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1.
Two parameters GO2– and HO2– are defined as the differences between respectively the Gibbs free energies and the enthalpies of formation of an oxide and its corresponding aqueous cation. The Gibbs free energies and enthalpies of formation of phosphates from their consituent oxides are shown to be linear functions of respectively GO2– and HO2– of their constituent cations.  相似文献   

2.
Fluoride-hydroxyl exchange equilibria between phlogopite-pargasite and phlogopite-tremolite mineral pairs were experimentally determined at 1,173K, 500 bars and 1,073–1,173 K, 500 bars respectively. The distribution of fluorine between phlogopite and pargasite was found to favor phlogopite slightly, G ex . (1,173 K)=–1.71 kJ anion–1, while in the case of phlogopite-tremolite, fluorine was preferentially incorporated in the mica, G ex . (1,073)=– 5.67 kJ anion–1 and G ex . (1,173K)=–5.84 kJ anion–1. These results have yielded new values of entropy and Gibbs energy of formation for fluortremolite, S f =–2,293.4±16.0JK–1 mol–1 and G f = –11,779.3±25.0 kJ mol–1, respectively. In addition, F-OH mineral exchange equilibria support a recent molten oxide calorimetric value for the Gibbs energy of fluorphlogopite, G f =–6,014.0±7.0 kJ mol–1, which is approximately 40 kJ mol–1 more exothermic than the tabulated value.This work performed in part at Sandia National Laboratories supported by the U.S. Department of Energy, DOE, under contract number DE-AC04-76DP00789  相似文献   

3.
Sector zoning has been experimentally reproduced in CaMgSi2O6-CaTiAl2O6 clinopyroxene crystals by isothermal crystallization using seed crystals. Element partitioning in different growth sectors and between the core and rim portions in single crystals was analysed in relation to growth rate R and degree of supercooling T. The TiO2 and Al2O3 contents increase with increase in R and T, but when they are compared between different sectors in a single crystal grown at the same T, they correlate negatively with R. The order of faces in respect of contents of TiO2 and Al2O3 is (100)>(110)(010)(111) at T= 13° C and 18° C but changes to (110)>(100)>(010)>(111) at T= 25° C. The growth mechanism is concluded to be controlled by interface kinetics at T= 13–25° C for all these faces, while at T=45° C this relation holds for (100) and (010) faces, but not for (110) and (111), based on the growth rate versus supercooling relation and surface microtopographic observations. The interface kinetics play the essential role in the formation of sector zoning, when the layer growth mechanism takes place.  相似文献   

4.
The discrepancy between the tabulated Gibbs Energies of Formation for Al2SiO5 and corundum relative to muscovite and kaolinite is considered to lie principally with the latter two minerals. New values for heat of formation of gibbsite [Gbs] will affect the tabulated H f 0 , G f(298,1) 0 for the other aluminous minerals which are referred to gibbsite as calorimetric aluminum reference. Gibbs Energy Difference Functions, calculated from phase equilibria in the system CaO-Al2O3-SiO2-(H2O-CO2), can be used to estimate consistent H f 0 , G f(298,1) 0 values for aluminous minerals. A self consistent data set is presented referred to G f(298,1) 0 [Corundum]=–378.08 kcal mol–1. Two independent values for G f(298,1) 0 [Anorthite]=–961.52 and –960.29 kcal, from a recalculation of the H f 0 [Anor] based upon the revised H f(298,1) 0 [Gbs]=–309.325 kcal mol–1 and from measurement of silica activity on the anorthite-saturated part of the CaO-Al2O3-SiO2 liquidus, respectively, are considered to show the magnitude of the discrepancy and are used in the calculations.  相似文献   

5.
Kyser, O'Neil, and Carmichael (1981, 1982) measured the 18O values of coexisting minerals from peridotite nodules in alkali basalts and kimberlites, interpreting the nodules as equilibrium assemblages. Using Ca-Mg-Fe element-partition geothermometric data, they proposed an empirical18O/16O geothermometer: T(°C)=1,151–173–68 2, where is the per mil pyroxene-olivine fractionation. However, this geothermometer has an unusual crossover at 1,150 °C, and in contrast to what might be expected during closed-system equilibrium exchange, the most abundant mineral in the nodules (olivine) shows a much greater range in 18O (+4.4 to +7.5) than the much less abundant pyroxene (all 50 pyroxene analyses from spinel peridotites lie within the interval +5.3 to +6.5). On 18O-olivinevs. 18O-pyroxene diagrams, the mantle nodules exhibit data arrays that cut across the 18O=zero line. These arrays strongly resemble the non-equilibrium quartzfeldspar and feldspar-pyroxene 18O arrays that we now know are diagnostic of hydrothermally altered plutonic igneous rocks. Thus, we have re-interpreted the Kyser et al. data as non-equilibrium phenomena, casting doubt on their empirical geothermometer. The peridotite nodules appear to have been open systems that underwent metasomatic exchange with an external, oxygen-bearing fluid (CO2, magma, H2O, etc.); during this event, the relatively inert pyroxenes exchanged at a much slower rate than did the coexisting olivines and spinels, in agreement with available exchange-rate and diffusion measurements on these minerals. This accounts for the correlation between 18O pyroxene-olivine and the whole-rock 18O of the peridotites, which is a major difficulty with the equilibrium interpretation.Contribution No. 3978, Publications of the Division of Geological and Planetary Sciences, California Institute of Technology  相似文献   

