Synthesis and stability of the garnet calderite in the system Fe-Mn-Si-O

The rare garnet end member calderite, Mn ₃ ²⁺ Fe ₂ ³⁺ Si₃O₁₂, has been synthesized, under the oxygen fugacity of the hematite/magnetite buffer, at pressures not lower than 22 kbar. The synthetic crystals are generally zoned and may contain up to 3 mol% of the Fe²⁺-(=skiagite-) or 10 mol% of the Mn³⁺-(=blythite-) end members, but, under equilibrium conditions, the stable garnets have a restricted compositional range with about 1–4 mol% skiagite. Mn³⁺ represents only a residue of the Mn₂O₃ used in the starting material. At temperatures above 720° C (at 24 kbar) to 850° C (at 30 kbar) these garnets break down into coexisting pairs of magnetite-jacobsite and pyroxmangite-FeSiO₃ solid solutions. No indication for divariancy of this breakdown reaction could be established so that the observed coexistence of garnet and breakdown products over a PT interval must be due to disequilibrium. Although extrapolations of the high-pressure stability data towards lower pressures are hazardous, it is clear that nearly pure calderite garnets can only form in metamorphic environments characterized by geothermal gradients not exceeding some 10°–15° C/km, that is in subduction zone metamorphism. A low-pressure end of the calderite stability is likely because, at temperatures below 250°–300° C, pyroxmangite probably becomes unstable and hydrous Mn²⁺-silicates appear among the low-temperature breakdown products of calderite. Since the upper temperature stability limits of the common garnet end members spessartine and andradite lie some 800° C above that for calderite, solid solutions with these components will drastically stabilize the garnet phase towards both higher temperatures and lower pressures. This explains why garnets containing around 70 mol% calderite can be formed in amphibolitefacies metamorphism.     

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.     

Fractionation of carbon and oxygen isotopes and magnesium between coexisting metamorphic calcite and dolomite

Fractionations of carbon and oxygen isotopes and magnesium between coexisting dolomite and calcite have been determined for marbles and calcareous schists of a wide variety of metamorphic environments from Vermont and the Grenville Province of Ontario. Concordant equilibrium fractionations are given by 83% of the samples. Calibration of the isotopic thermometers using the Mg-calcite solvus thermometer gave in the temperature range: 650°>T°>100°C $$ \begin{gathered} 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.45 (10^6 T^{ - 2} ) - 0.40 \hfill \\ 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.18 (10^6 T^{ - 2} ) + 0.17. \hfill \\ \end{gathered} $$ These isotopic fractionation expressions differ significantly from the experimentally derived relations, including the dolomite-Mg-calcite C¹³ partial exchange experiments of this study. Temperature ranges obtained for the metamorphic zones of Vermont are: chlorite zone, 210° to 295° C; biotite zone, 255° to 400° C; staurolite-kyanite zone, 110° to 550° C. In amphibolite-facies rocks the quenched partition relations can be complex. The temperature of quench or recrystallization may be as large as 400° C below the inferred metamorphic maximum. Oxygen isotope disequilibrium in high grade rocks, particularly from the Chester dome area, Vermont, is characterized by large negative δO _D ¹⁸ –δO _Ct ¹⁸ values. The size of the equilibrium exchange system for carbon and oxygen isotopes and magnesium is small, less than a few inches across the inferred relict bedding. This is attributed to the lack of a mobile pore fluid except in systems undergoing decarbonation. C¹³/C¹² ratios in Grenville and Vermont marbles and O¹⁸/O¹⁶ ratios in Grenville and greenschist-facies Vermont carbonates span the range of ancient limestones. Staurolite-kyanite zone calcareous schists and marbles from the Chester dome area, Vermont are depleted in O¹⁸(δO¹⁸=12 to 20‰) due to equilibrium or disequilibrium decarbonation and some partial exchange. Extrapolation of the dolomite-calcite fractionation expressions to 20° C indicates that dolomite is enriched in O¹⁸ by about 4.9‰ and in C¹³ by about 2.4‰.     

