Arrested charnockite formation in southern India and Sri Lanka

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.     

Rare earth element geochemistry of the Scourian complex N.W. Scotland — Evidence for the granite-granulite link

Medium-to high-pressure granulite facies complexes represent samples of lower crustal material and are, therefore, important in the study of crustal processes. New rare earth element data for the Scourian granulite facies terrain of the Precambrian Lewisian complex of N.W. Scotland indicate that:

1. Overall, the Scourian complex has a light rare earth enriched pattern with a small but distinct positive Eu anomaly;
2. While some rare earth element trends for the complex as a whole (e.g., Σ REE vs SiO₂) are similar to those observed in upper crustal cogenetic sequences, others (e.g., Eu/Eu* vs SiO₂) are reversed;
3. Compared to average upper crust, the Scourian complex is depleted in REE (except Eu) by a factor of 2 to 3.

These new data, along with previously reported major and trace element data, isotopic abundances, and trace element modelling support the hypothesis that the Scourian terrain is the residuum left after genesis and removal of granitic melts.     

The role of fluids in the formation and subsequent development of early continental crust

A petrogenetic model is developed to explain the evolution and geochemical character of granitic rocks in early Archean (pre 3.6 Gyr) continental crust taking into account the following important geological constraints, viz.:

1. High geothermal gradients (probably in excess of 90 ° C/km) and resulting widespread granulite facies metamorphism even at relatively shallow depths
2. The fractionation of certain major and trace elements under granulite facies conditions
3. The composition and geochemical behaviour of fluids which emanate from or pass through terrains undergoing granulite facies metamorphism viz. carbonic fluids containing significant amounts of SO₂ and halogens.

In this model tonalitic and trondhjemitic intrusives are regarded as being derived dominantly by partial melting of mafic granulite. The ubiquitous potassic granites, which typical post-date sodic plutonic activity are interpreted to be anatectic melts generated under granulite or amphibolite facies conditions from the previously formed ‘plagiogranites’. The presence of a postulated granulite facies source area for Archean tonalitic rocks, and the geochemical character of fluids which accompany metamorphism under such conditions explains the HREE geochemistry of these suites and casts doubt on the validity of applying currently used trace element fractional melting or crystallization models to these terrains. Similarly it suggests that petrogenetic interpretations based on Sr and Pb isotopic systems must be reevaluated because of the extreme mobility of both parent and daughter elements under granulite facies conditions.     

Carbon Dioxide in igneous petrogenesis: I

A number of experimental CO₂ solubility data for silicate and aluminosilicate melts at a variety of P- T conditions are consistent with solution of CO₂ in the melt by polymer condensation reactions such as SiO _4(m ^4? +CO_2(v)+Si _n O _3n+1(m) ⁽²ⁿ⁺¹⁾ ?Si _n+1O _3n+4(m) ^(2n+4)? +CO _3(m ^)2? . For various metalsilicate systems the relative solubility of CO₂ should depend markedly on the relative Gibbs free change of reaction. Experimental solubility data for the systems Li₂O-SiO₂, Na₂O-SiO₂, K₂O-SiO₂, CaO-SiO₂, MgO-SiO₂ and other aluminosilicate melts are in complete accord with predictions based on Gibbs Free energies of model polycondesation reactions. A rigorous thermodynamic treatment of published P- T-wt.% CO₂ solubility data for a number of mineral and natural melts suggests that for the reaction CO_2(m) ? CO_2(v)

