首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

2.
A thermodynamic solution model is developed for minerals whose compositions lie in the two binary systems Mg2SiO4-Fe2SiO4 and Mg2Si2O6-Fe2Si2O6. The formulation makes explicit provision for nonconvergent ordering of Fe2+ and Mg2+ between M1 and M2 sites in orthopyroxenes and non-zero Gibbs energies of reciprocal ordering reactions in both olivine and orthopyroxene. The calibration is consistent with (1) constraints provided by available experimental and natural data on the Fe-Mg exchange reaction between olivine and orthopyroxene ± quartz, (2) site occupancy data on orthopyroxenes including both crystallographic refinements and Mössbauer spectroscopy, (3) enthalpy of solution data on olivines and orthopyroxenes and enthalpy of disordering data on orthopyroxene, (4) available data on the temperature and ordering dependence of the excess volume of orthopyroxene solid solutions, and (5) direct activity-composition determinations of orthopyroxene and olivine solid solutions at elevated temperatures. Our analysis suggests that the entropies of the exchange [Mg(M2)Fe(M1)Fe(M2)Mg(M1)] and reciprocal ordering reactions [Mg(M2)Mg(M1)+ Fe(M2)Fe(M1)Fe(M2)Mg(M1)+Mg(M2)Fe(M1)] cannot differ significantly (± 1 cal/K) from zero over the temperature range of calibration (400°–1300° C). Consideration of the mixing properties of olivine-orthopyroxene solid solutions places tight constraints on the standard state thermodynamic quantities describing Fe-Mg exchange reactions involving olivine, orthopyroxene, pyralspite garnets, aluminate spinels, ferrite spinels and biotite. These constraints are entirely consistent with the standard state properties for the phases-quartz,-quartz, orthoenstatite, clinoenstatite, protoenstatite, fayalite, ferrosilite and forsterite which were deduced by Berman (1988) from an independent analysis of phase equilibria and calorimetric data. In conjunction with these standard state properties, the solution model presented in this paper provides a means of evaluating an internally consistent set of Gibbs energies of mineral solid solutions in the system Mg2SiO4-Fe2SiO4-SiO2 over the temperature range 0–1300° C and pressure interval 0.001–50 kbars. As a consequence of our analysis, we find that the excess Gibbs energies associated with mixing of Fe and Mg in (Fe, Mg)2SiO4 olivines, (Fe, Mg)3Al2Si3O12 garnets, (Fe, Mg)Al2O4 and (Fe, Mg)Fe2O4 spinels, and K(Mg, Fe)3AlSi3O10(OH)2 biotites may be satisfactory described, on a macroscopic basis, with symmetric regular solution type parameters having values of 4.86±0.12 (olivine), 3.85±0.09 (garnet), 1.96±0.13 (spinel), and 3.21±0.29 kcals/gfw (biotite). Applications of the proposed solution model demonstrate the sensitivity of petrologic modeling to activity-composition relations of olivine-orthopyroxene solutions. We explore the consequences of estimating the activity of silica in melts forming in the mantle and we develop a graphical geothermometer/geobarometer for metamorphic assemblages of olivine+orthopyroxene+quartz. Quantitative evaluation of these results suggests that accurate and realistic estimates of silica activity in melts derived from mantle source regions,P-T paths of metamorphism and other intensive variables of petrologic interest await further refinements involving the addition of trace elements (Al3+ and Fe3+) to the thermodynamic formulation for orthopyroxenes.  相似文献   

