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1.
Multisystem nets are topological analogs of real and potentially real phase diagrams which can be constructed given only the chemography of phases of interest. Combinatorial analysis of c-component (c + 4)-phase multisystems suggests the existence of [(c + 4)!/2] [2(c +4) ? 2 (c + 4)] distinct nets. (c + 4)-phase multisystem nets are characterized by three different invariant point stability levels, four different reaction stability levels, and three invariant points along each univariant reaction. Invariant points at the intermediate stability level occur in two disjoint networks. Unlike (c + 3)-phase multisystems, in which all nets are related by transposition, (c + 4)-phase nets form distinct equivalence classes under transposition based on identities of those invariant points at the intermediate stability level. A position matrix is introduced to denote adjacency/connectivity relationships, and a relationship is suggested between the number of nets in each equivalence class under transposition and the number of ways of assigning stability levels to invariant points of an arbitrary position matrix.  相似文献   

2.
A new convenient combinatorial method is developed here to derive the invariant points in multisystem closed nets – the absent phase substitution (APS) method. It substantially simplifies the derivation of the closed nets in multisystems with many components and phases. For the multisystems whose total phase number (NPS) ≤ twice the number of the absent phases (m) in an invariant assemblage, the method can yield regular closed nets with or without globally absent phases; for other multisystems, the method can yield the regular closed nets with globally absent phases. As examples, the APS method was used to predict: (1) the regular closed nets of unary to quinary n + 4‐phase multisystems, unary 6‐phase multisystem and ternary 8‐phase multisystem; (2) the basic properties of the regular closed nets of the quaternary and quinary multisystems with n + 4 and n + 5 phases. Two multisystems were chosen to demonstrate how to select a realistic closed net from the numerous possible closed nets of a complex multisystem, and how to derive a realistic partially closed‐net, closed‐net‐diagram and the related realistic straight‐line‐net‐diagram. Comparisons of our APS method for the derivation of complicated closed nets with other methods indicate that this method is much simpler and more efficient.  相似文献   

3.
Multisystems of n+k (k > 3) phases are very complicated and knowledge of them has suffered as a result. The successful solution of the topological relationships in n+ 3 phase multisystems by Zen (1966, 1967) and Zen & Roseboom (1972) has aroused much interest regarding what will happen in a multisystem of more than n+ 3 phases. Since 1979, some important research results on this topic have been published. These results have expounded the substantial rules governing the appearance of phase relations in phase diagrams of n - k (k > 3) phase multisystems. The most significant conclusions include: (1) It is impossible to incorporate all the possible phase relations in an n+k (k > 3) phase multisystem in a single closed net. Therefore, it is no longer enough to use only a single closed net to depict the topological relations involved in these types of multisystems. Instead, one or more groups of closed nets, namely the complete system(s) of closed nets are necessary for this purpose. (2) A principle called the Combination Principle has been proposed and proved. It states: Any closed net of one n+k (k > 3) phase multisystem must be a combination of two or more distinct n+ 3 order submultisystem closed nets belonging to the given n+k phase multisystem, if it is not one of the n+ 3 order submultisystem closed nets itself. The combination principle provides both a theoretical basis and a practical method for the construction of closed nets and, hence, for the derivation of the real phase diagrams for any n+k (k > 3) phase multisystem. (3) A theorem on divariant-assemblage-characteristic-stability-polygons is also important to our understanding of the n+k (k± 3) phase multisystem closed nets. This theorem can be stated as follows: A divariant assemblage of an n+k (k± 3) phase multisystem will be stable in an l-polygon lacking diagonals in an appropriate set of closed-net-diagrams, and this l-polygon may be at least a triangle, and at most a k-polygon. In addition, the closed-net-diagrams of unary and binary n+ 4 phase multisystems derived respectively by Guo (1980b, 1980c, 1981a) and by Roseboom & Zen (1982) have also been summarized. The combination principle is applied to a practical petrological problem in this paper, dealing with 7 phases in the system FeO-Fe2O3-SiO2.  相似文献   