1. CO₂-melt mixing may be considered ideal (i.e., { \(a_{{\text{CO}}_{\text{2}} }^m = X_{{\text{CO}}_{\text{2}} }^m \) );
2. \(\bar V_{{\text{CO}}_{\text{2}} }^m \) , the partial molal volume of CO₂ in the melt, is approximately equal to 30 cm³ mole^?1 and independent of P and T;
3. Δ C _p ⁰ is approximately equal to zero in the T range 1,400° to 1,650 °C and
4. enthalpies and entropies of the dissolution reaction depend on the ratio of network modifiers to network builders in the melt. Analytic expressions which relate the CO₂ content of a melt to P, T, and \(f_{{\text{CO}}_{\text{2}} } \) for andesite, tholeiite and olivine melilite melts of the form

$$\ln X_{{\text{CO}}_{\text{2}} }^m = \ln f_{{\text{CO}}_{\text{2}} } - \frac{A}{T} - B - \frac{C}{T}(P - 1)$$ have been determined. Regression parameters are (A, B, C): andesite (3.419, 11.164, 0.408), tholeiite (14.040, 5.440,0.393), melilite (9.226, 7.860, 0.352). The solubility equations are believed to be accurate in the range 3<P<30 kbar and 1,100°<T<1,650 °C. A series of CO₂ isopleth diagrams for a wide range of T and P are drawn for andesitic, tholeiitic and alkalic melts.     

Experimental investigation of the mechanism of the reaction: 1 tremolite+11 dolomite ⇌ 8 forsterite+13 calcite+9 CO2+1H2O

Stoichiometric mixtures of tremolite and dolomite were heated to 50° C above equilibrium temperatures to form forsterite and calcite. The pressure of the CO₂-H₂O fluid was 5 Kb and \(X_{{\text{CO}}_{\text{2}} }\) varied from 0.1 to 0.6. The extent of the conversion was determined by the amount of CO₂ produced. The resulting mixtures of unreacted tremolite and dolomite and of newly-formed forsterite and calcite were examined with a scanning electron microscope. All tremolite and dolomite grains showed obvious signs of dissolution. At fluid compositions with \(X_{{\text{CO}}_{\text{2}} }\) less than about 0.4, the forsterite and calcite crystals are randomly distributed throughout the charges, indicating that surfaces of the reactants are not a controlling factor with respect to the sites of nucleation of the products. A change is observed when \(X_{{\text{CO}}_{\text{2}} }\) is greater than about 0.4; the forsterite and calcite crystals now nucleate and grow at the surface of the dolomite grains, thus indicating a change in mechanism at medium CO₂ concentrations. As the reaction progresses, the dolomite grains become more and more surrounded by forsterite and calcite, finally forming armoured relics of dolomite. Under experimental conditions this characteristic texture can only be formed if the CO₂-concentration is greater than about 40 mole %. These findings make it possible to estimate the CO₂-concentration from the texture of the dolomite+tremolite+forsterite+calcite assemblage. The results suggest a dissolution-precipitation mechanism for the reaction investigated. In a simplified form it consists of the following 4 steps:

1. Dissolution of the reactants tremolite and dolomite.
2. Diffusion of the dissolved constituents in the fluid.
3. Heterogeneous nucleation of the product minerals.
4. Growth of forsterite and calcite from the fluid.

Two possible explanations are discussed for the development of the amoured texture at \(X_{{\text{CO}}_{\text{2}} }\) above 0.4. The first is based upon the assumption that dolomite has a lower rate of dissolution than tremolite at high \(X_{{\text{CO}}_{\text{2}} }\) values resulting in preferential calcite and forsterite nucleation and growth on the dolomite surface. An alternative explanation is the formation of a raised CO₂ concentration around the dolomite grains at high \(X_{{\text{CO}}_{\text{2}} }\) values, leading to product precipitation on the dolomite crystals.     