3.
The petrochemistry of kimberlites from Yakutia and Lesotho has been studied using a silicate melt model with the SiO2, CO2 and H2O derivatives as the main anions.A model has been developed, according to which the dissolution of H2O in an ultramafic melt results in orthosilicates (H2SiC 4 -2 , H3SiO 4 – , H4SiO4 etc.) rather than metasilicates, while the dissolution of CO2 produces additional hydrocarbonate complexes. It suggests that at high PCO 2 1 , and where the orthosilicic calcium salt clusters are likely to be present in the magma, the kimberlite melt can break down into carbonate and silicate liquids. Therefore, the composition of kimberlite magma will be determined by the H2O/CO2 ratio under the relatively constant fluid pressure. This can be seen from the distinct fluidrs trend in the H2O-CO2-SiO2 diagram for the Yakutia and Lesotho diamond-bearing kimberlites. The H2O/CO2 ratio changes with the liquidus temperature along this trend (Perchuk and Vaganov 1977) which suggests that liquid immiscibility predominates over the simple CO2 solubility in the melts of kimberlite composition. The well-known Boyd's diagrams for the equilibrium PT-conditions in peridotites have been applied along with new experimental data to natural Cpx and Opx, and the PT-parameters were correlated for peridotite inclusions in kimberlite pipes in Yakutia and Lesotho. The liquidus temperatures for the extrapolated area of these correlations gave depths (pressures) at which kimberlite magmas are formed (200–250 km).The hypothesis on SiO2 partitioning between the melt and the fluid was used to calculate the composition of dry initial kimberlite which characterised the average mantle composition: SiO2 — 45.12; TiO2 — 2.49; Al2O3 — 3.58; Cr2O3 — 0.12; FeO — 9.32; MnO — 0.16; CoO — 0.11; MgO — 23.47; CaO — 13.44; Na2O — 0.20; K2O — 1.12; P2O5 — 0.69; S — 0.18; sum — 100 wt.%. This kimberlite is close to wehrlite in composition.  相似文献   

4.
Reactions which occur at the lower boundary of the hornblende-hornfels facies and in the so-called pyroxene-hornfels facies were experimentally investigated for an ultrabasic rock at 500, 1000 and 2000 bars H2O pressure.The starting material used was a mixture of natural chlorite, talc, tremolite and quartz such that its composition, except for surplus quartz, corresponded to that of an ultrabasic rock. The atomic ratio Fe2++Fe2+/Mg+Fe3++Fe3+ in the system was 0.16.The lower boundary of the hornblende-hornfels facies was defined by the formation of the orthorhombic amphibole anthophyllite and hornblende according to the following idealized reaction: chlorite+talc+tremolite+quartz hornblende+anthophyllite+H2O In effect, this reaction consists of the two bivariant reactions: chlorite+tremolite+quartz hornblende+anthophyllite+H2O talc+chlorite anthophyllite+quartz+H2OThe equilibrium temperatures obtained for the two reactions in the given system are practically the same and are as follows: 535±10°C at 500 bars H2O pressure 550±20°C at 1000 bars H2O pressure 560±10°C at 2000 bars H2O pressure 580±10°C at 4000 bars H2O pressureAt 2000 bars and higher temperatures within the hornblende-hornfels facies, anorthite is formed in addition to hornblende and anthophyllite, probably according to the following reaction: hornblende1+quartz hornblende2+anthophyllite+anorthite+H2O; because of the formation of anorthite it is to be expected that the hornblende in this case is poorer in aluminium than the hornblende at 500 and 1000 bars. Winkler (1967) suggests renaming the pyroxene-hornfels facies as K-feldspar-cordierite-hornfels facies which, in turn, is subdivided into a lower-temperature orthoamphibole subfacies without orthopyroxene and a higher-temperature orthopyroxene subfacies without orthoamphibole. The orthopyroxene subfacies itself may in its lower temperature part still carry hornblende which finally disappears in the higher temperature part.The appearance of orthopyroxene characterizes the transition from the orthoamphibole to the orthopyroxene subfacies of the K-feldspar-cordierite hornfels facies. The following reaction takes place at pressures lower than 2000 bars: hornblende1+anthophyllite hornblende2+enstatite+anorthite+H2OSince at 2000 bars an Al-poor hornblende already exists in the hornblende-hornfels facies, it is very likely that here only anthophyllite breaks down to give enstatite+quartz+H2O.The equilibrium temperatures for these reactions which give rise to enstatite are: 650±10°C at 250 bars H2O pressure 690±10°C at 500 bars H2O pressure 715±10°C at 1000 bars H2O pressure 770±10°C at 2000 bars H2O pressureOnly after an increase in temperature to about 710°C at 500 bars and about 770°C at 1000 bars does hornblende in the system investigated here break down completely according to the reaction: hornblende = enstatite+anorthite+diopside+H2OExcept at very small H2O-pressures (see Fig. 3), there exists, therefore, a region within the orthopyroxene subfacies where hornblende, enstatite and anorthite coexist. As a result we have, as mentioned above, a lower-temperature and a higher-temperature part of the orthopyroxene subfacies, and it is only in the latter part that the parageneses correspond to the pyroxene-hornfels facies as stated by Eskola (1939).Summing up, the starting material consisting of chlorite, talc, tremolite plus quartz remains unchanged in the albite-epidote-hornfels facies; this gives rise in the hornblende-hornfels facies to the paragenesis hornblende+anthophyllite, or — at higher pressures — to hornblende+anthophyllite+anorthite. For the particular composition of the starting material, however, no reactions take place at the transition of the hornblende-hornfels facies to the orthoamphibole subfacies of the K-feldspar-cordierite-hornfels facies as this transition is typified by the breakdown of muscovite in the presence of quartz. However, at the end of the orthoamphibole subfacies the breakdown of anthophyllite, by which orthopyroxene is formed, heralds the onset of the orthopyroxene subfacies. In this subfacies — at greater than about 300 bars — hornblende is still present and coexists with enstatite and anorthite, but with rising temperature hornblende breaks down to give way to the paragenesis enstatite+anorthite+diopside. The experimentally determined parageneses confirm known petrographic occurrences.