6.
An analytical approach to the analysis of zoning profiles in minerals is presented that simultaneously accounts for all of the possible continuous reactions that may be operative in a given assemblage. The method involves deriving a system of simultaneous linear differential equations consisting of a Gibbs-Duhem equation for each phase, a set of linearly independent stoichiometric relations among the chemical potentials of phase components in the assemblage, and a set of equations describing the total differential of the slope of the tangent plane to the Gibbs free energy surface of solid solution phases. The variables are the differentials of T, P, chemical potentials of all phase components, and independent compositional terms of solid solution phases. The required input data are entropies, volumes, the compositions of coexisting phases at a reference P and T, and an expression for the curvature of the Gibbs functions for solid solution phases. Results derived are slopes of isopleths (dP/dT, dX/dT or dX/dP) which can be used to contour P-T diagrams with mineral composition.To interpret mineral zoning, T and P can be expressed as functions of n independent composition parameters, where n is the variance of the mineral assemblage. The total differentials of P and T are differential equations that can be solved by finite difference techniques using the derivatives obtained from the analytical formulation of phase equilibria.Results calculated from Zone I and Zone IV garnets of Tracy et al. (1976) indicate that Zone I garnets grew while T increased (T+72° C) and P decreased sharply (P–3 kb). Zone IV garnets zoned in response to decreasing T (T–17° C) and P (P–1 kb). A P-T path calculated for a zoned garnet from the Greinerschiefer series, western Tauern Window, Austria, also indicates growth during decompression (–3kb) and heating (T+15° C). A P-T path calculated for the Wissahickon schist (Crawford and Mark 1982) indicates growth during cooling and compression (T–25 C, P+2.2 kb). The calculated P-T paths differ according to structural environment and can be used to relate mineral growth to tectonic processes.  相似文献   

7.
The abundance of coexisting structural units in K-, Na-, and Li-silicate melts and glasses from 25° to 1654°C has been determined with in-situ micro-Raman spectroscopy. From these data an equilibrium constant, Kx, for the disproportionation reaction among the structural units coexisting in the melts, Si2O5(2Q3)SiO3(Q2)+SiO2(Q4), was calculated (Kx is the equilibrium constant derived by using mol fractions rather than activities of the structural units). From ln Kx vs l/T relationships the enthalpy (Hx) for the disproportionation reaction is in the range of-30 to 30 kJ/mol with systematic compositional dependence. In the potassium and sodium systems, where the disproportionation reaction shifts to the right with increasing temperature, the Hx increases with silica content (M/Si decreases, M=Na, K). For melts and supercooled liquids of composition Li2O·2SiO2 (Li/Si=1), the Hx is indistinguishable from 0. By decreasing the Li/Si to 0.667 (composition LS3) and beyond (e.g., LS4), the disproportionation reaction shifts to the left as the temperature is increased. For a given ratio of M/Si (M=K, Na, Li), there is a positive, near linear correlation between the Hx and the Z/r2 of the metal cation. The slope of the Hx vs Z/r2 regression lines increases as the system becomes more silica rich (i.e., M/Si is decreased). Activity coefficients for the individual structural units, i, were calculated from the structural data combined with liquidus phase relations. These coefficients are linear functions of their mol fraction of the form i=a lnX i+b, where a is between 0.6 and 0.87, and X i is the mol fraction of the unit. The value of the intercept, b, is near 0. The relationship between activity coefficients and abundance of individual structural units is not affected by temperature or the electronic properties of the alkali metal. The activity of the structural units, however, depend on their concentration, type of metal cation, and on temperature.  相似文献   