Diffusion controlled growth of pyroxene-bearing margins on amphibolite bands in the granulite facies of Rogaland (Southwestern Norway): implications for granulite formation

In the Rogaland granulites of Southern Norway, thin anhydrous pyroxene-bearing margins (5–10 mm) are observed mainly in migmatitic banded gneisses at the contact between hornblende-rich metabasites and charnockites. According to field data, the development of these margins post-dates any deformation. Petrographic data show that they are zoned. Three different types have been recognized:

1. Metabasite/plagioclase + orthopyroxene/plagioclase + clinopyroxene/gneiss
2. Metabasite/plagioclase + orthopyroxene + clinopyroxene/plagioclase + clinopyroxene/gneiss
3. Metabasite/plagioclase + orthopyroxene/gneiss

The first zone corresponds to the reaction of amphibole and biotite of the metabasite into pyroxenes. The second zone, which is not present in the third type, developed essentially at the expense of gneiss and the Z1/Z2 boundary is likely to correspond to the original contact between metabasite and gneiss. When the anorthite content of plagioclase and the Fe no. of pyroxenes are strongly different between adjacent metabasite (An_38–40 for plagioclase; Fe no. [Fe/(Fe + Mg)], 0.51–0.52 for orthopyroxene) and gneiss (An_22–26; Fe no., 0.58–0.59), the solid solution compositions evolve continuously through the margin from the value in the metabasite to that in the gneiss. On the other hand, a margin is also present when plagioclase and pyroxenes have similar compositions in the adjacent rocks implying that reactions can also take place in the absence of contrasted mineral compositions. The continuous change in solid solution composition as well as evidence of transport in both directions indicates diffusion rather than infiltration as the dominant metasomatic mechanism. The small thickness of the margins is also more typical of a diffusion process. Isocon diagrams demonstrate that Al, Ti, and P are perfectly inert components and that no significant mass or volume change occurred during the margin development. Mass balance of this small-scale granulite formation has been estimated with reference to a perfectly inert component (Ti) and assuming that the metabasite bands were compositionally homogeneous. Most of the geochemical variation is mineralogically controlled. Relative to metabasite, Si and Na are increased due to pyroxenes crystallization and to compositional change of plagioclase when it occurs. Potassium decreases because of biotite disappearance. There is no significant variation in U content but Th is slightly decreased. Zirconium and Hf are not affected whereas Nb, Ta and Mn display the largest increase that requires the involvement of a larger volume of metabasite than that observed in the margin. The K/Rb ratio is increased. Fluorine is strongly depleted due to destabilization of amphibole and biotile. The rare-earth element content in margins is either similar to that of the metabasite or intermediate between that of gneiss and metabasite. This last feature is induced by the development of margins at the expense of both adjacent rock types. Saturation surfaces in chemical potential space provide a graphical method for determination of the parameters controlling the diffusion process. In the simplified system CaO?MgO?SiO₂?Al₂O₃?H₂O, these chemical potential diagrams show that evolution along a $(\mu )_{H_2 O} $ gradient cannot take into account the three different types of margins. A $(\mu )_{H_2 O} $ gradient is thus not prerequisite to the margin development. On the other hand, the succession of zones observed in the different types of margins can be obtained in a $(\mu )_{CaO} - (\mu )_{MgO} - (\mu )_{SiO_2 } $ diagram. This suggests that the $(\mu )_{SiO_2 } $ gradient existing between the two adjacent rocks controls the margin development in all cases. Moreover, the variable contrast of plagioclase composition between the adjacent rocks is responsible for the presence of one or two pyroxenes is the first zone. The absence of the second clinopyroxene-bearing zone in the third type of margin is likely due to the scarcity of orthopyroxene in the gneiss.     

Factors effecting the stability field of Ca-poor pyroxene and the origin of the Ca-poor minimum in Ca-rich pyroxenes from tholeiitic intrusions

