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1.
The partition of Ni between olivine and monosulfide-oxide liquid has been investigated at 1300–1395° C, =10–8-9–10–6.8, and =10–2.0–10–0.9, over the composition range 20–79 mol. % NiS. The product olivine compositions varied from Fo98 to Fo59 and from 0.06 to 3.11 wt% NiO. The metal/sulfur ratio of the sulfide-oxide liquid increases with increase in , decrease in , and increase in NiS content. The Ni/Fe exchange reaction has been perfectly reversed using natural olivine and pure forsterite as starting materials. The FeO and NiO contents of olivine from runs equilibrated at the same and form isobaric distributions with NiS content, which, to a first approximation, are dependent at constant temperature and total pressure on a variable term, –0.5 log ( / ). The Ni/Fe distribution coefficient (K D3) exhibits only a weak decrease from 35 to 29 with increase in from the IW buffer to close to the FMQ buffer. At values higher than FMQ, the sulfide-oxide liquid has the approximate composition (Ni,Fe)3±xS2K D358. The present K D3 vs O/(S+O) data define a trend which extrapolates to K D320 at 10 wt% oxygen in the sulfide-oxide liquid. The compositions of olivine and Ni-Cu sulfides associated with early-magmatic basic rocks and komatiites are consistent, at 1400° C, with a value of -log ( / ) of about 7.7, which is equivalent to 0.0 wt% oxygen in the hypothesized immiscible sulfide-oxide liquid. Therefore, K D3 would not be reduced significantly from the 30 to 35 range for sulfide-oxide liquids with low oxygen contents.  相似文献   

2.
In the Rogers Pass area of British Columbia the almandine garnet isograd results from a reaction of the form: 5.31 ferroan-dolomite+8.75 paragonite+4.80 pyrrhotite+3.57 albite+16.83 quartz+1.97 O2=1.00 garnet+16.44 andesine+1.53 chlorite+2.40 S2+1.90 H2O+10.62 CO2. The coefficients of this reaction are quite sensitive to the Mn content of ferroan-dolomite.Experimental data applied to mineral compositions present at the isograd, permits calculation of two intersecting P, T equilibrium curves. P=29088–39.583 T is obtained for the sub-system paragonite-margarite (solid-solution), plagioclase, quartz, ferroan-dolomite, and P=28.247 T–14126 is obtained for the sub-system epidote, quartz, garnet, plagioclase. These equations yield P=3898 bars and T=638° K (365° C). These values are consistent with the FeS content of sphalerite in the assemblage pyrite, pyrrhotite, sphalerite and with other estimates for the area.At these values of P and T the composition of the fluid phase in equilibrium with graphite in the system C-O-H-S during the formation of garnet is estimated as: bars, bars, bars, bars, bars, bars, bars, bars, , bars, bars.  相似文献   

3.
Ignimbrites from the central North Island consist mainly of glass or its devitrified product (70–95%); their phenocryst mineralogy is varied and includes plag., hyp., ti-mag., ilm., aug., hblende, biot., san., qtz, ol., with accessory apatite, zircon and pyrrhotite. The Fe-Mg minerals can be used to divide the ignimbrites into four groups with hyp.+aug. reflecting high quench temperatures and biot.+hblende +hyp.+aug., low quench temperatures. Oxygen fugacities lie above the QMF buffer curve and even in ignimbrites with low crystal contents the solid phases apparently buffered fO2. Some ignimbrites contain the assemblage actinolite, gedrite, magnetite and hematite, reflecting post-eruption oxidation. The mineralogy also allows estimation of using pyrrhotite and thence , . The assemblage biotite-sanidine can be used to estimate and thence . Water fugacity is calculated in a variety of ways using both biotite and hornblende as well as the combining reaction . It is high and approaches P total in most ignimbrites (~4kb) but is lower in unwelded pumice breccias. Comparison of temperature estimates using mineral geothermometers for the various phenocryst phases suggests that the ignimbrite magmas showed temperature differences of 60–100 °C and pressure differences of several kilobars. Individual magma chambers therefore, would have extended over several kilometres vertically. The chemical potential of water may have been constant through the magma.  相似文献   