Für die Förderung dieser Arbeit danken wir der Deutschen Forschungsgemeinschaft vielmals. Der Dank von Choudhuri gilt dem Akademischen Auslandsamt der Universität Göttingen für ein Stipendium, das ihm den Abschluß seiner Studien an der Universität Göttingen ermöglichte.  相似文献   

5.
Fine-grained peraluminous synkinematic leuco-monzogranites (SKG), of Cambro-Ordovician age, occur as veins and sills (up to 20–30 m thick) in the Deep Freeze Range, within the medium to high-grade metamorphics of the Wilson Terrane. Secondary fibrolite + graphite intergrowths occur in feldspars and subordinately in quartz. Four main solid and fluid inclusion populations are observed: primary mixed CO2+H2O inclusions + Al2SiO5 ± brines in garnet (type 1); early CO2-rich inclusions (± brines) in quartz (type 2); early CO2+CH4 (up to 4 mol%)±H2O inclusions + graphite + fibrolite in quartz (type 3); late CH4+CO2+N2 inclusions and H2O inclusions in quartz (type 4). Densities of type 1 inclusions are consistent with the crystallization conditions of SKG (750°C and 3 kbar). The other types are post-magmatic: densities of type 2 and 3 inclusions suggest isobaric cooling at high temperature (700–550°C). Type 4 inclusions were trapped below 500°C. The SKG crystallized from a magma that was at some stage vapour-saturated; fluids were CO2-rich, possibly with immiscible brines. CO2-rich fluids (±brines) characterize the transition from magmatic to post-magmatic stages; progressive isobaric cooling (T<670°C) led to a continuous decrease off O 2 can entering in the graphite stability field; at the same time, the feldspars reacted with CO2-rich fluids to give secondary fibrolite + graphite. Decrease ofT andf O 2 can explain the progressive variation in the fluid composition from CO2-rich to CH4 and water dominated in a closed system (in situ evolution). The presence of N2 the late stages indicates interaction with external metamorphic fluids.Contribution within the network Hydrothermal/metamorphic water-rock interactions in crystalline rocks: a multidisciplinary approach on paleofluid analysis. CEC program: Human Capital and Mobility  相似文献   