Distribution of Al between coexisting micas in metamorphic rocks from the Central Alps

In 61 pairs of coexisting biotites and muscovites from the Central Alps total Al scatters considerably, but in both series a gradual increase is noticed with increasing metamorphic grade. The ratio Al _Mu ^tot /Al _Bi ^tot remains virtually constant (1.61 average for greenschist facies, 1.57 for amphibolite facies). Tetrahedral Al varies little in biotites and increases in muscovites-phengites with rising metamorphic grade; accordingly the ratio Al _Mu ^IV /Al _Bi ^IV increases slightly with grade. Far the best control of metamorphism is evidenced by octahedral Al. In the muscovite series, and still more pronounced in the biotite series, Al^VI increases with increasing metamorphic grade. Consequently 1 $$K_D = \frac{{Al_{Mu}^{VI} }}{{Al_{Bl}^{VI} }}$$ decreases from 14 to 3. A map (Fig. 6) representing the regional distribution of the K_D values locates a 100 km long and 23 km broad central zone with low K_D. The outline of this central core almost coincides with the isograds anorthite-diopside-calcite and labradorite-pyroxene-hornblende of the Tertiary regional metamorphism; with some deviations this core also agrees with the zone in which phenomena of partial anatexis are observed. The K_D values of micas from anateotic pegmatites agree with those of associated gneisses and schists. The study demonstrates that in the course of progressive regional metamorphism equilibrium has been approached to an unexpected extent and that the two micas coexisted in a strict sense.     

Origin of garnet in the basic granulites around Saltora,W. Bengal,India

Garnetiferous basic granulites occur, as parts of hornblende-pyroxene- and pyroxene granulites, in a Precambrian terrain around Saltora. The chemistry of the garnetiferous basic granulites is broadly similar to that of the hornblende-pyroxene granulites, their immediate precursors, but in detail they have distinctly higher Fe/Mg ratios. The compositions of the major mafic silicates of the garnetiferous varieties do not reflect higher pressures of formation: the Jd/Ts ratios in calcic pyroxenes are similar to those from the non-garnetiferous varieties, and the pyrope contents of garnets are low. Exchange equilibrium in respect of major elements was established among the mafic silicates in spite of garnets being late overprints. The orthopyroxene — calcic pyroxene pairs from the garnetiferous granulites show lower values of K _D(Mg-Fe) ^opx-cpx than those from the non-garnetiferous granulites, pointing to lower temperature of equilibration. The K _D(Mg-Fe) ^opx-hbl K _D(Mg-Fe) ^cpx-hbl relations show that the more magnesian triads equilibrated at lower temperatures; viewed against experimental data regarding the effect of Mg/Fe ratios on the appearance of garnets in basic rocks, formation of garnets by cooling is strongly indicated. Several intergrowth textures, especially garnet-ilmenite and garnet-quartz (±albite) symplectites, and modal relations argue in favour of composite reactions of the type hornblende+ quartz-→calcic pyroxene+garnet+albite+H₂O, which couple hornblende breakdown reactions with orthopyroxene+anorthite→garnet reactions. The approximate range of pressure and temperature conditions, estimated from experimental data, are 6–8.5 kb and 750–830° C. Since garnets formed by cooling in iron-rich granulites, the garnetiferous granulites do not represent higher pressure subfacies of the granulite facies.     