4.
Redox states of lithospheric and asthenospheric upper mantle   总被引:31,自引:7,他引:24  
The oxidation state of lithospheric upper mantle is heterogeneous on a scale of at least four log units. Oxygen fugacities ( ) relative to the FMQ buffer using the olivine-orthopyroxene-spinel equilibrium range from about FMQ-3 to FMQ+1. Isolated samples from cratonic Archaean lithosphere may plot as low as FMQ-5. In shallow Proterozoic and Phanerozoic lithosphere, the relative is predominantly controlled by sliding Fe3+-Fe2+ equilibria. Spinel peridotite xenoliths in continental basalts follow a trend of increasing with increasing refractoriness, to a relative well above graphite stability. This suggests that any relative reduction in lithospheric upper mantle that may occur as a result of stripping lithosphere of its basaltic component is overprinted by later metasomatism and relative oxidation. With increasing pressure and depth in lithosphere, elemental carbon becomes progressively refractory and carbon-bearing equilibria more important for control. The solubility of carbon in H2O-rich fluid (and presumably in H2O-rich small-degree melts) under the P,T conditions of Archaean lithosphere is about an order of magnitude lower than in shallow modern lithosphere, indicating that high-pressure metasomatism may take place under carbon-saturated conditions. The maximum in deep Archaen lithosphere must be constrained by equilibria such as EMOG/D. If the marked chemical depletion and the orthopyroxene-rich nature of Archaean lithospheric xenoliths is caused by carbonatite (as opposed to komatiite) melt segregation, as suggested here, then a realistic lower limit may be given by the H2O +C=CH4+O2 (C-H2O) equilibrium. Below C –H2O a fluid becomes CH4 rather than CO2-bearing and carbonatitic melt presumably unstable. The actual in deep Archaean lithosphere is then a function of the activities of CO2 and MgCO3. Basaltic melts are more oxidized than samples from lithospheric upper mantle. Mid-ocean ridge (MORB) and ocean-island basalts (OIB) range between FMQ-1 (N-MORB) and about FMQ +2 (OIB). The most oxidized basaltic melts are primitive island-arc basalts (IAB) that may fall above FMQ+3. If basalts are accurate probes of their mantle sources, then asthenospheric upper mantle is more oxidized than lithosphere. However, there is a wide range of processes that may alter melt relative to that of the mantle source. These include partial melting, melt segregation, shifts in Fe3+/Fe2+ melt ratios upon decompression, oxygen exchange with ambient mantle during ascent, and low-pressure volatile degassing. Degassing is not very effective in causing large-scale and uniform shifts, while the elimination of buffering equilibria during partial melting is. Upwelling graphite-bearing asthenosphere will decompress along -pressure paths approximately parallel to the graphite saturation surface, involving reduction relative to FMQ. The relative will be constrained to below the CCO equilibrium and will be a function of . Upwelling asthenosphere whose graphite content has been exhausted by partial melting, or melts that have segregated and chemically decoupled from a graphite-bearing residuum will decompress along -decompression paths controlled by continuous Fe3+-Fe2+ solid-melt equilibria. These equilibria will involve increases in relative to the graphite saturation surface and relative to FMQ. Melts that finally segregate from that source and erupt on the earth's surface may then be significantly more oxidized than their mantle sources at depth prior to partial melting. The extent of melt oxidation relative to the mantle source may be directly proportional to the depth of graphite exhaustion in the mantle source.  相似文献   

5.
Near-liquidus phase relationships of a spinel lherzolite-bearing olivine melilitite from Tasmania were investigated over a P, T range with varying , , and . At 30 kb under MH-buffered conditions, systematic changes of liquidus phases occur with increasing ( = CO2/CO2 +H2O+olivine melilitite). Olivine is the liquidus phase in the presence of H2O alone and is joined by clinopyroxene at low . Increasing eliminates olivine and clinopyroxene becomes the only liquidus phase. Further addition of CO2 brings garnet+orthopyroxene onto the liquidus together with clinopyroxene, which disappears with even higher CO2. The same systematic changes appear to hold at higher and lower pressures also, only that the phase boundaries are shifted to different . The field with olivine- +clinopyroxene becomes stable to higher with lower pressure and approaches most closely the field with garnet+orthopyroxene+clinopyroxene at about 27 kb, 1160 °C, 0.08 and 0.2 (i.e., 6–7% CO2+ 7–8% H2O). Olivine does not coexist with garnet+orthopyroxene+clinopyroxene under these MH-buffered conditions. Lower oxygen fugacities do not increase the stability of olivine to higher and do not change the phase relationships and liquidus temperatures drastically. Thus, it is inferred that olivine melilitite 2927 originates as a 5% melt (inferred from K2 O and P2O5 content) from a pyrolite source at about 27kb, 1160 dg with about 6–7% CO2 and 7–8% H2O dissolved in the melt. The highly undersaturated character of the melt and the inability to find olivine together with garnet and orthopyroxene on the liquidus (in spite of the close approach of the respective liquidus fields) can be explained by reaction relationships of olivine and clinopyroxene with orthopyroxene, garnet and melt in the presence of CO2.  相似文献   