4.
A combinatorial and algebraic approach has been applied to the problem of determining the number of distinct configurations of univariant reaction lines about an invariant point, NC, in nondegenerate n-component systems. The resulting expression is $$NC = [1/(4n + 8)]\left( {\sum {[2^{d/2} (\phi (2n + 4)/d]) + (n + 2) 2^{\{ (n + 2)/2\} } } } \right) - 1$$ where the summation is taken over all values of d which divide (2n + 4)evenly but which do not divide (n + 2)evenly, [(n + 2)/2]is the smallest integer greater than or equal to (n + 2)/2,and ø[(2n + 4)/d]is the number of integers less than (2n + 4)/d whose only factor is common with (2n + 4)/d is 1.This concise expression is derived through the application of Burnside's lemma, which relates the number of equivalence classes into which a set S is divided by an equivalence relation induced by a permutation group of S to the number of elements of S left invariant by the members of the permutation group. In the derivation of the above expression, the set S is taken to be the set of all possible configurations and orientations of univariant lines about an invariant point, the permutation group is taken to be the set of rigid-body symmetries of S, and the equivalence classes are composed of the different orientations of each configuration. Although the methods used to obtain the above expression are probably unfamiliar to most geologists, they are standard mathematical techniques and represent just one application of these tools to problems of geologic interest.  相似文献   

5.
Graphical analysis of free-energy relationships involving binary quadruple points and their associated univariant equilibria in the system CO2-H2O suggests the presence of at least 2 previously unrecognized quadruple points and a degenerate binary invariant point involving an azeotrope between CO2-rich gas and liquid. Thermodynamic data extracted from the equilibrium involving clathrate (hydrate), gas, and ice (H = G+I) are employed along with published data to calculate the P-T range of the 3-ice equilibrium curve, S+I = H, where S is solid CO2. This equilibrium curve intersects the H = G+I curve approximately where the latter curve intersects the S+H = G curve, thus confirming the existence of one of the inferred quadruple points involving the phases S, G, H, and I. Recognition of some binary equilibria probably have been hampered by extremely low mutual solubilities of CO2 and H2O in the fluids phases which, for example, render the S+H = G virtually indistinguishable from the CO2-sublimation curve.To make the published portion of the L(liquid CO2)-G-H equilibrium “connect” with the other new quadruple point involving S, L, G, and H, it is necessary to change the sense of the equilibrium from L = G+H at higher pressures to L+H = G at lower pressures by positing a L = G azeotrope at very low concentrations of H2O. At the low-pressure origin of the azeotrope, which is only a few bars above the CO2-triple point, the azeotrope curve intersects the 3-phase curve tangentially, creating a degenerate invariant point at which the 3-phase equilibrium changes from L+H = G at lower pressures to L = G+H at higher pressures. The azeotrope curve is offset at slightly lower temperature from the L = G+H curve until the 3-phase equilibrium terminates at the quadruple point involving G, L, H, and W (water). With further increase in pressure the azeotrope curve tracks the L = G+W equilibrium and apparently terminates at a critical end point in close proximity to critical endpoints for the CO2-saturation curve and the L = G+W curve.Thermodynamic data for clathrate extracted from the slope of the H = G+I curve are consistent with a solid-state phase transformation in CO2-clathrate between 235 and 255 K. Published work shows that the type-I clathrate phase, whose atomic structure is a framework of water molecules with CO2 molecules situated in large “guest” sites within the framework, is variable in composition with ∼1 guest site vacancy per unit cell at the high-temperature limit of its stability; the number of water molecules, however, remains constant. The formula (CO2)8-y·46H2O, where y is the number of vacancies per unit cell, is in keeping with the atomic structure, whereas the traditional formula, CO2·nH2O, where n (hydration number) = 5.75, is misleading.Ambient P-T conditions in the Antarctic and Greenland ice sheets are compatible with sequestering large amounts of carbon as liquid CO2 and/or clathrate.  相似文献   