Carbon isotope thermometry in marbles of the Adirondack Mountains, New York

Abstract Carbon isotope thermometry has been applied to coexisting calcite and graphite in marbles from throughout the Adirondack Mountains, New York. Eighty-nine calcite-graphite pairs from the amphibolite grade NW Adirondacks change systematically in temperature north-westwards from 680 to 640 to 670° C over a 30-km distance, reflecting transitions from amphibolite facies towards granulite facies to the north-west and to the south-east. Temperature contours based on calcite-graphite thermometry in the NW Adirondacks parallel mineral isograds, with the orthopyroxene isograd falling above 675° C, and indicate that regional metamorphic temperatures were up to 75° C higher than temperatures inferred from isotherms based on cation and solvus thermometry (Bohlen et al. 1985). Fifty-five calcite-graphite pairs from granulite grade marbles of the Central Adirondacks give regional metamorphic temperatures of 670–780° C, in general agreement with cation and solvus thermometry. Data for amphibolite and granulite grade marbles show a 12%oo range in δ¹³C_cal and δ¹³C_gr. A strong correlation between carbon isotopic composition and the abundance of graphite (C_gr/C_rock) indicates that the large spread in isotopic compositions results largely from exchange between calcite and graphite during closed system metamorphism. The trends seen in δ¹³C _vs. C_gr/C_rock and δ¹³C_cal vs. δ¹³C_gr could not have been preserved if significant amounts of CO₂-rich fluid had pervasively infiltrated the Adirondacks at any time. The close fit between natural data and calculated trends of δ¹³C vs. C_gr/C_rock indicates a biogenic origin for Adirondack graphites, even though low δ¹³C values are not preserved in marble. Delamination of 17 graphite flakes perpendicular to the c-axis reveals isotopic zonation, with higher δ¹³C cores. These isotopic gradients are consistent with new graphite growth or recrystallization during a period of decreasing temperature, and could not have been produced by exchange with calcite on cooling due to the sluggish rate of diffusion in graphite. Samples located >2km from anorthosite show a decrease of 0.5-0.8%oo in the outer 100 μ of the grains, while samples at distances over 8 km show smaller core-to-rim decreases of c.0.2%oo. Correlation between the degree of zonation and distance to anorthosite suggests that the isotopic profiles reflect partial overprinting of higher temperature contact metamorphism by later granulite facies metamorphism. Core graphite compositions indicate contact metamorphic temperatures were 860–890° C within 1 km of the Marcy anorthosite massif. If samples with a significant contact metamorphic effect (Δ(_cal-gr) <3.2%oo) are not included, then the remaining 38 granulite facies samples define the relation Δ¹³C(_cal-gr) = 3.56 ± 10⁶T^-2 (K).     

Ultra high temperature metamorphism of mafic granulites from South Altyn Orogen,West China: A result from the rapid exhumation of deeply subducted continental crust

The South Altyn orogen in West China contains ultra high pressure (UHP) terranes formed by ultra‐deep (>150–300 km) subduction of continental crust. Mafic granulites which together with ultramafic interlayers occur as blocks in massive felsic granulites in the Bashiwake UHP terrane, are mainly composed of garnet, clinopyroxene, plagioclase, amphibole, rutile/ilmenite, and quartz with or without kyanite and sapphirine. The kyanite/sapphirine‐bearing granulites are interpreted to have experienced decompression‐dominated evolution from eclogite facies conditions with peak pressures of 4–7 GPa to high pressure (HP)–ultra high temperature (UHT) granulite facies conditions and further to low pressure (LP)–UHT facies conditions based on petrographic observations, phase equilibria modelling, and thermobarometry. The HP–UHT granulite facies conditions are constrained to be 2.3–1.6 GPa/1,000–1,070°C based on the observed mineral assemblages of garnet+clinopyroxene+rutile+plagioclase+amphibole±quartz and measured mineral compositions including the core–rim increasing anorthite in plagioclase (X_An = 0.52–0.58), core–rim decreasing jadeite in clinopyroxene (X_Jd = 0.20–0.15), and TiO₂ in amphibole (Ti^M2/2 = 0.14–0.18). The LP–UHT granulite facies conditions are identified from the symplectites of sapphirine+plagioclase+spinel, formed by the metastable reaction between garnet and kyanite at <0.6–0.7 GPa/940–1,030°C based on the calculated stability of the symplectite assemblages and sapphirine–spinel thermometer results. The common granulites without kyanite/sapphirine are identified to record a similar decompression evolution, including eclogite, HP–UHT granulite, and LP–UHT granulite facies conditions, and a subsequent isobaric cooling stage. The decompression under HP–UHT granulite facies is estimated to be from 2.3 to 1.3 GPa at ~1,040°C on the basis of textural records, anorthite content in plagioclase (X_An = 0.25–0.32), and grossular content in garnet (X_Grs = 0.22–0.19). The further decompression to LP–UHT facies is defined to be >0.2–0.3 GPa based on the calculated stability for hematite‐bearing ilmenite. The isobaric cooling evolution is inferred mainly from the amphibole (Ti^M2/2 = 0.14–0.08) growth due to the crystallization of residual melts, consistent with a temperature decrease from >1,000°C to ~800°C at ~0.4 GPa. Zircon U–Pb dating for the two types of mafic granulite yields similar protolith and metamorphic ages of c. 900 Ma and c. 500 Ma respectively. However, the metamorphic age is interpreted to represent the HP–UHT granulite stage for the kyanite/sapphirine‐bearing granulites, but the isobaric cooling stage for the common granulites on the basis of phase equilibria modelling results. The two types of mafic granulite should share the same metamorphic evolution, but show contrasting features in petrography, details of metamorphic reactions in each stage, thermobarometric results, and also the meaning of zircon ages as a result of their different bulk‐rock compositions. Moreover, the UHT metamorphism in UHP terranes is revealed to represent the lower pressure overprinting over early UHP assemblages during the rapid exhumation of ultra‐deep subducted continental slabs, in contrast to the cause of traditional UHT metamorphism by voluminous heat addition from the mantle.     