8.
The plots of axial ratios, X/Y and Y/Z, of deformed pebbles of quartz and quartzite occupy the constriction field. It is proved by comparision of observed data with the theoretical models, that the finite shapes of deformed pebbles showing constriction-type deformation ellipsoid has resulted due to superimposition of the schistosity forming flattening-type deformation of F2 phase on the nappe forming flattening-type of F1 deformation phase. The deformed shapes of pebbles indicate that the principal direction of maximum extension (X) of the finite deformation ellipsoid lie parallel to subparallel to the axial directions of F2 and F3 folds.
Zusammenfassung Diagrammdarstellungen der Achsenverhältnisse X/Y und Y/Z ergeben für deformierte Quarz- und Quarzitgerölle eine Lage im Konstriktionsfeld. Durch Vergleich der Beobachtungsdaten mit theoretischen Modellen wird nachgewiesen, daß die finiten Umrisse deformierter Gerölle mit einem Deformationsellipsoid vom Konstriktionstyp sich aus der überlagerung der die Schieferung verursachenden Deformationsphase F2 mit Plättungstyp über die deckenbildende Deformationsphase F1 mit Plättungstyp ergaben. Die deformierten Umrisse der Gerölle zeigen, daß die Hauptrichtung größter Extension (X) des finiten Deformationsellipsoides parallel oder annähernd parallel zur Achsenrichtung der F2- und F3-Falten liegt.
Résumé Les diagrammes de rapports d'axes X/Y et Y/Z relatifs à la déformation de galets de quartz et de quartzite montrent une localisation dans un champ de constriction. En comparant les données de l'observation avec des modèles théoriques on voit que les contours des galets déformés suivant un ellipsoÏde de déformation du type constriction résultent de la superposition de la phase de déformation F2, du type applatissement, déterminant la schistosité, sur la phase de déformation F1, du mÊme type, liée aux nappes. Les contours déformés des galets montrent que la direction principale de la plus grande extension (X) de l'ellipsoÏde de déformation affine est parallèle, ou approximativement parallèle, à la direction des axes des plis F2 et F3.
X/Y Y/Z . , F2, , F1 . , (X) , F2 F3.
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9.
Grenville dolomitic marbles and calc-silicates at Stephen Cross Quarry, Québec, underwent contact metamorphism and metasomatism associated with the intrusion of the Wakefield syenite at ambient pressures of 0.4GPa at 1090–1070Ma. Fluid infiltration produced exoskarns, calcite+periclase+forsterite±diopside±orthoclase assemblages in the marbles, and quartz±calcite±wollastonite±diopside±anorthite assemblages in the calc-silicates. Phase-equilibria in the CaO–MgO–Al2O3–SiO2–H2O–CO2 system suggest that fluid infiltration occurred close to the thermal peak of contact metamorphism (715–815°C) and that the fluids hadXCO20.15. In the metasediments, 18O values of calcite (Cc) are as low as 8.6, suggesting that the fluids were in isotopic equilibrium with the syenites (18O =8.8–10.2). Marble 13C(Cc) values are-0.1 to-3.2; the lack of correlation between 13C(Cc) and 18O(Cc) is consistent with the infiltration of water-rich fluids. The resetting of stable isotopes and the mineralogical changes can be explained by time-integrated fluid fluxes of up to 110 m3/m2 (4×106 mol/m2), corresponding to actual fluxes of 3×10-11 to 3×10-12 m3/m2-s and intrinsic permeabilities of 10-18 to 10-20 m2 for fluid flow lasting 0.1-1Ma. Marble 18O(Cc) values do not correlate well with distance from the syenite, and fluids were probably channelled across lithological layering. The correlation between the degree of resetting of marble 18O(Cc) values with the abundance of submillimetre-wide veins, suggests that fluid focussing may have resulted from variations in fracture density. Late, lower temperature (<500°C), fluid flow formed serpentine (Serp) and brucite (Br) from periclase and forsterite. 18O(Br) and 18O(Scrp) values correlate with 18O(Cc), suggesting that retrogression involved only limited volumes of fluid. The observation that 18O(Cc-Br) and 18O(Cc-Serp) values are higher in marbles that have lower 18O(Cc) values is interpreted as indicating that fluid flow persisted to lower temperatures in those rocks due to higher intrinsic permeabilities. Calcite in the syenite was also formed by the influx of fluids during cooling. Syenite 18O(Cc) values are approximately in isotopic equilibrium with the high-temperature silicate minerals, suggesting that again only minor volumes of fluid were involved. In detail fluid flow was prolonged and complex, creating problems for the application of quantitative fluid flow models.This paper is a contribution to IGCP 304, Lower Crustal Processes  相似文献   

10.
Explosive eruptions of this large Quaternary rhyolitic volcano have produced voluminous pumice fall deposits and ignimbrites. A stratigraphie study reveals more than 30 fall deposits, totalling more than 90 km3, which have come from many different vents. Some are of plinian type, and one is among the largest known in the world. The main ignimbrite (Rio Caliente) is of intra-plinian type. In all, 140 km3 of rhyolitic material were erupted during the past 105 years, of which 50 km5 are dispersed well outside the volcano. The dense rock equivalent volume is 60 km3, of which fall deposits, ignimbrites and lava bodies comprise 45 %, 25 % and 30 % respectively. The average output rate of 0.06 km3 per century is nearly an order of magnitude less than for the most productive rhyolitic volcanoes known. A circular area 10 km across in the centre of La Primavera contains updomed lacustrine ashes and associated sediments, including a remarkable giant pumice bed, which probably accumulated in a caldera lake. La Primavera has no record of historical eruptions, and hot springs are the only signs of present activity, but the updoming is thought to be due to the uprise of a new acid pluton beneath the volcano and future eruptions are probable.
Zusammenfassung Explosionsartige Eruptionen des gro\en quartÄren Rhyolith-Vulkans La Primavera haben mÄchtige Bimstuffe und Ignimbrite aufgehÄuft. Eine stratigraphische Untersuchung hat über 30 Aschelagen erkennen lassen, die aus verschiedenen Schloten stammen und insgesamt mehr als 90 km3 an Volumen ausmachen. Einige davon gehören zum plimanischen Typ, von denen eine sogar die grö\te bisher bekannte Lage der Erde ist. Der Haupt-Ignimbrit (Rio Caliente) gehört zum intraplimanischen Typ. Insgesamt wurden in den letzten 100 000 Jahren 140 km3 rhyolithisches Material ausgeworfen, von denen 50 km3 deutlich au\erhalb des eigentlichen Vulkans liegen. Das Äquivalentvolumen des dichten Gesteins betrÄgt 60 km3, von dem 45 % auf Tuffe, 25 % auf Ignimbrite und 30 % auf Lavakörper entfallen. Die durchschnittliche Auswurfrate von 0,06 km3 pro Jahrhundert liegt fast eine Grö\enordnung unter den meisten bekannten aktiven Rhyolith-Vulkanen. Ein kreisrundes Gebiet von 10 km Durchmesser im Zentrum des La Primavera zeigt aufgewölbte lakustrine Aschen und damit assoziierte Sedimente, darunter eine bemerkenswerte riesige Bimslage, die wahrscheinlich in einem Caldera-See abgelagert wurde. Der Vulkan La Primavera ist in historischer Zeit nicht ausgebrochen und hei\e Quellen sind die einzigen Anzeichen heutiger AktivitÄt, aber die Aufwölbung wird als Hinweis auf das Hochdringen eines neuen sauren Plutons unter dem Vulkan angesehen, so da\ zukünftige Eruptionen wahrscheinlich sind.
Résumé Des éruptions explosives de ce grand volcan rhyolitique quaternaire ont produit de volumineux dépÔts de ponces et d'ignimbrites. Une étude stratigraphique fait apparaÎtre plus de 30 dépÔts totalisant plus de 90 km3 provenant de nombreuses bouches volcaniques différentes. Certaines sont du type plinien, dont l'une est parmi les plus grandes connues au monde. L'ignimbrite principale (Rio Caliente) est du type intraplinien. En tout 140 km3 de matériaux rhyolitiques ont été rejetés au cours des 105 dernières années, dont 50 km3 ont été dispersés bien au delà du volcan. Le volume de roche compact équivalent est de 60 km3, parmi lequel les tuffs, les ignimbrites et les laves occupent respectivement 45%, 25% et 30%. L'émission moyenne, de 0,06 km3 par siècle, est d'un ordre de grandeur moindre que pour la plupart des volcans rhyolitiques les plus productifs actuellement connus. Une région circulaire de 10 km de diamètre dans le centre de La Primavera contient des domes de cendres lacustres et autres sédiments associés, et parmi eux une couche géante de ponce remarquable, qui s'est probablement accumulée dans un lac-caldère. On ne connaÎt pas d'éruptions historiques de la Primavera, et seules des sources chaudes témoignent d'une activité actuelle; toutefois on pense que l'allure en dome est due à la poussée d'un nouveau pluton acide sous le volcan, et que des éruptions sont probables dans le futur.
- . 30 , ; 90 3. , . - - - . 3 100 000 140 3 , 50 3 . 60 , 45% , 25% 30% . 0,06 ; , . 10 - , , , . - , , , , .
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11.
New sulphur and sulphate-oxygen isotope measurements for the main discordant and stratiform lead-zinc-barite orebodies at Silvermines Co. Tipperary, allow reappraisal of previously offered differing interpretations (Graham, 1970; Greig et al., 1971) of the bearing of sulphur isotopes on the genesis of this important Irish deposit. The following aspects of the data are confirmed: barite 34 S-values range from 17–21, similar to lower Carboniferous seawater sulphate: stratiform sulphide lens pyrites have 34 S-values ranging from –13 to –36; vein sulphide 34 S-values range from –8 to 4; sulphide 34 S-values increase upwards and outwards respectively in the related discordant and stratiform G orebodies; galena-sphalerite isotope palaeotemperatures are not too consistent, ranging from 40 to 430°C (using the calibration of Czamanske and Rye (1974). New facts are as follows: barite 18O-values range from –13 to –17, stratiform barites ranging from 13 to 14.5; sulphides separated from a single stratiform ore lens hand specimen usually have 34 Ssl > 34 Sga > 34 Spy; the outward decrease in 34 S-values in the stratiform G orebody is confined to the first few hundred feet only; pyrite 34 S-values progressively increase downwards through one stratiform sulphide orebody; yet variations of 13 occur within a single colloform pyrite structure from another stratiform orebody. It is concluded that there were at least two sources of sulphur, seawater sulphate and deep-seated sulphur. The former was the dominant source of all sulphate and, via biogenic reduction, of the sulphur in the bulk of the stratiform sulphide. The latter was the source of the sulphur in the vein sulphides. There was minimal isotopic interaction between the cool seawater sulphate and the warm unwelling ore fluid sulphur species, even though the latter precipitated under near isotopic equilibrium conditions when the temperature dropped and/or the pH and Eh increased. The lack of isotopic equilibrium between pyrite and ore sulphides in the stratiform ore lenses may result from the latter having precipitated slightly later than the former because of solubility relationships. Overall the present isotopic evidence supports considerable geological evidence favoring a syngenetic origin for the stratiform Silvermines orebodies.  相似文献   