Ca-poor pyroxene ceases to crystallise towards the end of fractionation in tholeiitic intrusions and is usually replaced by Fe-rich olivine. Using the data of Nicholls et al. (1971), the \(a_{{\text{SiO}}_2 }\) at which olivine and pyroxene can coexist has been calculated at different temperatures and pressures. From these calculations it is clear that the Fe/Mg ratio of the last Ca-poor pyroxene to crystallise from a melt is increased by raising the temperature or pressure of crystallisation. The Ca-poor pyroxene-Fe-rich olivine relationship is also dependent on the \(a_{{\text{SiO}}_2 }\) of the melt. In magmas which crystallise Fe-rich olivine before quartz, inicreasing their \(a_{{\text{SiO}}_2 }\) will raise the Fe/Mg ratio of the last Ca-poor pyroxene to crystallise. If the \(a_{{\text{SiO}}_2 }\) of the magma is so high that SiO₂ saturation is reached before the appearance of cumulus Fe-rich olivine, any further increase in the \(a_{{\text{SiO}}_2 }\) of the melt will not influence the stability field of Ca-poor pyroxene. The replacement of Ca-poor pyroxene by Fe-rich olivine requires the magma to reach a high level of a _FeO late in its fractionation. If a magma fractionates with an FeO depletion trend, Ca-poor pyroxene is replaced by Ca-rich pyroxene. The reaction is initiated by the appearance of cumulus K-feldspar which results in a marked reduction in the amount of anorthite crystallising from the magma. This increases the a _CaO of the melt so that Ca-poor pyroxene is replaced by Ca-rich pyroxene.     

On the nonstoichiometry and point defects of olivine

This paper presents the point-defect thermodynamics for fayalite and olivine solid solutions (Fe _x Mg_1?x )₂SiO₄. By means of thermogravimetry, the metal-to-oxygen ratio of these silicates has been determined as a function of oxygen potential, compositionx and temperature. Experiments were performed in the range of 1,000° C≦T≦1,280° C and 0.2≦x≦1.0. It is found that V _Me ^″ , Fe _Me ^· and the associate {Fe′ _Si ^′ Fe _Me ^· } are the majority defects. With this knowledge it is possible to calculate the nonstoichiometry at given temperature as a function of \(p_{O_2 } \) and \(a_{SiO_2 } \) . The cation vacancy concentration shows a \(p_{O_2 }^{1/5} \) -dependence (forx≧0.2) and increases at givenT and \(p_{O_2 } \) almost exponentially with compositionx. In the composition range studied here, the silicates show an oxygen excess, and FeO is more soluble in the olivine than SiO₂.     

Fluid inclusions in rocks from the amphibolite-facies gneiss to charnockite progression in southern Karnataka, India: direct evidence concerning the fluids of granulite metamorphism

Abstract Fluid inclusion studies of rocks from the late Archaean amphibolite-facies to granulite-facies transition zone of southern India provide support for the hypothesis that CO₂,-rich H₂O-poor fluids were a major factor in the origin of the high-grade terrain. Charnockites, closely associated leucogranites and quartzo-feldspathic veins contain vast numbers of large CO₂-rich inclusions in planar arrays in quartz and feldspar, whereas amphibole-bearing gray gneisses of essentially the same compositions as adjacent charnockites in mixed-facies quarries contain no large fluid inclusions. Inclusions in the northernmost incipient charnockites, as at Kabbal, Karnataka, occasionally contain about 25 mol. % of immiscible H₂O lining cavity walls, whereas inclusions from the charnockite massif terrane farther south do not have visibile H₂O Microthermometry of CO₂ inclusions shows that miscible CH₄ and N₂ must be small, probably less than 10mol.%combined. Densities of CO₂ increase steadily from north to south across the transitional terrane. Entrapment pressures calculated from the CO₂ equation of state range from 5 kbar in the north to 7.5 kbar in the south at the mineralogically inferred average metamorphic temperature of 750°C, in quantitative agreement with mineralogic geobarometry. This agreement leads to the inference that the fluid inclusions were trapped at or near peak metamorphic conditions. Calculations on the stability of the charnockite assemblage biotite-orthopyroxene-K-feldspar-quartz show that an associated fluid phase must have less than 0.35 H₂O activity at the inferred P and T conditions, which agrees with the petrographic observations. High TiO₂ content of biotite stabilizes it to lower H₂O activities, and the steady increase of biotite TiO₂ southward in the area suggests progressive decrease of aH₂O with increasing grade. Oxygen fugacities calculated from orthopyroxene-magnetite-quartz are considerably higher than the graphite CO₂-O₂ buffer, which explains the absence of graphite in the charnockites. The present study quantifies the nature of the vapours in the southern India granulite metamorphism. It remains to be determined whether CO₂-flushing of the crust can, by itself, create large terranes of largeion lithophile-depleted granulites, or whether removal of H₂O-bearing anatectic melts is essential.     