6.
Outside the Bergell tonalite contact aureole, ophicarbonate rocks consist of blocks of antigorite schist embedded in veins of calcite ± tremolite. An antigorite schistosity predates some of these calcite veins. Mono- and bimineralic assemblages occur in reaction zones associated with the veins. Within the aureole, the ophicarbonate veining becomes less distinct and polymineralic assemblages become more frequent. A regular sequence of isobaric univariant assemblages is found, separated by isograds corresponding to isobaric invariant assemblages. In order of increasing grade the invariant assemblages are: antigorite+diopside+olivine+tremolite+calcite antigorite+dolomite+olivine+tremolite+calcite antigorite+olivine+talc+magnesite antigorite+dolomite+olivine+tremolite+talc These assemblages match a previously derived topology in P-T-XCO2 space for the system CaO-MgO-SiO2-H2O-CO2; the field sequence can be used to adjust the relative locations of calculated invariant points with respect to temperature. Isobaric univariant and invariant assemblages are plotted along a profile map to permit direct comparison with the phase diagram.It is inferred that, during the formation of the ophicarbonate veins, calcite precipitated from fluid introduced into the serpentinite. During contact metamorphism, however, the compositions of pore fluids evolved by reaction in the ophicarbonate rocks were largely buffered by the solid phases. This control occurred on a small scale, because there are local variations in the buffering solid assemblages within a centimeter range.  相似文献   

7.
Abstract End-member, continuous and degenerate reactions are derived for the multisystem with the six components Na2O, CaO, (Mg/Fe)O, Al2O3, SiO2, H2O among the phases plagioclasess, garnetss, amphiboless, cpx, opx, olivine, spinel, quartz and an aqueous fluid. The chemography of this system is degenerate due to the co-linearity 2Opx = Ol + Qtz. This co-linearity has its implications both on reaction space and phase equilibria. From a total of 28 reaction systems, reaction space is derived for nine subsystems (phases in parentheses are absent): Case A1: (Cpx,Ol) (Cpx,Opx) and (Cpx,Qtz), Case A2: (Spl,Ol) (Spl,Opx) and (Spl,Qtz), Case B: (Ol,Opx) (Ol,Qtz) and (Opx,Qtz). In the absence of either cpx or spl (case A), three reactions form an invariant point, either [Cpx] or [Spl], where the co-linear phases olivine, opx and quartz coexist on the transformation line 2Opx = Ol + Qtz. Changing mineral compositions force invariant points to move along the line with the different reaction curves changing their relative position according to Schreinemakers’rules. Zero contours, i.e. the location where (a) phase(s) disappear(s) in reaction space correspond to singular points in phase diagrams. Two types are distinguished; singular points of indispensable and of substitutable phases. In the first case the phase disappears from the entire bundle while in the second it disappears from a single reaction. In the specific case where the substitutable phases are also the co-linear ones, two of the three co-linear phases disappear simultaneously. Two of the three reaction curves coincide. In the system including Cpx and Spl (Case B) three reactions, (Ol,Opx) (Ol,Qtz) and (Opx,Qtz), oppose three invariant points, [Ol], [Opx] and [Qtz]. Invariant points no longer move along the line 2Opx = Ol + Qtz. The coincidence of the zero contours of all three co-linear phases in reaction space-the result of the chemographic degeneracy-causes the respective singular points to coincide in the phase diagrams. This is the location where curves must be rearranged in a bundle to conform Schreinemakers’rules. The reaction Grs1Prp2= 2 Ol + An is fourth order degenerate and part of all nine subsystems (cases A and B). It can be used to relate the different phase diagrams to one another.  相似文献   

8.
Abstract Considering the minerals cordierite (Cd), sapphirine (Sa), hypersthene (Hy), garnet (Ga), spinel (Sp), sillimanite (Si) and corundum (Co) in the system FeO-MgO-Al2O3-SiO2 (FMAS), the stable invariant points are [Co], [Ga], [Cd] and [Sa]. Constraints imposed by experimental data for the system MAS indicate that under low P H2o conditions the invariant points occur at high temperature (> 900° C) and intermediate pressure (7-10 kbar). This temperature is higher than that commonly advocated for granulite facies metamorphism. In granulites Fe-Mg exchange geothermometers may yield temperatures of 100–150° C below peak metamorphic conditions and evidence for peak temperatures is best preserved by relict high-temperature assemblages and by Al-rich cores in orthopyroxene. Application of the FMAS grid to some well-documented granulite occurrences introduces important constraints on their P-T histories. Rocks of different bulk compositions, occurring in close proximity in the field, may record distinct segments of their P-T paths. This applies particularly to rocks with evidence for reaction in the form of coronas, symplectites and zoned minerals. Consideration of curved reaction boundaries and XMs isopleths may explain apparently contradictory results for the stability of cordierite obtained from low-temperature experiments and thermochemical calculations on the one hand and hightemperature experimental data on the other.  相似文献   