12.
Oxygen and hydrogen isotope analyses have been made of mineral separates from eclogites, glaucophanites and glaucophane schists from the eastern Sesia zone (Italian Western Alps). Regularities in (1) hydrogen isotope compositions, (2) order of 18O enrichment among coexisting minerals, and (3) 18O (quartz-rutile) and 18O (quartz-phengite) imply attainment of a high degree of isotopic equilibrium. However, some scattering of 18O values of individual minerals indicates that the eclogitic assemblage did not form in the presence of a thoroughly pervasive fluid. Minerals from an eclogitic lens enclosed in marble have 18O values distinctly different from those measured in the other rocks. The 18O values are high in comparison with other type C eclogites of the world, and it is proposed that the fluid present during the high pressure metamorphism has to a large extent been inherited from the precursor rocks of amphibolite facies.An average formation temperature of 540 ° C is inferred from the oxygen isotope fractionations between quartz and rutile and between quartz and white mica. This temperature is in accordance with petrologic considerations and implies subduction of the precursor rocks into the upper mantle to achieve the high pressures required.  相似文献   

13.
DC and AC electrical conductivities were measured on samples of two different crystals of the mineral aegirine (NaFeSi2O6) parallel () and perpendicular () to the [001] direction of the clinopyroxene structure between 200 and 600 K. Impedance spectroscopy was applied (20 Hz–1 MHz) and the bulk DC conductivity DC was determined by extrapolating AC data to zero frequency. In both directions, the log DC – 1/T curves bend slightly. In the high- and low-temperature limits, differential activation energies were derived for measurements [001] of EA 0.45 and 0.35 eV, respectively, and the numbers [001] are very similar. The value of DC [001] with DC(300 K) 2.0 × 10–6 –1cm–1 is by a factor of 2–10 above that measured [001], depending on temperature, which means anisotropic charge transport. Below 350 K, the AC conductivity () (/2=frequency) is enhanced relative to DC for both directions with an increasing difference for rising frequencies on lowering the temperature. An approximate power law for () is noted at higher frequencies and low temperatures with () s, which is frequently observed on amorphous and disordered semiconductors. Scaling of () data is possible with reference to DC, which results in a quasi-universal curve for different temperatures. An attempt was made to discuss DC and AC results in the light of theoretical models of hopping charge transport and of a possible Fe2+ Fe3+ electron hopping mechanism. The thermopower (Seebeck effect) in the temperature range 360 K < T <770 K is negative in both directions. There is a linear – 1/T relationship above 400 K with activation energy E 0.030 eV [001] and 0.070 eV [001]. 57Fe Mössbauer spectroscopy was applied to detect Fe2+ in addition to the dominating concentration of Fe3+.  相似文献   

14.
Mean and turbulent velocity measurements of supersonic mixing layers   总被引：1，自引：0，他引：1  
The behavior of supersonic mixing layers under three conditions has been examined by schlieren photography and laser Doppler velocimetry. In the schlieren photographs, some largescale, repetitive patterns were observed within the mixing layer; however, these structures do not appear to dominate the mixing layer character under the present flow conditions. It was found that higher levels of secondary freestream turbulence did not increase the peak turbulence intensity observed within the mixing layer, but slightly increased the growth rate. Higher levels of freestream turbulence also reduced the axial distance required for development of the mean velocity. At higher convective Mach numbers, the mixing layer growth rate was found to be smaller than that of an incompressible mixing layer at the same velocity and freestream density ratio. The increase in convective Mach number also caused a decrease in the turbulence intensity ( u /U).List of Symbols a speed of sound - b total mixing layer thickness betweenU 1 – 0.1U andU 2 + 0.1U - f normalized third moment ofu-velocity,f u 3/(U)3 - g normalized triple product ofu 2 v,g u 2 v/(U)3 - h normalized triple product ofu v 2, h uv' 2/(U)3 - l u axial distance for similarity in the mean velocity - l u axial distance for similarity in the turbulence intensity - M Mach number - M c convective Mach number (for 1=2),M c (U 1–U 2)/(a 1+a 2) - P static pressure - r freestream velocity ratio,rU 2/U 1 - Re unit Reynolds number,Re U/ - s freestream density ratio,s 2/ 1 - T t total temperature - u instantaneous streamwise velocity - u deviation ofu-velocity,u u–U - U local mean streamwise velocity - U 1 primary freestream velocity - U 2 secondary freestream velocity - U average of freestream velocities, ¯U (U 1 +U 2)/2 - U freestream velocity difference,U U 1 –U 2 - v instantaneous transverse velocity - v deviation ofv-velocity,v v – V - V local mean transverse velocity - x streamwise coordinate - y transverse coordinate - y 0 transverse location of the mixing layer centerline - ensemble average - ratio of specific heats - boundary layer thickness (y-location at 99.5% of free-stream velocity) - similarity coordinate, (y –y 0)/b - compressible boundary layer momentum thickness - viscosity - density - standard deviation - dimensionless velocity, (U –U 2)/U - 1 primary stream - 2 secondary stream A version of this paper was presented at the 11th Symposium on Turbulence, October 17–19, 1988, University of Missouri-Rolla  相似文献   

15.
A thermodynamic analysis of the intermediate solid solution (Iss) of near-cubanite composition has been attempted by considering an Fe–Zn exchange equilibrium between Iss and sphalerite. The interchange free-energy parameter of Fe–Zn mixing in Iss (WIss) and the free energy of the exchange equilibrium (G1,T ) have been deduced at 500, 600, 700 and 723° C using the compositional data of sphalerite and Iss from phase equilibrium experiments and by the standard method of linear regression analysis. For sphalerite, two independent activity-composition models have been chosen. The extracted values of G1,T and WIss, using both models, are compared. Although the values match, the errors in the extracted parameters are relatively larger when Hutcheon's model is used. Both G1,T and WIss show linear variations with temperature, as given by the following relations: G1,T = –35.41 + 0.033 T in kcal (SE=0.229)WISS= 48.451 – 0.041 T in kcal (SE=0.565) Activity-composition relations and different mixing parameters have been calculated for the Iss phase. A large positive deviation from ideality is observed in Iss on the join CuFe2S3–CuZn2S3. No geothermometric application has been attempted in this study, even though Iss of cubanite composition (isocubanite) in association with sphalerite, pyrite and pyrrhotite is reported from seafloor hydrothermal deposits. This is due to the fact that: (a) the temperatures of formation of these deposits are significantly lower than 500° C, the lower limit of appropriate experimental data base; (b) microprobe data of the coexisting isocubanite and sphalerite in the relevant natural assemblages are not available.Symbols a J i activity of component i in phase J - G1, T standard free energy change of reaction (cal) - GIM free energy of ideal mixing (cal) - GEM free energy of excess mixing (cal) - G M ex free energy of mixing (cal) - G i excess free energy of mixing at infinite dilution (cal) - i J activity coefficient of component i in phase J - i J, 0 standard chemical potential of component i in phase J (cal) - ; i J chemical potential of component i in phase J (cal) - R universal gas constant (1.98717 cal/K·mol) - T temperature in degree (K) - WJ interchange free energy of phase J in (cal) - X J i mole fraction of component i in phase J  相似文献   

16.
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   

17.
Denudation and vertical crustal movements are linked through the isostatic equation for conservation of lithospheric mass. Recent empirical results from a wide range of sources are presented on the rates of these processes. Denudation alone can cause non-tectonic (isostatic) surface uplift of the right magnitude predicted by theory. A case is made, following Ahnert, for a single linear relationship (although with much scatter) between denudation rate and mean drainage basin relief for large basins. Some recent determinations of denudational time constants have neglected to include tectonic and isostatic terms which oppose the reduction of relief by denudation. Application of diffusional transport models to determine the rate of sediment deposition are severely limited by inherent one-dimensionality and neglect of suspended and washload contributions. Basin infill sequences may be used to determine past sediment transfer coefficients from a hinterland, but problems arise in the apportionment of the various hinterland fluxes that occur in »real-world« three dimensional basins. Sediment yields in smaller half-graben and growth fold basins must reflect the magnitude of drainage basins and the complex local controls upon sediment yields. Examples are given from extensional basins in the Western USA and Greece. The »length« of tectonic relief produced in tilt blocks and growth folds will control the area of drainage basin developed (through the fractal form of Hack's Law) and hence the magnitude of deposition in sedimentary basins adjoining tectonic uplands.
Zusammenfassung Denudation und vertikale Krustenbewegungen sind verbunden durch das isostatische Gesetz über den Erhalt der lithosphärischen Masse. Neuerliche empirische Ergebnisse aus einem weiten Quellenbereich werden im Verhältnis zu diesen Prozessen präsentiert. Denudation allein, kann nicht tektonisch bedingte (isostatische) Oberflächenhebungen hervorrufen, die in der richtigen Größenordnung liegen, wie sie auch theoretisch ermittelt wurden. Es wird in Anlehnung an Ahnert ein Fall geschaffen, in der eine einfach lineare Beziehung (obgleich mit vielen Streuungen) zwischen der Denudationsrate und dem durchschnittlichen Abflußbeckenrelief für große Becken vorliegt. Einige neue Ermittlungen der Denudationszeitkonstanten wurden vernachlässigt, um tektonische und isostatische Begriffe einzufügen, welche sich der Verringerung des Reliefs durch Denudation widersetzen. Die Anwendung des Verbreitungstransportmodells zum Bestimmen der Sedimentationsrate sind streng begrenzt durch die ihm innewohnende Eindimensionalität, und der Vernachlässigung der Schwebe- und Schwämmfrachtbeteiligung. Bekkenfüllungssequenzen können benutzt werden um vergangene Sedimenttransferkoeffizienten aus dem Hinterland festzulegen; aber es treten auch Probleme bei der Verteilung der verschiedenen Hinterlandeinträge auf, die bei einem realen dreidimensionalen Becken vorhanden sind. Sedimenteinträge in kleineren Halbgräben und Growth-fold Becken müssen die Größe des Abflußbeckens widerspiegeln, sowie die komplexen lokalen Steuerungen auf die Sedimenteinträge. Beispiele von Dehnungsbecken aus dem Westen der USA und Griechenlands werden angesprochen. Die Länge des tektonischen Reliefs in verkippten Blöcken und Growth-Folds wird die Fläche des entwickelten Abflußbeckens kontrollieren (durch die fraktale Form des Gesetzes von Hack), und daher die Ablagerungsmenge von Sedimentbecken in der Nähe von tektonischen Hochlagen.
Résumé L'érosion et les mouvements crustaux verticaux sont liés par l'équation isostatique de conservation de la masse lithosphérique. Des résultats empiriques récents provenant d'un large éventail de sources sont présentés en relation avec ces processus. L'érosion seule peut être la cause d'une montée non tectonique (isostatique) dont l'ampleur est prévue exactement par la théorie. Un cas est présenté, d'après Ahnert, qui montre, pour de grands bassins, une relation linéaire simple (mais avec une forte dispersion des points) entre le taux de dénudation et le relief moyen de l'aire de drainage. Certaines déterminations récentes des constantes de temps de dénudation ont omis de tenir compte des termes tectonique et isostatique qui s'opposent à la destruction du relief par érosion. L'utilisation de modèles de transport diffus en vue de déterminer le taux d'accumulation des sédiments est sévèrement limitée par le caractère unidimensionnel de tels modèles et par le fait qu'il ne tiennent pas compte de la fraction en suspension. Les séquences de comblement d'un bassin sédimentaire peuvent être utilisées pour déterminer les anciens cfficients de transfert à partir de l'hinterland; mais des difficultés surgissent à propos de la répartition des différents flux en provenance de l'hinterland dans le cas réel d'un bassin à 3 dimensions. Les apports sédimentaires dans les bassins de demi-graben et de »growth-fold« doivent traduire la grandeur des aires de drainage et les facteurs locaux complexes qui régissent ces apports. Des exemples sont présentés, relatifs à des bassins d'extension de l'ouest des USA et de Grèce. La »longueur« des reliefs tectoniques en relation avec les blocs basculés et les »growth-folds« déterminent, par la forme fractale de la loi de Hack, la surface des aires de drainage ainsi engendrées et, en conséquence, l'importance des dépôts dans les bassins sédimentaires voisins des reliefs tectoniques.
. , . () , . , ( ) . , , , . , . , , ; , . « » (GrowthFolds) . . — « » Hack'a , , .
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18.
Temperature dependencies of magnetic rotation were measured in micron-sized silicates dispersed in ethanol for two different samples of kaolinite. Magnetic rotation proceeded by balance between thermal agitation energy and magnetic anisotropy energy. Measurements were performed between 195 and 343 K. The field intensity required to achieve magnetic alignment of microcrystals increases with temperature, because of the temperature dependence of paramagnetic anisotropy, and the temperature dependence of thermal agitation energy. The results indicate that the values of magnetic anisotropy of nonmagnetic materials might partially derive from the paramagnetic moments, which derive from paramagnetic impurity ions. The present experiment provides a technical basis for determining the precise values of diamagnetic anisotropy ()DIA from minerals which have a concentration of paramagnetic ions and do not form a single crystal large enough to allow bulk measurements. The values of ()DIA can be obtained by extrapolating the –T relations, which follow the Curie law, to the temperature limits.  相似文献   