6.
The mineral paragonite, NaAl2[AlSi3O10 (OH)]2, has been synthesized on its own composition starting from a variety of different materials. Indexed powder data and refined cell parameters are given for both the 1M and 2M1 polymorphs obtained. The upper stability limit of paragonite is marked by its breakdown to albite + corundum + vapour. The univariant equilibria pertaining to this reaction have been established by reversing the reaction at six different pressures, the equilibrium curve running through the following intervals: 1 kb: 530°–550° C 2 kb: 555°–575° C 3 kb: 580°–600° C 5kb: 625°–640° C 6 kb: 620°–650° C 7 kb: 650°–670° C.Comparison with the upper stability limit of muscovite (Velde, 1966) shows that paragonite has a notably lower thermal stability thus explaining the field observation that paragonite is absent in many higher grade metamorphic rocks in which muscovite is still stable.The enthalpy and entropy of the paragonite breakdown reaction have been estimated. Since intermediate albites of varying structural states are in equilibrium with paragonite, corundum and H2O along the univariant equilibrium curve, two sets of data pertaining to the entropy of paragonite (S 298 0 ) as well as the enthalpy ( H f,298 0 ) and Gibbs free energy ( G f,298 0 ) of its formation were computed, assuming (1) high albite and (2) low albite as the equilibrium phase. The values are: (1) (2) S 298 0 67.8±3.9 cal deg–1 gfw–1 63.7±3.9 cal deg–1 gfw–1 H f,298 0 –1417.9±2.7 kcal gfw–1 –1420.2±2.6 kcal gfw–1 G f,298 0 –1327.4±4.0 kcal gfw–1 –1328.5±4.0 kcal gfw–1.Adapted from a part of the author's Habilitationsschrift accepted by the Ruhr University, Bochum (Chatterjee, 1968).  相似文献   

7.
Samples located near the Oregon Dome anorthosite massif in the south-central Adirondack Mountains, New York contain the fluid-buffering mineral assemblages: amphibole + clinopyroxene + orthopyroxene + quartz or biotite + quartz + orthopyroxene + K-feldspar. These rocks were metamorphosed under granulite-facies conditions (T=725°–750°C, P=7.5 kbar) during the Grenville orogeny. The Mg-rich nature of amphiboles, micas, and pyroxenes allow accurate calculation of water activities because corrections for the effects of solid solution are relatively small. The activity of water was low during the peak of granulite-facies metamorphism, with H2O0.15±0.14. Wollastonite occurrences indicate that the CO2 was low (<0.3) in nearby rocks, demonstrating that large quantities of CO2 did not infiltrate in a pervasive manner. The combination of low H2O with low CO2 is consistent with the hypothesis that magmatic processes were dominant, generating dry, fluid-absent conditions.Abbreviations fi Fugacity of species i in a fluid - Xi mole fraction of component i in a phase - T temperature - P lithostatic pressure - P F fluid pressure - i x activity of component i phase X  相似文献   

8.
A new determination, using high temperature drop-solution calorimetry, of the enthalpy of transformation of MgSiO3 pyroxene to ilmenite gives H 298 = 59.03 ±4.26 kJ/mol. The heat capacity of the ilmenite and orthopyroxene phases has been measured by differential scanning calorimetry at 170–700 K; Cp of MgSiO3 ilmenite is 4–10 percent less than that of MgSiO3 pyroxene throughout the range studied. The heat capacity differences are consistent with lattice vibrational models proposed by McMillan and Ross (1987) and suggest an entropy change of -18 ± 3 J-K-1 ·mol-1, approximately independent of temperature, for the pyroxene-ilmenite transition. The unit cell parameters of MgSiO3 ilmenite were measured at 298–876 K and yield an average volume thermal expansion coefficient of 2.44 × 10-5 K-1. The thermochemical data are used to calculate phase relations involving pyroxene, -Mg2SiO4 plus stishovite, Mg2SiO4 spinel plus stishovite, and ilmenite in good agreement with the results of high pressure studies.  相似文献   

9.
Arrested charnockite formation in southern India and Sri Lanka   总被引：7，自引：3，他引：7  
Arrested prograde charnockite formation in quartzofeldspathic gneisses is widespread in the high-grade terrains of southern India and Sri Lanka. Two major kinds of orthopyroxene-producing reactions are recognized. Breakdown of calcic amphibole by reaction with biotite and quartz in tonalitic/granitic gray gneiss produced the regional orthopyroxene isograd, manifest in charnockitic mottling and veining of mixed-facies exposures, as at Kabbal, Karnataka, and in the Kurunegala District of the Sri Lanka Central Highlands. Chemical and modal analyses of carefully chosen immediately-adjacent amphibole gneiss and charnockite pairs show that the orthopyroxene is produced by an open system reaction involving slight losses of CaO, MgO and FeO and gains of SiO2 and Na2O. Rb and Y are depleted in the charnockite. Another kind of charnockitization is found in paragneisses throughout the southern high-grade area, and involves the reaction of biotite and quartz±garnet to produce orthopyroxene and K-feldspar. Although charnockite formation along shears and other deformation zones at such localities as Ponmudi, Kerala is highly reminiscent of Kabbal, close pair analyses are not as suggestive of open-system behavior. This type of charnockite formation is found in granulite facies areas where no prograde amphibole-bearing gneisses exist and connotes a higher-grade reaction than that of the orthopyroxene isograd. Metamorphic conditions of both Kabbaltype and Ponmudi-type localities were 700°–800° C and 5–6 kbar. Lower P(H2O) in the Ponmudi-type metamorphism was probably the definitive factor.CO2-rich fluid inclusions in quartz from the Kabbaltype localities support the concept that this type of charnockite formation was driven by influx of CO2 from some deep-seated source. The open-system behavior and high oxidation states of the metamorphism are in accord with the CO2-streaming hypothesis. CO2-rich inclusions in graphitebearing charnockites of the Ponmudi type, however, commonly have low densities and compositions not predictable by vapor-mineral equilibrium calculations. These inclusions may have suffered post-metamorphic H2 leakage or some systematic contamination.Neither the close-pair analyses nor the fluid inclusions strongly suggest an influx of CO2 drove charnockite formation of the Ponmudi type. The possibility remains that orthopyroxene and CO2-rich fluids were produced by reaction of biotite with graphite without intervention of fluids of external origin. Further evidence, such as oxygen isotopes, is necessary to test the CO2-streaming hypothesis for the Ponmudi-type localities.  相似文献   

10.
Granulite xenoliths within alkali olivine basalts of the Pali-Aike volcanic field, southern Chile, contain the mineral assemblage orthopyroxene + clinopyroxene + plagioclase + olivine + green spinel. These granulites are thought to be accidental inclusions of the lower crust incorporated in the mantle-derived basalt during its rise to the surface. Symplectic intergrowths of pyroxene and spinel developed between olivine and plagioclase imply that the reaction olivine+plagioclase = Al-orthopyroxene + Al-clinopyroxene + spinel (1) occurred during subsolidus cooling and recrystallization of a gabbroic protolith of the granulites.Examination of fluid inclusions in the granulites indicates the ubiquitous presence of an essentially pure CO2 fluid phase. Inclusions of three different parageneses have been recognized: Type I inclusions occur along exsolution lamellae in clinopyroxene and are thought to represent precipitation of structurally-bound C or CO2 during cooling of the gabbro. These are considered the most primary inclusions present. Type II inclusions occur as evenly distributed clusters not associated with any fractures. These inclusions probably represent entrapment of a free fluid phase during recrystallization of the host grains. IIa inclusions are found in granoblastic grains and have densities of 0.68–0.88 g/cm3. Higher density (=0.90–1.02 g/cm3) IIb inclusions occur only in symplectite phases. Secondary Type III CO2+glass inclusions with =0.47–0.78 g/cm3 occur along healed fractures where basalt has penetrated the xenoliths. Type III inclusions appear related to exsolution of CO2 from the host basalt during its ascent to the surface. These data suggest that CO2 is an important constituent of the lower crust under conditions of granulite facies metamorphism, indicated by Type I and II fluid inclusions, and of the mantle, as indicated by Type III inclusions.Correlation of fluid inclusion densities with P-T conditions calculated from both two-pyroxene geothermometry and reation (1) indicate emplacement of a gabbroic pluton at 1,200–1,300° C, 4–6 kb; cooling was accompanied by a slight increase in pressure due to crustal thickening, and symplectite formation occurred at 850±35° C, 5–7 kb. Capture of the xenoliths by the basalt resulted in heating of the granulites, and CO2 from the basalt was continuously entrapped by the xenoliths over the range 1,000–1,200° C, 4–6 kb. Examination of fluid inclusions of different generations can thus be used in conjunction with other petrologic data to place tight constraints on the specific P-T path followed by the granulite suite, in addition to indicating the nature of the fluid phase present at depth.  相似文献   

