinesshows that the latter display hydroxyl stretching patterns reminiscentof equilibrium with magnesiowüstite, although undoubtedlyolivine in the Earth’s mantle coexists with orthopyroxene.This may be attributed to a metasomatic overprint by a low-silicafluid and/or melt that was in reaction relationship with orthopyroxene.A likely metasomatic agent is a carbonatitic melt. When carbonatiticmelts decompose to oxides and CO2, they may temporarily imposea low-aSiO2 environment inherited by the olivine structure.If this suggestion proves true, Fourier transform IR spectroscopymay be used to fingerprint metasomatic episodes in the lithosphericmantle. KEY WORDS: FTIR spectrometry; olivine; mantle; metasomatism; water  相似文献   
4.
The common upper mantle assemblage olivine-orthopyroxene-spinelmay be used to calculate the oxygen fugacity at which mantle-derivedperidotites have equilibrated. The equilibrium has been calibratedusing the large amount of existing data on the thermodynamicproperties of each phase in this assemblage. A by-product ofthis procedure is a new calibration of the olivine-spinel Mg-Fe2+exchange geothermometer. Application of the equilibrium to avariety of peridotite xenoliths indicates that the oxygen fugacityof the upper mantle lies between the quartz-fayalite-magnetite(QFM) and w?stite-magnetite (WM) oxygen buffers; the few apparentexceptions to this rule may be due to analytical error, particularlyin the Fe3+ content of the spinet phase. In fact, the determinationof Fe3+ in spinet is at present the limiting factor in the accurateapplication of the method: within this limitation, the presentlyavailable evidence suggests that the oxygen fugacity of themantle may be laterally homogeneous over wide regions, but mayalso show small differences between these regions. The fluidspecies in the system C-H-O at such oxygen fugacities are predominantlyCO2 and/or H2O, and not CH4/H2 The minimum possible oxygen fugacity of the mantle is givenby the nickel content of olivine in equilibrium with orthopyroxene;for typical mantle compositions this minimum curve is virtuallycoincident with the iron-w?stite (IW) oxygen buffer.  相似文献   
5.
本工作首次在实验室条件下对浅生区紫硫镍矿(Ni,Fe)3S4交代镍黄铁矿(Ni,Fe)9S8水热反应的机理及动力学进行了研究。起始反应矿物采用高纯自然镍黄铁矿,合成纯镍黄铁矿或合成镍黄铁矿-磁黄铁矿集合体。反应pH值采用0.2M醋酸-醋酸纳缓冲溶液控制在3~5的范围内。反应进程由X-射线衍射物相定量分析及扫描电镜观察进行跟踪。结果表明,当反应温度恒定在80℃时,交代20(4)%的镍黄铁矿需792h。相同条件下加入少量H2S可将反应速率提高一倍。当反应在125℃饱和蒸汽压水热环境下进行时,完全交代纯镍黄铁矿需约168h。此过程由于磁黄铁矿的存在而被催化,交代集合体中的镍黄铁矿仅需68h,进一步反应磁黄铁矿被交代成白铁矿。磁黄铁矿的催化作用可能源于溶解产生的微裂纹加速了流体的传质过程。当反应温度升高至145℃时,速率反而下降,不遵循Arrhenius经验规律。动力学分析得80℃速率常数介于5.8×10-8~3.0×10-7/s之间,125℃及145℃速率常数分别介于2.8×10-6~2.08×10-5/s及1×10-6~5.1×10-6/s之间,远高于同温度下固相扩散反应的速率常数,表明该反应在地质时标上为一快速反应。此外,用背散射电子显微技术对矿物表面形貌进行了分析,发现交代产物紫硫镍矿具有颗粒细小及存在微裂纹等特征,与自然界浅生矿床中的紫硫镍矿非常相似;电镜实验还表明该交代作用是一个典型的耦合溶解-再沉淀反应。其耦合机制的驱动力可能与反应界面处微空隙对流体饱和度的控制有关。  相似文献   
6.
Chromium as Cr3+ substitutes for octahedrally coordinated Alin upper-mantle minerals, thereby reducing the activity of Al2O3in the system and hence the concentration of Al2O3 in partialmelts. The effect of Cr2O3 on melt compositions multiply saturatedwith the spinel lherzolite phase assemblage has been quantifiedin the system CaO–MgO–Al2O3–SiO2–Cr2O3at 1·1 GPa as a function of 100 Cr/(Cr + Al) in the spinel(Cr#sp). The decrease of Al2O3 in the melt with increasing Cr#spis accompanied by increasing MgO and SiO2, whereas CaO remainsalmost constant. Consequently, the CaO/Al2O3 ratio of the meltincreases with Cr#sp, and the melt becomes richer in normativediopside, hypersthene and quartz. The effect may explain certainmantle melts with unusually high CaO/Al2O3 ratios. The concentrationof Cr2O3 in the melt remains low even at high Cr#sp, which meansthat the strong effect of Cr2O3 on partial melting equilibriais not readily apparent from its concentration in the melt itself.The existence of a highly refractory major component such asCr2O3 nullifies simplified conclusions from the ‘inverseapproach’ in the experimental study of basalt petrogenesis,as there is insufficient information in the composition of thepartial melt to reconstruct the conditions of melting. KEY WORDS: basalt petrogenesis; partial melting; reversal experiment; spinel lherzolite; system CMAS–Cr2O3; CaO/Al2O3 of melt; effect of Cr2O3  相似文献   
7.