6.
Two metamorphic isograds cut across graphitic schist near Pecos Baldy, New Mexico. The southern isograd marks the first coexistence of staurolite with biotite, whereas the northern isograd marks the first coexistence of andalusite with biotite. The isograds do not record changes in temperature or pressure. Instead, they record a regional gradient in the composition of the metamorphic fluid phase. Ortega Quartzite, which contains primary hematite, lies immediately north of the graphitic schist. Mineral compositions within the schist change gradually toward the quartzite, reflecting gradients in and . The chemical potential gradients, locally as high as 72 cal/m in and 9 cal/m in , controlled the positions of the two mapped isograds. The staurolite-biotite isograd records where fell below 0.80, at near 10–23 bars; the andalusite-biotite isograd records where fell below 0.25, at near 10–22 bars. Dehydration and oxidation were coupled by graphite-fluid equilibrium.The chemical potential gradients apparently formed during metamorphism, as graphite in schist reacted with hematite in quartzite. Local oxidation of graphite formed CO2 which triggered dehydration reactions along the schistquartzite contact. This process created a C-O-H fluid which infiltrated into overlying rocks. Upward infiltration, local fluid-rock equilibration and additional infiltration proceeded until the composition of the infiltrating fluid evolved to that in equilibrium with the infiltrated rock. This point occurs very close to the staurolite-biotite isograd. Pelitic rocks structurally above this isograd show no petrographic evidence of infiltration, even though calculations indicate that volumetric fluid/rock ratios may have exceeded 15 and thin, rare calc-silicate beds show extensive K-metasomatism and quartz veining.  相似文献   

7.
Iron chlorites with compositions intermediate between the two end-members daphnite (Fe5Al2Si3O10(OH)8) and pseudothuringite (Fe4Al4Si2O10(OH)8) were synthesized from mixtures of reagent chemicals. The polymorph with a 7 Å basal spacing initially crystallized from these mixtures at 300 °C and 2 kb after two weeks. Conversion to a 14 Å chlorite required a further 6 weeks at 550 °C. Shorter conversion times were required at higher water pressures. The products contained up to 20% impurities.The maximum equilibrium decomposition temperature for iron chlorite, approximately 550 °C at 2kb, is at an between assemblages (1) and (2) listed below. Synthetic iron chlorite will break down by various reactions with variable P, T, and fugacity of oxygen. For the composition FeAlSi = 523, the sequence of high temperature breakdown products with increasing traversing the magnetite field for P total = =2kb is: (1) corierite+ fayalite+hercynite; (2) cordierite+fay alite+magnetite; (3) cordierite+magnetite+quartz; (4) magnetite+mullite+quartz. Almandine should replace cordierite in assemblages (1) and (2) but it did not nucleate. The significance of the relationship between iron cordierite and almandine in this system is discussed.At water pressures from 4 to 8.5 kb and at the nickel-bunsite buffer, iron chlorite+quartz break down to iron gedrite+magnetite with temperature 550 to 640 °C along the curve. At temperatures 50 °C greater and along a parallel curve, almandine replaces iron gedrite. For on this buffer curve, almandine is unstable below approximately 4 kb for temperatures to approximately 750 °C.  相似文献   