Geochemistry and origin of granitic rocks,Scourian Complex,NW Scotland

Concordant granite sheets from the granulite facies Scourian Complex, N.W. Scotland exhibit the following features:

1. a common planar fabric with their host pyroxene granulites;
2. the presence of an exsolved ternary feldspar phase;
3. a low-pressure, water-saturated minimum composition;
4. K/Rb ratios (450–1,350) distinctly higher than most upper crustal granites but similar to the surrounding granulites;
5. low absolute concentrations of the rare earth elements (REEs), light REE enrichment, and large positive Eu anomalies.

It is proposed that the granite sheets have originated by anatexis of gneisses undergoing granulite facies metamorphism — gneisses that were already essentially dry and depleted in incompatible elements. Their unusual trace element chemistry may be explained by either disequilibrium melting and/or sub-solidus reequilibration of the granite sheets with the surrounding gneisses. Isotopic and trace element data suggest that cross-cutting, potash-rich pegmatites represent reworking of the granite sheets during a later amphibolitization.     

The role of water in the 1944 Vesuvius eruption

The P-T path of magma associated with the 1944 Vesuvius eruption has been outlined on the basis of probe mineralogy and the relationships between the crystallising phases. Equilibrium P-T values, obtained from the reactions:

1. CaMgSi₂O_6(liq) = CaMgSi₂O_6(cpx)
2. NaAlSi₃O_{8 (liq)} = NaAlSi₃O_{8 (plag)}
3. CaAl₂Si₂O_{8 (plag)}=CaAl₂SiO_6(cpx)+SiO_2(liq) have been established for three intracrustal crystallisation stages: I) 8.0 kbar and 1255 °C; II) 4.0 kbar and 1178 °C; III) 0.5 kbar and 1105 °C.

The H₂O content in the magma has been estimated from an experimental calibration of \(a_{^{CaMgSi_2 O_6 } }^{liq}\) as a function of \(X_{H_2 O}^{liq}\) at P _tot = 2 kbar. The estimated water contents of the magma for the three stages, I) 0.7%; II) 0.9%; III) 1.1%, are consistent with the pattern of activity of the 1944 Vesuvius eruption and with the relationship between the lavas. The shallow depth of H₂O-saturation of the magma, 0.24 kbar at 1100 °C, is consistent with the eruption sequence of lava flows followed by lava fountain activity.     

Phase relationships in granulitic metapelites from the Ivrea-Verbano zone (Northern Italy)