Metamorphic Characteristics of Granulite Facies Rocks in the Laixi-Pingdu Area in Eastern Shandong Province

Abstract Granulite in eastern Shandong is mainly exposed in Laixi, Pingdu, Changyi and Anqiu, and the diagnostic mineral assemblage is Opx+Cpx+Hb+Pl ± Q ± Sea. The appearance of orthopyroxene and its coexistence with hornblende indicate that the reaction Hb+Q = Opx+Cpx+Pl+H₂O did not proceed completely and therefore these rocks belong to the amphibolite- granulite transition facies, i.e., belonging to hornblende-granulite subfacies. According to the data obtained from such geothermometers and geobarometers as Opx- Cpx, Opx- Hb, Cpx- Hb, Hb- PI, Sca- Pl and Fe- Ti oxides, it has been determined that the temperature of the main metamorphic stage was 720° – 810°C, the pressure 0.5 GPa and fo₂10^?15.5, showing a geothermal gradient of 41–46°C / km, and thus the rocks belong to “low-temperature” and low-pressure granulite facies.     

Stabilitätsbeziehungen zwischen Chlorit,Cordierit und Almandin bei der Metamorphose

The stability relations between cordierite and almandite in rocks, having a composition of CaO poor argillaceous rocks, were experimentally investigated. The starting material consisted of a mixture of chlorite, muscovite, and quartz. Systems with widely varying Fe²⁺/Fe²⁺+Mg ratios were investigated by using two different chlorites, thuringite or ripidolite, in the starting mixture. Cordierite is formed according to the following reaction: $${\text{Chlorite + muscovite + quartz}} \rightleftharpoons {\text{cordierite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} + {\text{H}}_{\text{2}} {\text{O}}$$ . At low pressures this reaction characterizes the facies boundary between the albite-epidotehornfels facies and the hornblende-hornfels facies, at medium pressures the beginning of the cordierite-amphibolite facies. Experiments were carried out reversibly and gave the following equilibrium data: 505±10°C at 500 bars H₂O pressure, 513±10°C at 1000 bars H₂O pressure, 527±10°C at 2000 bars H₂O pressure, and 557±10°C at 4000 bars H₂O pressure. These equilibrium data are valid for the Fe-rich starting material, using thuringite as the chlorite, as well as for the Mg-rich starting mixture with ripidolite. At 6000 bars the equilibrium temperature for the Mg-rich mixture is 587±10°C. In the Fe-rich mixture almandite was formed instead of cordierite at 6000 bars. The following reaction was observed: $${\text{Thuringite + muscovite + quartz}} \rightleftharpoons {\text{almandite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + H}}_{\text{2}} {\text{O}}$$ . Experiments with the Fe-rich mixture, containing Fe²⁺/Fe²⁺+Mg in the ratio 8∶10, yielded three stability fields in a P,T-diagram (Fig.1):

1. Above 600°C/5.25 kb and 700°C/6.5 kb almandite+biotite+Al₂SiO₅ coexist stably, cordierite being unstable.
2. The field, in which almandite, biotite and Al₂SiO₅ are stable together with cordierite, is restricted by two curves, passing through the following points:
   1. 625°C/5.5 kb and 700°C/6.5 kb,
   2. 625°C/5.5 kb and 700°C/4.0 kb.
3. At conditions below curves 1 and 2b, cordierite, biotite, and Al₂SiO₅ are formed, but no garnet.

An appreciable MnO-content in the system lowers the pressures needed for the formation of almandite garnet, but the quantitative influence of the spessartite-component on the formation of almandite could not yet be determined. the Mg-rich system with Fe²⁺/Fe²⁺+Mg=0.4 garnet did not form at pressures up to 7 kb in the temperature range investigated. Experiments at unspecified higher pressures (in a simple squeezer-type apparatus) yielded the reaction: $${\text{Ripidolite + muscovite + quartz}} \rightleftharpoons {\text{almandite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + H}}_{\text{2}} {\text{O}}$$ . Further experiments are needed to determine the equilibrium data. The occurence of garnet in metamorphic rocks is discussed in the light of the experimental results.     

Hydrogen and carbon in solid solution in oxides and silicates

The dissolution of H₂O and CO₂ in structurally dense, nominally anhydrous and non-carbonate oxide matrices such as MgO and CaO is reviewed. H₂O and CO₂ are treated as gaseous oxide components which enter into solid solution with the refractory oxide hosts. They form anion complexes associated with cation vacancy sites. Evidence is presented that OH^? pairs which derive from the dissolution of H₂O are subject to a charge transfer (CT) conversion into peroxy moieties and molecular hydrogen, O ₂ ^2? ... H₂. Because the O ₂ ^2? moiety is small (O^?-O^? distance ≈ 1.5 Å) high pressure probably favors the CT conversion. Mass spectroscopic studies show that molecular H₂ may be lost from the solid which retains excess oxygen in the form of O ₂ ^2? , leading to the release of atomic O. The dissociation of O ₂ ^2? moieties into a vacancy-bound O^? state and an unbound O^? state can be followed by measuring the internal redox reactions involving transition metal impurities, the transient paramagnetism of the O^? and their effect on the d.c. conductivity. Evidence is presented that CO₂ molecules dissolve dissociatively in the structurally dense oxide matrix, as if they were first to dissociate into CO+O and then to form separate solute moieties CO ₂ ^2? and O ₂ ^2? , both associated with cation vacancy sites. In the CO ₂ ^2? moiety (C-O^? distance 1.2–1.3 Å, OCO angle ≈ 130°) the C atom probably sits off center. The transition of the C atom into interstitial sites is accompanied by dissociation of the CO ₂ ^2? moiety into CO^? and O^?. This transition can be followed by infrared spectroscopy, using OH^? as local probes. Further support derives from magnetic susceptibility, thermal expansion, low frequency dielectric loss and low temperature deformation measurements. The recently observed emission of O and Mg atoms besides a variety of molecules such as CO, CO₂, CH₄, HCN and other hydrocarbons during impact fracture of MgO single crystals is presented and discussed in the light of the other experimental data.     

Experimental investigation and application of the equilibrium rutile + orthopyroxene = quartz + ilmenite

Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: $${\text{SiO}}_{\text{2}} + ({\text{Mg,Fe}}){\text{TiO}}_{\text{3}} {\text{ + (Mg,Fe)SiO}}_{\text{3}} $$ have been calibrated in the range 800–1100° C and 12–26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs_40–70, using Ag₈₀Pd₂₀ capsules with \(f_{{\text{O}}_{\text{2}} } \) buffered at or near iron-wüstite. Ilmenite compositions coexisting with orthopyroxene are \(X_{{\text{MgTiO}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.06 to 0.15 and \(X_{{\text{Fe}}_{\text{2}} {\text{O}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.00 to 0.01, corresponding toK _D values of 13.3, 10.2, 9.0 and 8.0 (±0.5) at 800, 900, 1000 and 1100° C, respectively, whereK _D =(XMg/XFe)^Opx/(XMg/XFe)^Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models for ilmenite available from the literature to calculatea/X relations in orthopyroxene of intermediate composition. Data from this study indicate that FeSiO₃?MgSiO₃ orthopyroxene exhibits small, positive deviations from ideality over the range 800–1100°C.     

Les glaucophanites et roches associées de l'île de Groix (Morbihan,France): étude minéralogique et pétrogénétique

The petrographic and mineralogic study of the different rock facies on île de Groix shows that two metamorphic episodes have affected the alkaline basic rocks and associated pelitic schists. The first is represented by a zonation (west-east): II-III-II-I-II where I= eclogite facies glaucophanites (8,5 bars, 530°C), II=glaucophane-epidote-garnet facies (8 kbars, 500°C), III=greenschist facies containing blue-green amphibole (7,5 kbars, 470°C). The second metamorphic episode has partially transformed these rocks to the albite-chlorite-epidote-blue green amphibole facies (6,5 kbars, 470°C). The variations of \(P_{O_2 } \) and \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) as they affect local assemblages is detailed.     

Manganocummingtonite from the mesoproterozoic,Sausar fold belt,central India

Manganocummingtonite occurs with spessartine, quartz and pyrolusite in the Chikmara area, Sausar fold belt, central India. Its composition is [Ca_0.3–0.35(Mg_3.3–3.5Mn_1.6–1.8Fe²⁺ _1.4–1.5)(Si_{7.931–7.997}Al^iv _{0.003–0.069})O₂₂(OH_1.5–2.0F_0.0–0.5)] being fairly rich in Ca, which is indicative of metamorphic temperature in the amphibolite facies. The garnet contains 77.5% spessartine, 13% almandine and minor andradite, grossular and pyrope components. Unusually, there is no carbonate, pyroxene, pyroxmangite, rhodonite, magnetite or hematite. The available Al in the rock stabilized garnet and this mineral incorporated minor Fe³⁺ present in the rock as andradite component. The manganocummingtonite-garnet pairs developed at ～600°C during amphibolite facies metamorphism in low $X_{CO_2 } $ system, stabilized with $X_{Mn/(Mn + Fe^{2 + } + Mg)} $ = 0.25 to 0.28 in the amphibole and 0.85 in the garnet and formed under unusually low fO ₂ conditions for the Sausar region, near channelized fluids which deposited quartz may have controlled the fO ₂ .     

Ore-forming solution and genesis of a rock crystal deposit in south Hunan,indicated by fluid inclusion studies

Si, Al, Ca, Mg, Fe, Na, K, CO ₃ ^?2 , F, etc. are detected from the fluid inclusion leachates. Among these constituents, Si, Na, and CO ₃ ^?2 are predominant, amounting to more than 80 percent. This indicates that the ore-forming solution must be alkaline with Si, Na, and CO ₃ ^?2 as its dominant components. Homogenization temperatures for the solution range from 80 to 360°C. Although rock quartz can crystallize at the above temperature interval, perfect crystals of economic importance are largely formed below 260°C. The temperature of formation increases toward the granite intrusives at a rate of about one degree per meter. It is estimated from the lithostatic load that the salinity of rock quartz is 17–23 (NaCl wt%), while that of vein quartz is relatively high as compared with the former. There is a tendency for the salinity of the ore-forming solution to increase with depth.     

Laihunite—A new iron silicate mineral

Laihuite reported in the present paper is a new iron silicate mineral found in China with the following characteristics:

1. This mineral occurs in a metamorphic iron deposit, associated with fayalite, hypersthene, quartz, magnetitc, etc.
2. The mineral is opaque, black in colour, thickly tabular in shape with luster metallic to sub-metallic, two perfect cleavages and specific gravity of 3.92.
3. Its main chemical components are Fe and Si with Fe³⁺>Fe²⁺. The analysis gave the formula of Fe Fe _1.00 ³⁺ ·Fe _0.58 ²⁺ ·Mg _0.03 ²⁺ ·Si_0.96O₄.
4. Its DTA curve shows an exothermic peak at 713°C.
5. The mineral has its own infrared spectrum distinctive from that of other minerals.
6. This mineral is of orthorhombic system; space group:C _2h ^/5 ?P2₁/c; unit cell:α=5.813ű0.005,b=4.812ű0.005,c=10.211ű0.005,β=90.87°.
7. The Mössbauer spectrum of this mineral is given, too.

     

Interdiffusion of NaSi—CaAl in peristerite

The ‘average’ interdiffusion coefficient ( \(\bar D\) ) for NaSi—CaAl exchange in plagioclase for the interval from An₀ to An₂₆ was estimated from experimentally determined homogenization times for peristerite exsolution lamellae. The average spacing between adjacent (unlike) lamellae is 554±77 Å. Dry heating in air at 1,100°C for 98 days produced no change in the exsolution microstructure; thus \(\bar D\) (dry)<10^?17 cm²/s. This limit is consistent with the recently reported ‘average’ \(\bar D\) (dry) values for the Huttenlocher interval (An_70–90) at this temperature. At 1.5 GPa with about 0.2 weight percent water added the ‘average’ diffusion coefficient from 1,100°C to 900°C is given by: \(\bar D\) (wet)=18 _?15 ⁺¹⁰⁸ (cm²/s) exp (?97±5 (kcal/mol)/RT), where R is the gas constant, and T is °K. This \(\bar D\) (wet) at 1,100°C is more than three orders of magnitude greater than \(\bar D\) (dry) for Na- and Ca-rich plagioclases.     

Existing forms of tungsten in hydrothermal solutions and forming conditions of scheelite

Experiments on the solubility of WO₃ in HCl and KCl solutions at 200°C show that tungsten cannot migrate in the form of chloride in solutions. In Cl-rich hydrothermal solutions of moderate salinity, tungsten migrates mainly as alkali salts of HWO ₄ ^? and WO ₄ ^2? . Determination of the solubility of WO₃ in HF and KHF₂ solutions at 100–300°C shows that tungsten migrates steadily as WO₃F^? and WO₂F ₃ ^? in F-rich hydrothermal solutions. Experiments and thermodynamic calculations also indicate that silico-wolframic acid, polymeric wolframic acid and sulfoxy wolframic acid cannot extensively occur in hydrothermal solutions. In addition, the physicochemical conditions of formation of scheelite are also discussed in the present paper.     

Thermodynamics of plagioclase II: Temperature evolution of the spontaneous strain at the I\bar 1 \leftrightarrow P\bar 1 phase transition in anorthite

The temperature dependence of the lattice parameters of pure anorthite with high Al/Si order reveals the predicted tricritical behaviour of the \(I\bar 1 \leftrightarrow P\bar 1\) phase transition at T _c ^* =510 K. The spontaneous strain couples to the order parameter Q° as x _i∝S _xQ ⁱ Q°² with S _xQ ¹ =4.166×10^?3, S _xQ ² =0.771×10^?3, S _xQ ³ =?7.223×10^?3 for the diagonal elements. The temperature dependence of Q° is $$Q^{\text{o}} = \left( {1 - \frac{T}{{510}}} \right)^\beta ,{\text{ }}\beta = \tfrac{{\text{1}}}{{\text{4}}}$$ A strong dependence of T _c ^* , S _xQ ⁱ and β is predicted for Al/Si disordered anorthite.     

A pyroxene-bearing meta-ironstone and other pyroxene-granulites from Tonagh Island, Enderby Land, Antarctica: further evidence for very high temperature (> 980°C) Archaean regional metamorphism in the Napier Complex

Abstract A suite of granulites including a meta-ironstone, pyroxenites, and spinel-lherzolites from East Tonagh Island, Enderby Land, Antarctica, preserve exsolution-recry-stallization features consistent with a shared metamorphic evolution that involves marked cooling from initial metamorphic temperatures of nearly 1000°C. Reintegrated pre-exsolution and pre-reaction grain compositions in the meta-ironstone indicate the former coexistence of metamorphic pigeonite (Wo₁₂En₃₈Fs₅₀) and ferroaugite (Wo₃₅En₃₁Fs₃₄) at temperatures in excess of 980°C for pressures of 7 kbar (0.7 GPa) using pyroxene quadrilateral thermometry (Lindsley, 1983). Intra-grain lamellae relationships indicate the exsolution of a second pigeonite (Wo₁₂En₃₅Fs₅₃) from the ferroaugite at temperatures in the range 930–970°C, prior to the c. 720–600°C exsolution of orthopyroxene and clinopyroxene (100) lamellae and later partial recrystallization at similar temperatures. Although pyroxenitic and iherzolitic granulites preserve a much less complete history, reintegrated porphyroclast compositions in these yield temperature estimates which approach those inferred from the metaironstone. Pyroxene thermometry based on neoblast compositions suggests that recrystallization post-dating a late, low intensity, deformation phase (D3) occurred at temperatures greater than 600°C. These results are consistent with the independent evidence obtained from studies of metapelitic and felsic rock types for very high temperature metamorphism throughout the Napier Complex followed by near-isobaric cooling and later deformation under lower-grade granulite facies conditions. Comparison with similar pyroxene data from Fyfe Hills (Sandiford & Powell, 1986) demonstrates further the regional significance of these high temperatures, and implies broadly isothermal metamorphic conditions over a large area (～ 5000 km²) and thickness (6–9 km) of lower crust at c. 3070 Ma.     

Multistage metamorphism of the Huangtuling granulite, Northern Dabie Orogen, eastern China: implications for the tectonometamorphic evolution of subducted lower continental crust

Granulites from Huangtuling in the North Dabie metamorphic core complex in eastern China preserve rare mineralogical and mineral chemical evidence for multistage metamorphism related to Palaeoproterozoic metamorphic processes, Triassic continental subduction‐collision and Cretaceous collapse of the Dabie Orogen. Six stages of metamorphism are resolved, based on detailed mineralogical and petrological studies: (I) amphibolite facies (6.3–7.0 kbar, 520–550 °C); (II) high‐pressure/high‐temperature granulite facies (12–15.5 kbar, 920–980 °C); (III) cooling and decompression (4.8–6.0 kbar, 630–700 °C); (IV) medium‐pressure granulite facies (7.7–9.0 kbar, 690–790 °C); (V) low‐pressure/high‐temperature granulite facies (4.0–4.7 kbar, 860–920 °C); (VI) retrograde greenschist facies overprint (1–2 kbar, 340–370 °C). The P–T history derived in this study and existing geochronological data indicate that the Huangtuling granulite records two cycles of orogenic crustal thickening events. The earlier three stages of metamorphism define a clockwise P–T path, implying crustal thickening and thinning events, possibly related to the assembly and breakup of the Columbia Supercontinent at c. 2000 Ma. Stage IV metamorphism indicates another crustal thickening event, which is attributed to Triassic subduction/collision between the Yangtze and Sino‐Korean Cratons. The dry lower crustal granulite persisted metastably during the Triassic subduction/collision because of the lack of hydrous fluid and deformation. Stage V metamorphism records the Cretaceous collapse of the Dabie Orogen, possibly due to asthenosphere upwelling or removal of the lithospheric mantle resulting in heating of the granulite and partial melting of the North Dabie metamorphic core complex. Comparison of the Huangtuling granulite in North Dabie and the high‐pressure–ultrahigh‐pressure metamorphic rocks in South Dabie indicates that the subducted upper (South Dabie) and lower (North Dabie) continental crusts underwent contrasting tectonometamorphic evolution during continental subduction‐collision and orogenic collapse.