8.
Thermal aureoles surrounding intrusions of the Nain complex, Labrador, contain many unique or unusual mineral assemblages in aluminous gneisses and granulites, ironstones, and ultramafic rocks. Some of the limiting assemblages are (in addition to feldspars±pyrrhotite±ilmenite±graphite ±biotite±magnetite): Ga-Ol-Hy-Sp, Ga-Cd-Hy-Sp, Ga-Hy-Ol-Qz, Cd-Hy-Os-Qz, Ga-Cd-Sp-Si, Cd-Sp-Co-Si, Ga-Ol-Hy-Sp, Ga-Cd-Hy-Sp, Hy-Ol-Qz-Aug, and Ol-Hy-Sp(±Chl±Ca-amph±Aug). On the basis of some of these assemblages are (in addition to feldspars±pyrrhotite±ilmenite±graphite from 3.7–6.6 kbar and temperatures from 645–915 ° C. The paucity of hydrous phases, the preponderance of Ksp-Plag-Qz or even Cd-Ksp-Qz without evidence of a melt at these temperatures, the stable occurrence of osumilite, and the common presence of graphite suggest that was extremely low. The presence of graphite-pyrrhotite, the compositions of ilmenites, the compositions of coexisting Fe-Ti oxides, and other mineralogical data indicate the was relatively low and, despite the wide range in bulk compositions and rock types, may have followed an approximately buffered trend. It is possible that the magmas of the Nain complex may have acted as an external buffer for the aureole rocks. The unique nature of these mineral assemblages appears to be a function of the extremely low .  相似文献   

9.
The oxygen fugacity ( ) of a C-O-H fluid in equilibrium with graphite has been determined in the range 10–30 kbar by equilibrating solid -buffer assemblages in graphite capsules containing C-O-H fluid. By using different buffers (FexO-Fe3O4, Ni-NiO, Co-CoO, Mo-MoO2), the of the graphite-saturated fluid is bracketed within a narrow range. This technique produces a calibration for the imposed on a sample contained within a graphite capsule. To achieve a thermodynamically-invariant system at fixed P and T, the was imposed on the system with an external buffer and the double-capsule technique. The experiments were performed in solid-media, high pressure apparatus with 19 mm tale-pyrex assemblies. A series of experiments at 10, 15, 20, 25, and 30 kbar, 800–1600° C, with imposed by the Fe2O3-Fe3O4-H2O equilibrium were conducted. The experimental results have been fitted to the following equation:
  相似文献   

10.
Summary Bastnaesites of Ce and La and their OH-analogs were synthesized and their stability relations were determined atPf = 1 kbar andT = 400 to 900°C in a part of the system (Ce,La)-F-H-C-0. The initial fluid compositions were such that and HF/(HF + H2O) ratios were 0 to 0.172. XRD and IR studies indicate that bastnaesites equilibrated in initial fluids low in HF are all F-enriched. The hydroxylbastnaesite-(La) is stable up to 810°C and the fluorbastnaesite-(La) is stable up to 860°C. Their condensed breakdown products are La2O2CO3 and LaOF, respectively. The stability of Ce bastnaesites is slightly dependent. The hydroxylbastnaesite-(Ce) is stable up to 660°C at the defined by the IQF buffer and up to 640°C by the MH buffer. The fluorbastnaesite-(Ce) is stable up to 800°C at the defined by the IQF and up to 760°C by the MH buffer. The condensed breakdown product for the hydroxyl end-member is simply CeO2 but for the fluorine one is a combination of CeO2, CeF3, and CeOF. Factors, such as OH vs F, , and bulk composition, that affect the stability of individual species are discussed. Petrogenic implications resulting from the present study include that bastnaesites can be stable from hydrothermal to magmatic conditions, that F-enriched species can form in an environment relatively low in F content, and that OH-species are rare and occur only in low-temperature environments essentially devoid of F.
Synthese und Stabilität von Bastndsil in einem Teil des Systems (Ce,La)-F-H-C-O
Zusammenfassung Ce- und La-Bastnäsite, sowie deren OH-Analoga wurden synthetisiert und ihre Stabilitätsbeziehunger beiP f = 1 kbar undT = 400 bis 900°C wurden im System (Ce,La)F-H-C-O bestimmt. Die anfänglichen Flüssigkeitszusammensetzungen waren so, daß und die HF/(HF + H2O)-Verhältnisse 0–0.172 waren. Röntgenpulver- und Ultrarot-Untersuchungen zeigten, daß Bastnäsite, die mit anfänglich HF-armen Flüssigkeiten equilibriert wurden, alle an F angereichert sind. Hydroxilbastndsit-(La) ist bis 810°C und Fluorbastnäsit-(La) bis 860°C stabil. Ihre festen Zersetzungsprodukte sind La2O2O3, bzw. LaOF. Die Stabilität der Ce-Bastnäsite hängt etwas von ab. Hydroxilbastnäsit-(Ce) ist bei des Eisen-Quarz-Fayalit-Puffers bis 660°C stabil und mit Magnetit-Hämatit-Puffer bis 640°C. Das feste Zerfallsprodukt ist für das Hydroxil-Glied nur CeO2, für das Fluor-Glied eine Mischung aus CeO2, CeF3 und CeOF. Faktoren, welche die Stabilität der einzelnen Spezies beeinflussen, werden diskutiert, wie das Verhältnis OH zu F, und die Gesamtzusammensetzung. Petrogenetische Folgerungen aus der vorliegenden Studie schließen ein, daß Bastnäsite von hydrothermalen bis zu magmatischen Bedingungen stabil sein können, daß sich an F angereicherte Glieder in relativ F-armer Umgebung bilden können, und daß OH-Glieder selten sind und nur unter Bildungsbedingungen niedriger Temperatur und weitgehender Abwesenheit von F auftreten.