9.
Subsolidus and vapor-saturated liquidus phase relations for a portion of the system CaO-MgO-SiO2-H2O, as inferred from experimental data for the composition regions CaMgSi2O6-Mg2SiO4-SiO2-H2O and CaMgSi2O6-Mg2SiO4-Ca3MgSi2O8 (merwinite)-H2O, are presented in pressure-temperature projection. Sixteen invariant points and 39 univariant reactions are defined on the basis of the 1 atm and 10 kbar (vapor-saturated) liquidus diagrams. Lack of experimental control over many of the reactions makes the depicted relations schematic in part.An invariant point involving orthoenstatite, protoenstatite, pigeonite, and diopside (all solid solutions) occurs at low pressure (probably between 1 and 2 kbar). At pressures below this invariant point, orthoenstatite breaks down at high temperature to the assemblage diopside + protoenstatite; with increasing temperature, the latter assemblage reacts to form pigeonite. At pressures above the invariant point, pigeonite forms according to the reaction diopside + orthoenstatite = pigeonite, and the assemblage diopside + protoenstatite is not stable. At 1 atm, both pigeonite and protoenstatite occur as primary liquidus phases, but at pressures above 6–7 kbar orthoenstatite is the only Ca-poor pyroxene polymorph which appears on the vapor-saturated liquidus surface.At pressures above approximately 10.8 kbar, only diopside, forsterite, and merwinite occur as primary liquidus phases in the system CaMgSi2O6-Mg2SiO4-Ca3MgSi2O8-H2O, in the presence of an aqueous vapor phase. At pressures between 1 atm and 10.2 kbar, both akermanite and monticellite also occur as primary liquidus phases. Comparison of the 1 atm and 10 kbar vapor-saturated liquidus diagrams suggests that melilite basalt bears a low pressure, or shallow depth, relationship to monticellite-bearing ultrabasites.  相似文献   

10.
A petrogenetic grid for metapelites in the system NKFMASH is presented. The P–T range is investigated in three sections: (1) The high‐ and ultrahigh‐pressure range is discussed in the system NFMASH because phengite is the only stable potassic phase. (2) The transition region is characterised by four NKFMASH‐invariant points that separate high‐pressure glaucophane‐bearing from medium‐pressure biotite‐bearing metapelites. (3) The medium‐pressure range contains the fifth NKFMASH‐invariant point. The univariant reactions of this point terminate the stability range of paragonite, which breaks down to form staurolite or kyanite and plagioclase during decompression and/or heating. As the growth of albitic plagioclase by decomposition of paragonite via continuous reactions may be conspicuous already before these staurolite‐ or kyanite‐producing reactions are reached, such albite porphyroblast schists are typical indicators of a former high‐pressure metamorphic history. Considering the preservation of high‐pressure metapelitic assemblages, those crossing the NKFMASH‐transition region during exhumation commonly dehydrate and preservation is unlikely. Three types of metapelites have a fairly good survival potential: (1) low‐temperature metapelites (up to c. 540 °C) with an exhumation path back into the chlorite + albite stability field, (2) assemblages with chloritoid + glaucophane, and (3) the relatively high‐temperature glaucophane + kyanite and jadeite + kyanite bearing parageneses, that are relatively dry at the onset of exhumation. A comparison with data from the literature shows that these rock types are the most abundant in nature.  相似文献   

11.
The theoreticalP-T grid for stability relations of the phases cordierite (Cd), sapphirine (Sa), hypersthene (Hy), garnet (Ga), spinel (Sp), sillimanite (Si), and quartz (Qz) of Hensen (1971), has proved useful in the interpretation of metamorphic mineral assemblages formed at low oxygen fugacity. Both experimental data and evidence from natural rocks indicate that at high oxygen fugacity compatability relations change as a result of the enlargement of the stability field of spinel, which causes a topological inversion and the stabilisation of the invariant points [Sa], [Ga], and [Cd]. This implies the stable existence of the univariant equilibria (for buffered conditions): Sp+Qz=Ga+Hy+Si+O2 (Sa, Cd), Cd+Sp+Qz=Hy+Si+O2 (Sa, Ga) and Sa+Sp+Qz=Hy+Si+O2 (Ga, Cd) and the divariant reaction: Sp+Qz=Hy+Si+O2 (Sa, Ga, Cd). These redox equilibria are restricted to conditions of high oxygen fugacity. The proposed theoreticalP-T grids, for both low and high oxygen fugacity, satisfactorily explain all experimental data and metamorphic mineral assemblages so far found in granulites.  相似文献   

12.
ABSTRACT The metasedimentary sequence of the Deep Freeze Range (northern Victoria Land, Antarctica) experienced high-T/low-F metamorphism during the Cambro-Ordovician Ross orogeny. The reaction Bt + Sil + Qtz = Grt + Crd + Kfs + melt was responsible for the formation of migmatites. Peak conditions were c. 700–750° C, c. 3.5–5 kbar and xH2Oc. 0.5). Distribution of fluid inclusions is controlled by host rock type: (1) CO2-H2O fluid inclusions occur only in graphite-free leucosomes; (2) CO2–CH4± H2O fluid inclusions are the most common type in leucosomes, and in graphite-bearing mesosomes and gneiss; and (3) CO2–N2–CH4 fluid inclusions are observed only in the gneiss, and subordinately in mesosomes. CO2–H2O mixtures (41% CO2, 58% H2O, 1% Nad mol.%) are interpreted as remnants of a synmig-matization fluid; their composition and density are compatible P–T–aH2O conditions of migmatization (c. 750° C, c. 4 kbar, xH2Oc. 0.5). CO2-H2O fluid in graphite-free leucosomes cannot originate via partial melting of graphite-bearing mesosomes in a closed system; this would have produced a mixed CO2–CH4 fluid in the leucosomes by a reaction such as Bt + Sil + Qtz + C ± H2O = Grt + Crd + Kfs + L + CO2+ CH4. We conclude that an externally derived oxidizing CO2-H2O fluid was present in the middle crust and initiated anatexis. High-density CO2-rich fluid with traces of CH4 characterizes the retrograde evolution of these rocks at high temperatures and support isobaric cooling (P–T anticlockwise path). In unmigmatized gneiss, mixed CO2–N2–CH4 fluid yields isochores compatible with peak metamorphic conditions (c. 700–750° C, c. 4–4.5 kbar); they may represent a peak metamorphic fluid that pre-dated the migmatization.  相似文献   

13.
Phase relations in the 6-component system Na-K-Mg-Ca-SO4-Cl-H2O have been calculated for halite saturation, 25°C and 1 atm pressure. Using a Jänecke projection with the apices Ca-Mg-K2-SO4, 27 stable invariant points have been located which are connected by 69 univariant curves. Polyhalite is the only quaternary solid, but anhydrite occupies the bulk of the interior tetrahedral space. Consequently, 24 of the invariant points lie very close to the Ca-free base, Mg-K2-SO4. The remaining three points involve tachyhydrite and/or antarcticite. All points but two (20,27) represent peritectic conditions. Metastable equilibria have been calculated for the Ca-free system and yield relations corresponding to the solar diagram.Seawater lies in the subspace anhydrite-halite-carnallite-kieserite-bischofite (point 20) and its evaporation has been discussed for conditions of equilibrium and fractional crystallization. After gypsum is converted to anhydrite, halite precipitates. The next phase, under equilibrium conditions, is glauberite, crystallizing at the expense of anhydrite. Continued evaporation leads to glauberite resorption and eventual replacement by polyhalite. Then follow the magnesium sulfates epsomite, hexahydrite and kieserite, which are joined by carnallite. Polyhalite is replaced by anhydrite and bischoflte is added at the final invariant condition. Kainite does not appear as a primary phase under equilibrium conditions, but it is an important phase during fractional crystallization, where Ca-phases are not allowed to back-react with the brine.Up to the appearance of glauberite, thickness ratios of halite: anhydrite couplets (equilibrium or fractionation) can vary from 0 to 7, the relative amount of halite increasing with more intense evaporation. During evaporation, the activity of H2O decreases from 0.98 (seawater) to 0.34 (final invariant brine). The data provided can be used to evaluate the effects of mineral precipitation, evaporation and brine mixing for a wide variety of natural brines.  相似文献   

14.
A computerised algorithm is used to arrange fluid-absent reactions about invariant points in P—T space for an end-member model of blueschist facies metamorphism at Port Macquarie, N.S.W., consisting of the nine phases quartz, albite, jadeite, lawsonite, zoisite, paragonite, glaucophane, pyrope and chlorite. Inspection of the print-out (a table of reaction take-off angles for each invariant point) indicates that this multisystem consists of two mutually exclusive sets of invariant points; lawsonite-absent, paragonite-absent and glaucophane-absent versus the other six. The algorithm is completely general for any two intensive variables and can treat solid solution minerals or degeneracy in reactions/invariant points.Terms ABS(X) Absolute value of X - A(J) Slope of reaction J in degrees - V(J) Denominator variable in the slope fraction for reaction J - R(K, J) Reaction coefficient of phase K in reaction J - S(K, J) Stability pointer for phase K in reaction J, in degrees - SGN (X) Library function: =–1 when X<0; =+1 when X0 - B(Q) Correct take-off angle for the Q-absent reaction in degrees  相似文献   

15.
Pyrope and quartz are stable with respect to aluminous enstatite and sillimanite at 1400 °C, 20 kb and at 1100 °C, 16 kb. The phase boundary limiting the coexistence of pyrope and quartz towards lower pressures is probably slightly curved. A slope of 15 bars/°C at 1400° and of 10 bars/°C at 1000 °C has been estimated from the experimental data. Between 1050 and 1100 °C the curve is intersected by the kyanite-sillimanite phase boundary. The calculated slope of the reaction aluminous enstatite + kyanite pyrope + quartz is negative (ca. 18–25 bars/°C). The existence of a negative slope has been demonstrated experimentally. Experimental evidence indicates that the assemblage aluminous enstatite and sillimanite is metastable with respect to sapphirine + quartz at high temperature. The invariant point involving the phases pyrope-sapphirine-aluminous enstatite-sillimanite-quartz is estimated to occur at 1125°±25 °C and 16±1 kb. A model phase diagram for the silicasaturated part of the system MgO-Al2O3-SiO2 has been constructed. The position of three invariant points in this system has been estimated on the basis of presently available data.  相似文献   

16.
An increasing number of occurrences of margarite have been reported in the last years. However, previous experimental investigations in the system CaO-Al2O3-SiO2-H2O are limited to the synthesis of margarite and to the upper stability limit according to the reaction (1) 1 margarite?1 anorthite +1 corundum +1 H2O (Chatterjee, 1971; Velde, 1971). Since margarite often occurs together with quartz, the upper stability limit of margarite in the presence of quartz is of special interest. Therefore, the reactions (5) 1 margarite +1 quartz ?1anorthite +1 kyanite/andalusite +1 H2O and (6) 4 margarite+3 quartz ? 2 zoisite+5 kyanite+3 H2O were investigated experimentally using mixtures of natural margarite (from Chester, Mass., USA), quartz, kyanite, andalusite, zoisite, and synthetic anorthite. The indicated equilibrium temperatures at water pressures equal to total pressure are: 515± 25°C at 4 kb, 545 ±15°C at 5 kb, 590±10°C at 7 kb, and 650±10°C at 9 kb for reaction (5), and 651±11°C at 10 kb, 648 ± 8°C at 12.5kb, and 643±13°C at 15kb for reaction (6), respectively. Besides this, additional brackets for equilibrium temperatures were determined for the above cited reaction (1): 520±10°C at 3 kb, 580±10°C at 5 kb, and 640± 20°C at 7 kb. On the basis of these experimentally determined reactions (1), (5), and (6) and of the reactions (3) 2 zoisite +1 kyanite? 4 anorthite +1 corundum +1 H2O (7) 2 zoisite +1 kyanite +1 quartz ? 4 anorthite +1 H2O and (10) 1 pyrophyllite ? 1 andalusite/kyanite+3 quartz+1 H2O for which experimental or, in the case of reaction (3), calculated data were already available, a pressure-temperature diagram with 3 invariant points and 11 univariant reactions was developed using the method of Schreinemakers. This diagram, summarizing both experimental and phase relation studies, allows conclusions about the conditions under which margarite has been formed in nature. Margarite is limited to low grade metamorphism at water pressures up to approximately 3.5 kb; in the presence of quartz, margarite is even limited to low grade metamorphism at water pressures up to 5.5 kb. Only at water pressures higher than the values stated before margarite, and margarite+quartz, respectively, can occur in medium grade metamorphism (as defined by Winkler, 1970 and 1973). For the combined occurrence of margarite+quartz and staurolite as reported by Harder (1956) and Frey (personal communication, 1973) it may be estimated that water pressure has been greater than approximately 5.5 kb, wheras temperature has been in the range from 550 to 650°C. Furthermore, the present study shows that the assemblage zoisite+kyanite (+ H2O) is an indicator of both pressure [P H 2 O> approximately 9kb]and temperature [T> approximately 640 to 650° Cat water Pressures up to 15 kb].  相似文献   

17.
The 10?-phase, Mg3Si4O10(OH)2 · nH2O, where n = 0.65÷2, belongs to the group of dense hydrous magnesium silicates (DHMS), which were produced in experiments and are regarded as hypothetical mineral carriers for H2O in the mantle. However, DHMS were almost never observed in nature. The only exception is the finding of the 10?-phase as nanoinclusions in olivines from mantle nodules in kimberlites. The inclusions with sizes of a few ten nanometers have a pseudohexagonal habit and are characterized by the presence of voids free of solids. The 10?-phase fills the equatorial parts of the inclusions, and, in the majority of inclusions, it is replaced by the low-pressure serpentine + talc assemblage. Based on the analysis of electron microscope images, a model was proposed for the solid-state formation of inclusions, the precursory material of which was transformed to the 10?-phase with the liberation of a water fluid. According to this model, the formation of hydrous nanoinclusions and their subsequent autoserpentinization occurred without the influx of H2O from the external medium through the mobilization of intrinsic hydroxyl-bearing point defects trapped during olivine crystallization. The subsequent autoserpentinization of the inclusions occurred during decompression owing to interaction between the inclusion material and the host olivine matrix. The process was accompanied by the partial exhaustion of the fluid phase and the replacement 10?-phase + H2O = Serp + Tc. The criterion for the credibility of the model is the conservation of the volume of material during the reaction at P = const and T = const. Original Russian Text ? N.R. Khisina, R. Wirth, 2008, published in Geokhimiya, 2008, No. 4, pp. 355–363.  相似文献   

18.
Isothermal or isobaric phase diagram sections as a function of fluid composition (X F) are widely used for interpreting the genetic history of metacarbonate rocks. This approach has the disadvantages that: (1) the influence of a key metamorphic variable, either pressure (P) or temperature (T), is obscured; (2) the diagrams are inappropriate for systems that are not fluid-saturated. These problems are avoided by constructing phase-diagram projections in which the volatile composition of the system is projected onto a P-T coordinate frame, i.e., a petrogenetic grid. The univariant curves of such P-T projections trace the conditions of the invariant points of isothermal or isobaric phase-diagram sections, thereby defining the absolute stability of high-variance mineral assemblages, with and without a coexistent fluid phase. Petrogenetic grids for metacarbonate rocks are most useful for the study of regional metamorphism and for systems in which fluid composition has not been externally controlled. A calculated example of a P-T projection for the system CaO−MgO−SiO2−H2O−CO2 suggests that many assemblages (e.g., calcite +tale, enstatite+fluid, magnesite+tremolite, antigorite+diopside+dolomite, and calcite+forsterite+tremolite) in mixed-volatile systems have stability fields that make them useful as P-T indicators. Consideration of the principles governing projection topology demonstrates that the univariant curves around a fluid present invariant point cannot be oriented independently with respect to the direction of compositional variation in the fluid phase. This has the interesting predictive implication that if the direction of compositional variation along one univariant curve around an invariant point is known, then the direction of compositional variation along the remaining curves can be determined solely from topologic constraints. The same constraints can be applied to systems containing simple mineral solutions or melts in order to predict compositional variations.  相似文献   

19.
Bowen's petrogenetic grid was based initially on a series of decarbonation reactions in the system CaO-MgO-SiO2-CO2 with starting assemblages including calcite, dolomite, magnesite and quartz, and products including enstatite, forsterite, diopside and wollastonite. We review the positions of 14 decarbonation reactions, experimentally determined or estimated, extending the grid to mantle pressures to evaluate the effect of CO2 on model mantle peridotite composed of forsterite(Fo)+orthopyroxene(Opx)+clinopyroxene(Cpx). Each reaction terminates at an invariant point involving a liquid, CO2, carbonates, and silicates. The fusion curves for the mantle mineral assemblages in the presence of excess CO2 also terminate at these invariant points. The points are connected by a series of reactions involving liquidus relationships among the carbonates and mantle silicates, at temperatures lower (1,100–1,300° C) than the silicate-CO2 melting reactions (1,400–1,600° C). Review of experimental data in the bounding ternary systems together with preliminary data for the system CaO-MgO-SiO2-CO2 permits construction of a partly schematic framework for decarbonation and melting reactions at upper mantle pressures. The key to several problems in the peridotite-CO2 subsystem is the intersection of a subsolidus carbonation reaction with a melting reaction at an invariant point near 24 kb and 1,200°C. There is an intricate series of reactions between 25 kb and 35 kb involving changes in silicate and carbonate phase fields on the CO2-saturated liquidus surfaces. Conclusions include the following: (1) Peridotite Fo+Opx+Cpx can be carbonated with increasing pressure, or decreasing temperature, to yield Fo+Opx+Cpx+Cd (Cd=calcic dolomite), Fo+Opx+Cd, Fo+Opx+Cm (Cm=calcic magnesite), and finally Qz+Cm. (2) Free CO2 cannot exist in subsolidus mantle peridotite with normal temperature distributions; it is stored as carbonate, Cd. (3) The CO2 bubbles in peridotite nodules do not represent free CO2 in mantle peridotite along normal geotherms. (4) CO2 is as effective as H2O in causing incipient melting, our preferred explanation for the low-velocity zone. (5) Fusion of peridotite with CO2 at depths shallower than 80 km produces basic magmas, becoming more SiO2-undersaturated with depth. (6) The solubility of CO2 in mantle magmas is less than about 5 wt% at depths to 80 km, increasing abruptly to about 40 wt% at 80 km and deeper. (7) Deeper than 80 km, the first liquids produced are carbonatitic, changing towards kimberlitic and eventually, at considerably higher temperatures, to basic magmas. (8) Kimberlite and carbonatite magmas rising from the asthenosphere must evolve CO2 at depths 100-80 km, which contributes to their explosive emplacement. (9) Fractional crystallization of CO2-bearing SiO2-undersaturated basic magmas at most pressures can yield residual kimberlite and carbonatite magmas.  相似文献   

20.
The prograde evolution of minerals in metapelites of a Barrovian sequence from the tri-state area (Massachusetts, Connecticut, New York) of the Taconic Range involves assemblages with garnet (Ga), chlorite (Ch), chloritoid (Ct), biotite (Bi) and staurolite (St). Detailed petrologic observations, mineral compositions and chemical zoning in garnet show: (1) garnet high in Mn and Fe but low in Mg is stable with chlorite at grades below those where chloritoid+biotite is found; (2) early formed garnet reacted partially to form Ct+Bi at intermediate grades; (3) at higher grades garnet (with low Mn)+chlorite is again produced, at the expense of chloritoid+biotite, suggesting a reversal in the continuous reaction involving the phases Ga, Ch, Ct and Bi. Thermodynamic modeling of the assemblage Ga+Ch+Ct+Bi±St in the MnKFMASH system reveals: (1) in the MnKFASH system the prograde reaction is Ga+Ch=Ct+Bi whereas in the KFMASH system the prograde reaction is the opposite: Ct+Bi=Ga+Ch; (2) the Ga–Ch–Ct–Bi–St invariant point in the KFMASH system occurs twice, at approximately 6.5 kbar, 545° C and 14.8 kbar, 580° C (although one of them may be metastable in a complex phase system); the appearance of the petrogenetic grid is markedly different from that of Albee, but similar to that of Spear and Cheney; (3) as a consequence, in the KFMASH system, chloritoid+biotite are stable over a wide range of P-T conditions whereas garnet+chlorite assemblages are restricted to a narrow band of P-T conditions; (4) MnO increases the stability field of Ga+Ch relative to both Ct+Bi at low temperatures, and St+Bi at high temperatures; (5) in natural samples the occurrence of Ct+Bi is controlled more by bulk Mg–Fe(-Mn) composition than P-T conditions. Specifically, Ct+Bi is restricted to bulk compositions with Fe/(Mg+Fe+Mn)>0.6. Rocks with Fe/(Mg+Fe+Mn)<0.5 are likely to display only chlorite+biotite at low grade. These observations are consistent with Wang and Spear and Spear and Cheney.  相似文献   

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