11.
OH structure of metamorphic fluids has been studied by high temperature infrared (IR) microspectroscopy on natural fluid inclusions contained in quartz veins, over the temperature range 25–370 °C. Blueschist-facies veins from Tinos island core complex (Cyclades, Greece) display H2O–NaCl–CaCl2–CO2 inclusions whereas greenschist-facies veins contain H2O–NaCl ± CO2 inclusions. From 25 to 370 °C, peak positions of OH stretching IR absorption bands increase quasi-linearly with slopes of 0.25 and 0.50 cm–1 °C–1 for inclusions trapped under blueschist and greenschist conditions, respectively. Extrapolation to 400 °C yield peak positions of 3,475 cm–1 for blueschist inclusions and 3,585 cm–1 for greenschist inclusions. Because the smaller wave number indicates the shorter hydrogen-bond distance between water molecules, fluids involved in the greenschist event have a loose structure compared with blueschist fluids. We suggest that these properties might correspond to a low wetting angle of fluids. This would explain the high mobility of aqueous fluids suggested by structural observation and stable isotope analysis.Editorial responsibility: J. Hoefs  相似文献   

12.
The upper-mantle source regions of basaltic magmas in oceanic regions contain both H2O and CO2. If the water content of the upper-mantle peridotite is (<0.4%) approx., then its solidus has a distinctive P,T character such that the geotherm for older oceanic regions will enter a zone of incipient (<2%) melting — the low-velocity zone (LVZ) — at depths of 85–95 km. This LVZ is overlain by a lithosphere of subsolidus amphibole-bearing peridotite in which there is a density increase at ~55 km due to the first appearance of garnet. An alternative model in which the LVZ is attributed to the presence of CO2 fluid phase bubbles is incompatible with experimental data showing high solubility of CO2 in basaltic magmas at the P,T conditions of the LVZ. The LVZ contains a small melt fraction as an intergranular film (aspect ratio <10−2); this melt is of olivine melilitite (CO2, H2O present) or olivine nephelinite (H2O only present) character and is interstitial to olivine > orthopyroxene > garnet > clinopyroxene mineralogy. Temperatures at the top of the LVZ are in the range 1000–1150°C. The lithosphere thickens with age and distance from the mid-oceanic ridges, reaching a stable configuration at a thickness of 85–95 km for t > 80 m.y. With increasing age of the oceanic crust, the velocities in the lithosphere increase, the LVZ becomes thinner, and the velocity contrast between the lithosphere and the LVZ decreases. The pyrolite petrological model and its velocity profile satisfactorily account for most of the geophysical data for various age provinces in oceanic regions.  相似文献   

13.
The univariant reaction governing the upper stability of heulandite (CaAl2Si7O18·6H2O), heulandite=laumontite+3 quartz+2H2O (1), has been bracketed through reversal experiments at: 155±6° C, 1000 bar; 175±6° C, 1500 bar; and 180±8° C, 2000 bar. Reversals were established by determining the growth of one assemblage at the expense of the other, using both XRD and SEM studies. The standard molal entropy of heulandite is estimated to be 783.7±16 J mol–1 K–1 from the experimental brackets. Predicted standard molal Gibbs free energy and enthalpy of formation of heulandite are –9722.3±6.3 kJ mol–1 and –10524.3±9.6 kJ mol–1, respectively. The reaction (1), together with the reaction, stilbite=laumontite+3 quartz+3 H2O, defines an invariant point at which a third reaction, stilbite=heulandite+ H2O, meets. By combining the present experimental data with past work, this invariant point is located at approximately 600 bar and 140° C. Heulandite, which is stable between the stability fields of stilbite and laumontite, can occur only at pressures higher than that of the invariant point, for = P total.These results are consistent with natural parageneses in low-grade metamorphic rocks recrystallized in equilibrium with an aqueous phase in which is very close to unity.  相似文献   

14.
The assemblage paragonite + quartz is encountered frequently in low- to medium-grade metamorphic rocks. With rising grade of metamorphism they react mutually to yield the condensed assemblage albite + Al2SiO5.The univariant curve pertaining to the equilibrium paragonite + quartz=albite + andalusite + H2O has been located experimentally. The reversed P H 2 O-T data are: 1 kb: 470–490° C 2 kb: 510–530° C 3 kb: 540–560° C 4 kb: 560–580° C 5 kb: 590–600° C The univariant curve pertaining to the equilibrium paragonite + quartz=albite + kyanite + H2O runs through the following P H 2 O-T-intervals: 5 kb: 570–625° C 6 kb: 600–630° C 7 kb: 620–640° C Thermodynamic calculations of S 298 0 , H f,298 0 and G f,298 0 of the phase paragonite from the experimental data presented above and those obtained from the equilibria of the reaction paragonite=albite + corundum + H2O (Chatterjee, 1970), agree within the limits of uncertainty. This prompts the idea that Zen's (1969) suggestion of a possible error of approximately 7 kcal in G f,298 0 of the Al2SiO5 polymorphs may in fact be due to an error of similar magnitude in G f,298 0 of corundum.A best estimate of S 298 0 , H f,298 0 and G f,298 0 of paragonite based on these considerations yield: S 298 0 : 67.61±3.9 cal deg–1 gfw–1 H f,298 0 : –1411.4±2.7 kcal gfw–1 G f,298 0 : –1320.9±4.0 kcal gfw–1 These numbers will be subject to change when better thermochemical data on corundum and albite are available.In medium-grade metamorphic rocks the assemblage paragonite + quartz is commonly found in stable coexistence with such other phases as muscovite, staurolite, andalusite, kyanite, but not with cordierite or sillimanite. However, the assemblage paragonite-sillimanite has been reported to be stable in the absence of quartz. All these petrologic observations can be explained on the basis of the stability data of the phases and phase assemblages concerned.  相似文献   

15.
Olivine clinopyroxenite xenoliths in the Oslo Rift,SE Norway   总被引：1，自引：0，他引：1  
Olivine clinopyroxenite xenoliths in a basalt flow at Krokskogen in the Oslo rift consist mainly of Al-Ti-rich clinopyroxene and alteration products after olivine (possibly also orthopyroxene). The clinopyroxene contains primary inclusions of Cr-Al-bearing titanomagnetite, pyrite and devitrified glass, and secondary fluid inclusions rich in CO2. On the basis of petrography, mineral compositions and bulk major and trace element chemistry, it is concluded that the xenoliths represent cumulates with about 5% trapped liquid, formed from a mildly alkaline basaltic magma. Microthermometrical analysis of secondary or pseudosecondary fluid inclusions give a minimum pressure of formation of 5.5 to 6 kbars, that is a depth greater than 16–17 km. The host lava has initial Nd=+4.16±0.17 and Sr=–5.50±0.26, which is believed to reflect the isotopic composition of the lithospheric mantle source region under south Norway in early Permian time. The isotopic character of the magma which gave rise to the xenoliths is preserved in clinopyroxenes which have Nd t =+1.9 to +2.6 and Sr t = –1.1 to –1.8. The isotopic differences between the host magma and the xenoliths reflect some degree of crustal contamination of the xenolith's parent magma.The xenoliths of this study represent an important source of information about the large masses of dense cumulates found at depth in the crust under the Oslo rift.  相似文献   

16.
Samples of granitic rock from south-central Maine contain primary igneous minerals altered by hydrothermal fluids. The reaction mechanisms (by which the over-all mineralogical change during the alteration was accomplished) involve several different mineral-fluid reactions at different reaction sites in the rock. The reactions involve both molecular and charged species in solution. The different reaction sites correspond to alteration of different primary igneous minerals. Biotite is partially converted to chlorite+sphene; microcline to muscovite; plagioclase to various combinations of muscovite, epidote, and calcite. The different reaction sites are linked by exchange of ions: some reaction sites produce ions consumed at other sites and vice versa. Physical conditions during the hydrothermal event are estimated from mineralogical and thermochemical data: P = 3,500 (±300) bars; T =425 ° (± 25 °)C. The fluid was characterized by X CO 2 = 0–0.13; ln([K+]/[H+ ]) = 10.0; ln([Ca2+]/[H+]2)=9.1; ln([Na+]/[H+]) = 10.5; Fe/(Fe+Mg) = 0.95. Amounts of secondary minerals in altered rock, when compared to the inferred mineral reactions that formed them, indicate that small but significant amounts (0.01–0.3mol/ 1,000cm3 altered rock) of CO2, H2O, H+, and K+ were added to the granites by fluids during the alteration, as well as lesser amounts (< 0.01–0.03 mol/1,000cm3 altered rock) of Mg2+, Fe2+, Fe3+, Mn2+, Na+, and Ti4+. The sole element leached from the granitic rocks during alteration was Ca in amounts 0.1–0.3 mol/1,000 cm3 rock. By estimating the composition of the hydrothermal fluids before and after reaction with the granites and by measuring the amount of material added to or subtracted from the granites during the alteration, the amount and volume of hydrothermal fluid involved can be calculated. Two independent calculations require minimum volumes in the range 100–1,000 cm3 fluid/1,000cm3 altered rock to participate in the hydrothermal event.  相似文献   