With 8 Figures  相似文献   

11.
Aenigmatite, sodic pyroxene and arfvedsonite occur as interstitial minerals in metaluminous to weakly peralkaline syenite patches in alkali dolerite, Morotu, Sakhalin. Aenigmatite is zoned from Ca, Al, Fe3+-rich cores to Ti, Na, Mn, Si-rich rims reflecting the main substitutions Fe2+Ti4+Fe3+, NaSiCaAl and Mn2+Fe2+. Aenigmatite replaces aegirine and ilmenite supporting the existence of a no-oxide field in — T space. In one case aenigmatite has apparently formed by reaction between ilmenite and arfvedsonite. Titanian aegirine (up to 3.0 wt% TiO2) and Fe-chlorite may replace aenigmatite. Sodic pyroxene occurs as zoned crystals with cores of aegirine-augite rimmed by aegirine and in turn by pale green aegirine containing 93 mol% NaFe3+Si2O6. Additional substitution of the type NaAlCaFe2+ is indicated by significant amounts (up to 6 mol%) of NaAlSi2O6. Arfvedsonite is zoned with rims enriched in Na, Fe and depleted in Ca which parallels the variation of these elements in the sodic pyroxenes.The high peralkalinity of the residual liquid from which the mafic phases formed resulted from the early crystallization of microperthite (which makes up the bulk of the syenites) leading to an increase in the Na2O/(Na2O+K2O) and (Na2O+K2O)/Al2O3 ratios of the remaining interstitial liquid which is also enriched in Ti, Fe, and Mn. Bulk composition of the melt, , temperature and volatile content were all important variables in determining the composition and stability of the peralkaline silicates. in the residual liquid appears to have been buffered by arfvedsonite-aegirine and later by the arfvedsonite-aenigmatite and aenigmatite-aegirine equilibria under conditions of a no-oxide field. An increase in , above that of the alkali buffer reactions, is inferred by an increase of Ti and Mn in aenigmatite rims. The latest postmagmatic vapour crystallization stage of the syenites is marked by extremely low which may have been facilitated by exsolution of a gas phase. Low is supported by the replacement of aenigmatite by titanian aegirine, and the formation of rare Ti-rich garnet with a very low (Ti4++Fe3+)/(Ti+Fe) ratio of 0.51, associated with leucoxene alteration of ilmenite.  相似文献   

12.
A simple modification was made to the reaction vessel designed by Shaw (1963) in order to use it as a hydrogen sensor instead of a hydrogen source, thereby allowing a continuous record of to be made during an experiment. The advantage of this arrangement is that (reversed) curves for minerals can be generated from a single experimental run. Other applications are possible.This method was successfully used in the determination of the Ni-NiO-H2O equilibrium between 580 ° and 830 °C at 2 kbar fluid pressure. The corrected 1 atm values are in agreement with electrochemical measurements. An Ag70Pd30 hydrogen permeable membrane was used for the experiment and flow rates of hydrogen through the membrane were calculated by monitoring the rate of increase or decrease in pressure with an induction pressure transducer. These flow rates range up to two times greater than those calculated for a pure platinum membrane.  相似文献   