The compositions of multiply saturated partial melts are valuablefor the thermodynamic information that they contain, but aredifficult to determine experimentally because they exist onlyover a narrow temperature range at a given pressure. Here wetry a new approach for determining the composition of the partialmelt in equilibrium with olivine, orthopyroxene, clinopyroxeneand spinel (Ol + Opx + Cpx + Sp + Melt) in the system CaO–MgO–Al2O3–SiO2(CMAS) at 1·1 GPa: various amounts of K2O are added tothe system, and the resulting melt compositions and temperatureare extrapolated to zero K2O. The ‘sandwich’ experimentalmethod was used to minimize problems caused by quench modification,and Opx and Cpx were previously synthesized at conditions nearthose of the melting experiments to ensure they had appropriatecompositions. Results were then checked by reversal crystallizationexperiments. The results are in good agreement with previouswork, and establish the anhydrous solidus in CMAS to be at 1320± 10°C at 1·1 GPa. The effect of K2O is todepress the solidus by 5·8°C/wt %, while the meltcomposition becomes increasingly enriched in SiO2, being quartz-normativeabove 4 wt % K2O. Compared with Na2O, K2O has a stronger effectin depressing the solidus and modifying melt compositions. Theisobaric invariant point in the system CMAS–K2O at whichOl + Opx + Cpx + Sp + Melt is joined by sanidine (San) is at1240 ± 10°C. During the course of the study severalother isobaric invariant points were identified and their crystaland melt compositions determined in unreversed experiments:Opx + Cpx + Sp + An + Melt in the system CMAS at 1315 ±10°C; in CMAS–K2O, Opx + Cpx + Sp + An + San + Meltat 1230 ± 10°C and Opx + Sp + An + San + Sapph +Melt at 1230 ± 10°C, where An is anorthite and Sapphis sapphirine. Coexisting San plus An in three experiments helpdefine the An–San solvus at 1230–1250°C. KEY WORDS: feldspar solvus; igneous sapphirine; mantle solidus; partial melting; systems CMAS and CMAS–K2O  相似文献   
8.
The effects of small amounts of H2O (<4 wt % in the melt)on the multiply saturated partial melting of spinel lherzolitein the system CaO–MgO–Al2O3–SiO2 ±Na2O ± CO2 have been determined at 1·1 GPa inthe piston-cylinder apparatus. Electron microprobe analysisand Fourier transform infrared spectroscopy were used to analysethe experimental products. The effects of H2O are to decreasethe melting temperature by 45°C per wt % H2O in the melt,to increase the Al2O3 of the melts, decrease MgO and CaO, andleave SiO2 approximately constant, with melts changing fromolivine- to quartz-normative. The effects of CO2 are insignificantat zero H2O, but become noticeable as H2O increases, tendingto counteract the H2O. The interaction between H2O and CO2 causesthe solubility of CO2 at vapour saturation to increase withincreasing H2O, for small amounts of H2O. Neglect of the influenceof CO2 in some previous studies on the hydrous partial meltingof natural peridotite may explain apparent inconsistencies betweenthe results. The effect of small amounts of H2O on multiplysaturated melt compositions at 1·1 GPa is similar tothat of K2O, i.e. increasing H2O or K2O leads to quartz-normativecompositions, but increasing Na2O produces an almost oppositetrend, towards nepheline-normative compositions. KEY WORDS: H2O; CO2; FTIR; hydrous partial melting; mantle melting; spinel lherzolite; system CaO–MgO–Al2O3–SiO2 ± H2O ± CO2 ± Na2O  相似文献   
9.
This paper presents a digital linear filter which maps composite resistivity transforms to apparent resistivities for any four—electrode array over a horizontally layered earth. A filter is provided for each of three sampling rates; the choice of filter will depend on resistivity contrasts and computational facilities. Two methods of filter design are compared. The Wiener-Hopf least-squares method is preferable for low sampling rate filters. The Fourier transform method is more successful in producing a filter with a high sampling rate which can handle resistivity contrasts of 100 000: 1.  相似文献   
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