Paragneisses of the Ivrea-Verbano zone exhibit over a horizontal distance of 5 km mineralogical changes indicative of the transition from amphibolite to granulite facies metamorphism. The most obvious change is the progressive replacement of biotite by garnet via the reaction: a $${\text{Biotite + sillimanite + quartz }} \to {\text{ Garnet + K - feldspar + H}}_{\text{2}} {\text{O}}$$ which results in a systematic increase in the modal ratio g = (garnet)/(garnet + biotite) with increasing grade. The systematic variations in garnet and biotite contents of metapelites are also reflected by the compositions of these phases, both of which become more magnesian with increasing metamorphic grade. The pressure of metamorphism has been estimated from the Ca₃Al₂Si₃O₁₂ contents of garnets coexisting with plagioclase, sillimanite and quartz. These phases are related by the equilibrium: b $$\begin{gathered} 3 CaAl_2 {\text{Si}}_{\text{2}} {\text{O}}_{\text{8}} \rightleftharpoons Ca_3 Al_2 {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} + 2 Al_2 {\text{SiO}}_{\text{5}} + {\text{SiO}}_{\text{2}} \hfill \\ plagioclase garnet sillimanite quartz \hfill \\ \end{gathered} $$ which has been applied to these rocks using the available data on the mixing properties of plagioclase and garnet solid solutions. Temperature and f _{H 2O} estimates have been made in a similar way using thermodynamic data on the biotite-garnet reaction (a) and the approximate solidus temperatures of paragneisses. Amphibolite to granulite facies metamorphism in the Ivrea-Verbano zone took place in the P-T ranges 9–11 kb and 700–820 °C. The differences in temperature and pressure of metamorphism between g= 0 and g = 1 (5 kms horizontal distance) were less than 50° C and approximately 1 kb. Retrogression and re-equilibration of garnets and biotites in the metapelites extended to temperatures more than 50° C below and pressures more than 1.5 kb below the peak of metamorphism, the degree of retrogression increasing with decreasing grade of the metamorphic “peak”. The pressure and temperature of the peak of metamorphism are not inconsistent with the hypothesis that the Ivrea-Verbano zone is a slice of upthrusted lower crust from the crust-mantle transition region, although it appears that the thermal gradient was too low for the zone to represent a near-vertical section through the crust. The most reasonable explanation of the granulite facies metamorphism is that it arose through intrusion of mafic rocks into a region already undergoing recrystallisation under amphibolite facies conditions.     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

A study on metamorphic temperature and pressure of Archean Miyun Group,Beijing

Metamorphic temperatures and pressures of the Archean Miyun Group were determined from orthopyroxene-clinopyroxene, garnet-clinopyroxene, garnet-biotite and δO _Q ¹⁸ -δO _Mt ¹⁸ geothermometers and orthopyroxene barometer. The results show that the temperature in the first metamorphic stage of the Miyun Group is 820°+50°C and the pressure about 10 kb, which suggests that the granulite facies occurs under moderate pressures with a geothermal gradient of 22°–25°C/km. The corresponding burial depth is about 35 km. The temperature prevailing during the second metamorphic stage is in the range 650°–700°C, indicating a moderate condition between granulite and high grade amphibolite facies. Oxygen isotope data also show that the temperature of later superimposed regression metamorphism of high green schist facies in this area may be within the range of 470°–560°C.     

Experimental study of the physico-chemical conditions of skarn formation

Experimental results show that skarns can—800°C and 500–1,000 bars. Starting materials include intermediate-acidic igneous rocks, volcanic rocks, metamorphic rocks, carbonates of various purities and chemical reagents of analytical purity-grade. Experimental media are: NaCl, NaCl+CaCl₂, NaCl+CaCl₂+MgCl₂, Na₂CO₃ and Na₂SiO₃ solutions. Experimental results show that skarns can be formed under wide physico-chemical conditions:T=400°–800°C,P=500–1,000 bars,pH=4–11, and \(f_{O_2 } = 10^{ - 23} - 10^{ - 11} \) bar. The mineralogy of skarns and the chemical compositions of skarn minerals are generally controlled by the combined factors: the chemical composition of the original rocks, pH values, redox conditions, temperatures and pressures. Isomorphous substitution may have agreat effect on the temperature of formation andfo ₂ of some major skarn minerals. It is found that skarnization occurs preferentially in NaCl and NaCl+CaCl₂ solutions and subortinately in MaCO₃ and Na₂SiO₃ soiutions.     