13.
Deerite, Fe 12 2+ Fe 6 3+ [Si12O40](OH)10, thus far known from ten localities in glaucophane schist terranes, was synthesized at water pressures of 20–25 kb and temperatures of 550–600 °C under the of the Ni/NiO buffer. The X-ray powder diagram, lattice constants and infrared spectrum of the synthetic phase are closely similar to those of the natural mineral. A solid solution series extends from this ferri-deerite end member to some 20 mole % of a hypothetical alumino-deerite, Fe 12 2+ Al 6 3+ [Si12O40](OH)10. The upper temperature breakdown of ferri-deerite to the assemblage ferrosilite +magnetite+quartz+water occurs at about 490 °C at 15 kb, and 610 °C at 25 kb fluid pressure for the of the Ni/NiO buffer. Extrapolation of these data to lower water pressures indicates that deerite can be a stable mineral only in very low-temperature, high-pressure environments.  相似文献   

14.
The phenocryst assemblage of cummingtonite, orthopyroxene, quartz, titanomagnetite and ilmenite in rhyolites of New Zealand has been used to calculate P total and . The values of P total and depend strongly upon whether an ideal mixing, or an ordered, model is used for the solid-solutions, but in both cases P total.The rhyolite magma contained over 9 per cent water (by weight) when the cummingtonite phenocrysts precipitated, and possibly as much as 12 per cent, so that it is surprising that one of these rhyolites is a coherent lava. The calculated values of P total and are very sensitive to uncertainty in both the composition of the solid-solutions and temperature. Calculations show that >0.7–0.8 P total for cummingtonite to precipitate in rhyolites, and that iron-rich olivine and cummingtonite could only exist in rhyolites over a small temperature range at a pressure near 5 kilobars. Hornblende phenocrysts co-existing with fayalitic olivine in rhyolites accordingly have a very low activity of Mg7Si8O22(OH)2.  相似文献   

15.
The proportions of species in a C-O-H-S fluid in equilibrium with graphite, pyrite and pyrrhotite were calculated for a range of pressure, temperature and conditions, using the equilibrium constants and mass balance method, for ideal and non-ideal mixing in the fluid. Under typical metamorphic conditions, H2O, CO2, CH4 and H2S are the principal fluid species with H2S favored by higher temperatures, lower pressures and lower conditions. The dominance of H2S in the fluid at high temperatures leads to values of becoming significantly less than 1, and causes hydrous minerals to dehydrate at lower temperatures than the case when . The production of H2S-bearing fluids provides a mechanism for the selective transfer of sulfur from a graphite-pyrite-pyrrhotite bearing pelite into a pluton via a fluid phase, without requiring wholesale melting and assimilation of rocks. Such a process is feasible if a magma is intruded by stoping, which allows a significant volume of pelite country rock to be raised rapidly to temperatures approaching that of the magma. H2S-bearing fluids produced from graphite-pyrite-pyrrhotite pelites (due either to magmatic intrusion or regional metamorphism) may also mobilize ore-forming metals as sulfide complexes.  相似文献   

16.
Microphenocrystic pyrrhotites were observed in the glassy groundmass of two dacite rocks from Satsuma-Iwojima, southwest Kyushu, Japan. It suggests that the dacite magma was saturated with respect to pyrrhotite at the time of eruption, and thus the sulfur contents in the groundmass can be taken as the solubility of sulfur in the dacite magma. The solubility of sulfur in the dacite rocks thus calculated is 65 to 72 ppm sulfur at the estimated conditions of T=900±50°C, and atm.  相似文献   

17.
To investigate the point defect chemistry and the kinetic properties of manganese olivine Mn2SiO4, electrical conductivity () of single crystals was measured along either the [100] or the [010] direction. The experiments were carried out at temperatures T=850–1200 °C and oxygen fugacities atm under both Mn oxide (MO) buffered and MnSiO3 (MS) buffered conditions. Under the same thermodynamic conditions, charge transport along [100] is 2.5–3.0 times faster than along [010]. At high oxygen fugacities, the electrical conductivity of samples buffered against MS is 1.6 times larger than that of samples buffered against MO; while at low oxygen fugacities, the electrical conductivity is nearly identical for the two buffer cases. The dependencies of electrical conductivity on oxygen fugacity and temperature are essentially the same for conduction along the [100] and [010] directions, as well as for samples coexisting with a solid-state buffer of either MO or MS. Hence, it is proposed that the same conduction mechanisms operate for samples of either orientation in contact with either solid-state buffer.The electrical conductivity data lie on concave upward curves on a log-log plot of vs , giving rise to two regimes with different oxygen fugacity exponents. In the low- regime , the exponent, m, is 0, the MnSiO3-activity exponent, q, is 0, and the activation energy, Q, is 45 kJ/mol. In the high regime 10^{ - 7} {\text{atm}}} \right)$$ " align="middle" border="0"> , m=1/6, q=1/4–1/3, and Q=45 and 200 kJ/mol for T<1100 °c=" and=">T>1100 °C, respectively.  相似文献   