19.
We have developed a new technique for the experimental determination of the activities of oxide components in melts and minerals using the equilibrium between Pd alloy, oxygen, and the oxide component in the sample of interest. If a melt or mineral sample is equilibrated with Pd metal at fixed P, T, and f O 2, a small amount of each constituent oxide will reduce to metal and dissolve into the Pd, forming an alloy. Due to the extraordinary stability of dilute alloys of Pd with Mg, Al, and Si, these metals dissolve into the Pd in amounts easily measured with the electron microprobe at f O 2 s that can be achieved with conventional gas-mixing techniques. We determined the activity-composition relations for Pd–Mg, –Al, and –Si alloys by equilibrating Pd at fixed f O 2and T with periclase, corundum, and cristobalite (a oxide1). Because Mg, Al, and Si have constant activity coefficients in Pd at low concentrations, the activity of the oxide of each metal is a simple function of the ratio of the concentration of the metal in Pd in equilibrium with the sample to that in Pd in equilibrium with the pure oxide. Therefore, if Pd plus a melt or mineral and Pd plus pure oxide standards are equilibrated simultaneously at fixed T and f O 2, the precision of the analytical technique is the major limitation on the determination of oxide activities. We used Pd-oxide equilibration to explore activities in silicate melts analogous to Type B Ca–Al-rich inclusions (CAIs) from carbonaceous chondrites; the measured activities deviate systematically from model valves but agree to within 1–30%. The activities imply that Type B CAIs did not condense as liquids from a gas of solar composition, and that only very aluminous compositions are potential liquid condensates from the solar nebula. We also used Pd-oxide equilibration to determine the free energy of formation from the oxides, G f /O , of the spinel end-member MgAl2O4 at 1150 to 1400°C to a precision of 2–19% (1). Because the technique reflects equilibration at high temperature, the G f /O s accurately represent the mineral with equilibrium Mg–Al disorder at temperature, a feature not true of drop calorimetric results because of partial reordering during quenching. Our results indicate more negative G f Emphasis>/O and hence higher entropy of formation, S f Emphasis>/O , than given in most compilations of thermodynamic data for spinel.Division of Geological and Planetary Sciences Contribution #5278  相似文献   

20.
Morphological and geological investigations along the Western Rift in the Lake Mobutu area (formerly Lake Albert), Uganda, East Africa are reviewed.Morphotectonic analyses reveal a complex interplay between rift faulting, erosion processes and sedimentation; an inversion of laterite surfaces in zones of subsidence and sedimentation is suggested. At least three phases of rift faulting can be recorded. The initiation of rift faulting is regarded as younger than the upper latente surface but pre lower Miocene.
Zusammenfassung Morphologische und geologische Untersuchungen am westlichen Zweig des ostafrikanischen Grabens im Bereich des Mobutu-Sees (früher Albert-See) in Uganda werden zusammen mit den Ergebnissen der bisherigen Arbeiten in einer Gesamtschau dargestellt.Morphotektonische Analysen ergeben ein kompliziertes Wechselspiel zwischen Grabentektonik, Erosions- und Sedimentationsprozessen, Eine Inversion der latente surfaces im Absenkungs- und Sedimentationsbereich wird angenommen.Wenigstens drei Bewegungsphasen an der Grabenrandverwerfung sind zu erfassen. Das Einsetzen der aktiven Grabentektonik beginnt nach Bildung des upper latente surface und vor der Ablagerung unter-miozäner Sedimente.
Résumé Des recherches géologiques et morphologiques du rift occidental dans la région du lac Mobutu (préalablement de lac Albert) en Ouganda, coordonnées avec les résultats d'études antérieures, sont offertes en vue d'ensemble.Les analyses morpho-tectoniques font ressortir des relations complexes entre la tectonique du fossé, l'érosion et la sédimentation. La possibilité d'une « inversion » des horizons latéritiques dans la région de subsidence et sédimentation s'annonce.Au moins trois phases de mouvement ont été ofservées le long de la faille qui délimite le fossé. L'activité tectonique du fossé commence après la formation de la «surface latéritique supérieure » et avant la sédimentation des couches du Miocène Inférieur.
- — — . - . « » «laterite surfaces» . - . «upper laterite surface» - .
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