Phase equilibria among pumpellyite,lawsonite, epidote and associated minerals in low grade metamorphic rocks

Phase relations of pumpellyite, epidote, lawsonite, CaCO₃, paragonite, actinolite, crossite and iron oxide are analysed on an Al-Ca-Fe³⁺ diagram in which all minerals are projected from quartz, albite or Jadeite, chlorite and fluid. Fe²⁺ and Mg are treated as a single component because variation in Fe²⁺/Mg has little effect on the stability of phases on the diagram. Comparison of assemblages in the Franciscan, Shuksan, Sanbagawa, New Caledonia, Southern Italian, and Otago metamorphic terranes reveals several reactions, useful for construction of a petrogenetic grid:

1. lawsonite+crossite + paragonite = epidote+chlorite + albite + quartz + H₂O
2. lawsonite + crossite = pumpellyite + epidote + chlorite + albite+ quartz + H₂O
3. crossite + pumpellyite + quartz = epidote + actinolite + albite + chlorite + H₂O
4. crossite + epidote + quartz = actinolite + hematite + albite + chlorite + H₂O
5. calcite + epidote + chlorite + quartz = pumpellyite + actinolite + H₂O + CO₂
6. pumpellyite + chlorite + quartz = epidote + actinolite + H₂O

     

Experimental investigation of the metamorphism of siliceous dolomites

For the reaction: 1 diopside+3 dolomite ?2 forsterite+4 calcite+2 CO₂ (14) the following P _total?T-brackets have been determined experimentally in the presence of a gasphase consisting of 90 mole%CO₂ and 10 mole%H₂O∶1 kb, 544°±20° C; 3kb, 638°±15° C; 5kb, 708°±10° C; 10kb, 861°±10° C. The determination was carried out with well defined synthetic minerals in the starting mixture. The MgCO₃-contents of the magnesian calcites formed by the reaction in equilibrium with dolomite agree very well with the calcite-dolomite miscibility gap, which can be recalculated from the activities and the activity coefficients of MgCO₃ as given by Gordon and Greenwood (1970). The equilibrium constant K _14b was calculated with respect to the reference pressure P ₀=1 bar using the experimentally determined \(P_{total} TX_{CO_2 }\) brackets, the activities of MgCO₃ and CaCO₃ (Gordon and Greenwood 1970; Skippen 1974) and the fugacities of CO₂ Holloway (1977) considering the correction of Flowers (1979). Results are plotted as function of the absolute reciprocal temperature in Fig. 1. For the temperature range of 530° to 750° C the following linear expression can be given for the natural logarithm of K_14b: (g) $$[ln K_{14b} ]_T^P = - \frac{{18064.43}}{{T\left( {^\circ K} \right)}} + 38.58 + \frac{{0.308(P - 1 bar)}}{{T\left( {^\circ K} \right)}}$$ where P is the total pressure in bars and T the temperature in degrees Kelvin. Combining Equation (g) with the activities of MgCO₃ and CaCO₃ gives the equilibrium fugacity \(f_{CO_2 }\) : (i) $$[ln f_{CO_2 } ]_T^P = - \frac{{11635.44}}{{T\left( {^\circ K} \right)}} + 21.09 + \frac{{0.154(P - 1 bar)}}{{T\left( {^\circ K} \right)}}$$ Equation (i) and the fugacities of CO₂ permit to calculate the equilibrium data in terms of \(P_{CO_2 }\) and T (see Fig. 3) or P _total, T and \(X_{CO_2 }\) (see Fig. 5). Combining the \(P_{total} TX_{CO_2 }\) equilibrium data of the above reaction with those of the previously investigated reaction (Metz 1976): 1 tremolite+11 dolomite ?8 forsterite+13 calcite+9 CO₂+1 H₂O yields the stability conditions of the four-mineral assemblage: diopside+calcian dolomite+forsterite +magnesian calcite and the stability conditions of the five-mineral assemblage: tremolite+calcian dolomite+forsterite +magnesian calcite+diopside both shown in Fig. 6. Since these assemblages are by no means rare in metamorphic siliceous dolomites (Trommsdorff 1972; Suzuki 1977; Puhan 1979) the data of Fig. 6 can be used to determine the pressure of metamorphism and to estimate the composition of the CO₂-H₂O fluid provided the temperature of the metamorphic event was determined using the calcite-dolomite geothermometer.     