17.
A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe3O4–FeCr2O4 spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe1-x2+ Fex3+)[Fex2+Fe2-2y-x3+Cr2y]O4, and their thermodynamic properties depend strongly on Fe2+–Cr3+ cation mixing. Mixing of Fe2+–Fe3+ and Fe3+–Cr3+ can be accepted as ideal. If Fe2+, Fe3+ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x2/((1–x)(2–2y–x)))= G13* + (1–2x)W13+y(W14–W13–W34) where G13* is the difference between the Gibbs energy of inverse and normal magnetite, Wij is a Margules parameter of cation mixing and G13*, J/mol =–23,000+13.4 T, W14=36 kJ/mol, W13=W34=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe3O4–FeCr2O4 spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.  相似文献   

18.
The behaviour of synthetic Mg-ferrite (MgFe2O4) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K0=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by a0+a1*(T–298)+a2/(T–298)2, where a0=9.1(1) 10–6 K–1, a1=4.9(2) 10–9 K–2 and a2= 5.1(5) 10–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol–1 and =–17.6(± 1.2) kJ mol–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe2O4, which shows that the high-pressure transition from spinel to orthorombic CaMn2O4-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe2O3.  相似文献   

19.
Density measurements on nine liquids in the CaCO3–Li2CO3–Na2CO3–K2CO3 quaternary system were performed at 1 bar between 555 and 969 °C using the double-bob Archimedean method. Our density data on the end-member alkali carbonate liquids are in excellent agreement with the NIST standards compiled by Janz (1992). The results were fitted to a volume equation that is linear in composition and temperature; this model recovers the measured volumes within experimental error (±0.18% on average, with a maximum residual of ±0.50%). Our results indicate that the density of the CaCO3 component in natrocarbonate liquids is 2.502 (±0.014) g/cm3 at 800 °C and 1 bar, which is within the range of silicate melts; its coefficient of thermal expansion is 1.8 (±0.5)×10–4 K–1 at 800 °C. Although the volumes of carbonate liquids mix linearly with respect to carbonate components, they do not mix linearly with silicate liquids. Our data are used with those in the literature to estimate the value of in alkaline silicate magmas (20 cm3/mol at 1400 °C and 20 kbar), where CO2 is dissolved as carbonate in close association with Ca. Our volume measurements are combined with sound speed data in the literature to derive the compressibility of the end-member liquids Li2CO3, Na2CO3, and K2CO3. These results are combined with calorimetric data to calculate the fusion curves for Li2CO3, Na2CO3, and K2CO3 to 5 kbar; the calculations are in excellent agreement with experimental determinations of the respective melting reactions.Editorial responsibility: I Carmichael  相似文献   

20.
The curve of the reaction: 1 Rhodochrosite + 1 Quartz Pyroxmangite was determined experimentally using gas mixtures with different CO2H2O ratios at a total pressure of 2 kb. In pure CO2, the equilibrium temperature is 508±2° C. By plotting the equilibrium data in terms of InXCO2 versus reciprocal temperature, a H of reaction of 51.7 kcal was obtained. This plot shows a straight-line relationship, indicating internal consistency of the data, and is in good agreement with previous findings that CO2 and H2O mix ideally within the investigated temperature range (400–600° C). When applied to pyroxmangites formed during moderate greenschist facies metamorphism, these data indicate a high acitivity of H2O.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号