18.
The interdependence of the Fe(Mg)–1 (e.g., FeO-MgO in silicate melt; CaFeSi2O6-CaMgSi2O6 in pyroxene) and TiAl2(MgSi2)–1 exchange reactions between silicate melts and coexisting Ca-pyroxene has been examined. High-calcium clinopyroxenes were grown in 1 atmosphere melting and crystallization experiments on rock powders spanning the composition range tholeiite to melilitite (1,0922+Mg2+ exchange and suggest that at given values of extent of Fe(Mg)–1 substitution is strongly coupled with the TiAl2(MgSi2)–1 substitution in pyroxenes near the five-component space CaMg(Si2O6-CaFe(Si)2O6-CaTi(Al)2O6-CaFe(Al,Si)2O6-CaAl(Al,Si)2O6. The inferred stabilization of Ti in iron-rich relative to magnesium pyroxene is consistent with the operation of Fe2+Ti4+ intervalence charge transfer interactions (e.g., Rossman 1980) and observations on zoning in natural titanaugites (e.g., Tracy and Robinson 1977). Although the rims of some pyroxenes grown in some melting experiments exhibit prominent zoning in TiAl2(MgSi2)–1, the average values of inferred from the compositions of these pyroxenes, together with those of the relatively homogeneous pyroxenes produced in crystallization experiments, exhibit a 11 correlation with values of derived from the solution model of Ghiorso et al. (1983) with a standard error of 750 calories. The Ti contents of Ca-rich pyroxenes crystallizing from a wide range of natural silicate liquids can therefore be predicted.  相似文献   

19.
Fluid inclusions occur in a composite xenolith from the Lunar Crater Volcanic Field, Nevada, U.S.A. The xenolith is an amphibole-bearing wehrlite that is cut by an andesine-amphibole vein. The compositions of individual fluid inclusions in both portions of the xenolith have been determined using microthermometry and micro Laser-Raman spectroscopy. Fluids in the host wehrlite are nearly pure CO2 (>99 mol%) whereas those in the vein contain from 8.5 to 12.0 mol % CO in CO2. Chemical modelling shows that the composition of the vein fluids at T room is representative of the composition at the high P, T conditions of trapping. Graphite has not been observed by optical microscopy in any of the fluid inclusions. Graphite is probably absent (although stable at T<800° C) most probably because of the kinetically unfavorable CO decomposition reaction and rapid quenching. By combining the measured fluid compositions with fluid P-V-T data and the chemical equilibrium CO2CO +1/2 O2, we have calculated the oxygen fugacity of the fluid inclusions at 1200° C: log 8.6 (vein) and –6 (host). If the of the fluid in the vein represents that in equilibrium with the magma that crystallized to produce the vein, then the of the basalt magma is near QFM at 1200° C and 10.3 kbar. This is similar to values reported for extrusive basaltic lavas. If the much lower intrinsic oxygen fugacity-values for divines and spinels from alkali basalt nodules are representative of upper mantle conditions, then oxidation of basaltic magmas must occur in the upper mantle prior to ascent to the surface. Implications for the origin of CO2-rich fluids and carbon isotope geochemistry are also discussed.  相似文献   

20.
The compositions of coexisting pyroxmangites, rhodonites, rhodochrosites and manganese calcites in regional metamorphosed manganese cale-silicate marbles from Val Scerscen and Alagna were analysed by microprobe and permit definition of critical tie lines at metamorphic grades appropriate to temperatures between 400 and 450 °C.Variations in composition of coexisting mineral pairs in one and the same locality are attributed to variations in and not to metamorphic temperatures. From the analysed assemblages isothermal plots (with SiO2 as excess component) were constructed for the system CaO-MnO-SiO2-CO2.  相似文献   

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