Carbon-isotope constraints on fluid advection during contrasting examples of incipient charnockite formation

Abstract Incipient charnockite formation within amphibolite facies gneisses is observed in South India and Sri Lanka both as isolated sheets, associated with brittle fracture, and as patches forming interconnected networks. For each mode of formation, closely spaced drilled samples across charnockite/gneiss boundaries have been obtained and δ¹³C and CO₂ abundances determined from fluid inclusions by stepped-heating mass spectrometry. Isolated sheets of charnockite (c.50 mm wide) within biotite–garnet gneiss at Kalanjur (Kerala, South India) have developed on either side of a fracture zone. Phase equilibria indicate low-pressure charnockite formation at pressures of 3.4 ± 1.0 kbar and temperatures of about 700°C (for X_H2O= 0.2). Fluid inclusions from the charnockite are characterized by δ¹³C values of ?8% and from the gneiss, 2 m from the charnockite, by values of ?15%. The large CO₂ abundances and relatively heavy carbon-isotope signature of the charnockite can be traced into the gneiss over a distance of at least 280 mm from the centre of the charnockite, whereas the reaction front has moved only 30 mm. This suggests that fluid advection has driven the carbon-isotope front through the rock more rapidly than the reaction front. The carbon-front/reaction-front separation at Kalanjur is significantly larger than the value determined from a graphite-bearing incipient charnockite nearby, consistent with the predictions of one-dimensional advection models. Incipient charnockites from Kurunegala (Sri Lanka) have developed as a patchy network within hornblende–biotite gneiss. CO₂ abundances rise to a peak near one limb of the charnockite, and isotopic values vary from δ¹³C of c.?5.5% in the gneiss to ?9.5% in the charnockite. The shift to lighter values in the charnockite can be ascribed to the formation of a CO₂-saturated partial melt in response to influx of an isotopically light carbonic fluid. Thus, incipient charnockites from the high-grade terranes of South India and Sri Lanka reflect a range of mechanisms. At shallower structural levels non-pervasive CO₂ influxed along zones of brittle fracture, possibly associated with the intrusion of charnockitic dykes. At deeper levels, in situ melting occurred under conditions of ductile deformation, leading to the development of patchy charnockites.     

Titanian hydroxyl-clinohumite: Formation and breakdown in antigorite rocks (Malenco,Italy)

Petrographic evidence is presented for the breakdown of titanian hydroxyl-clinohumite to olivine+magnesian ilmenite (or geikielite)±magnetite in the outermost zone of the Bergell aureole in the Malenco Serpentinite, Prov. Sondrio, Italy. The breakdown coincides in the field with the isograd reaction: antigorite+diopside=olivine+tremolite+H₂O. It is therefore concluded that this variety of clinohumite is unstable above approximately 520° C at a pressure of 3 kbars. Elsewhere in the Malenco Serpentinite, titanian hydroxyl-clinohumite may be found to have reacted with CO₂ to produce antigorite, magnesian ilmenite and magnesite. Titanian hydroxyl-chondrodite was detected in one sample. Under crustal pressures, the stability field of F-free clinohumite is entirely contained inside that of antigorite. The stable occurrence of titanian clinohumite in high-grade metamorphic ultrabasic rocks may be attributed to the substitution of F for OH.     

The compositions of coexisting pyroxenes and garnet in the system CaO-MgO-Al2O3-SiO2 at 900°–1,100°C and high pressures

The compositions of coexisting orthopyroxene, clinopyroxene and garnet in the CaO-MgO-Al₂O₃-SiO₂ system are fixed at any givenP andT. Reversed hydrothermal experiments over theP/T range 15–40 kb/900°–l,100° C indicate that the garnet composition is nearly constant at Py₈₆Gr₁₄; the Alcontent and Ca/Ca+Mg values of the pyroxenes vary significantly, however: