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1.
The compositional variations in epidotes, Ca2Al2(Fe3+, Al)-Si3O12(OH), from a prograde Mesozoic rock series in the Eastern Alps, Austria, are systematically related to metamorphic grade and the oxidation state of the rock. With increasing metamorphic grade the average composition of the zoned epidotes shifts to Fe3+-poorer compositions reflecting not only the effect of temperature and total pressure but also the concomitant decrease of the oxidation state of the rocks. Oxidized hematite-bearing assemblages are: 90 mole % Al2FeEp (greenschists) 70 mole % Al2FeEp (garnet amphibolites) 58 mole % Al2FeEp (eclogites); reduced sulfidebearing assemblages are: 42 mole % Al2FeEp (greenschists) 24 mole % Al2FeEp (garnet amphibolites) 23 mole % Al2FeEp (eclogites).A similar compositional evolution of the epidotes as in the spatial sequence of the samples can be observed within the single zoned crystals, reflecting the temporal changes of temperature, total pressure and oxygen fugacity during the prograde crystallization. The Fe3+-contents of core and rim decrease with increasing metamorphic grade and decreasing oxidation state. Generally the zoned epidotes consist of a Fe3+-rich core (90 to 63 mole % Al2FeEp) and a Fe3+-poorer rim (55 to 23 mole % Al2FeEp). Core and rim of the epidote crystals are separated by a compositional gap the extension of which is independent of the bulk rock composition, the oxidation state, and the mineralogical composition of the assemblages but becomes smaller with increasing metamorphic grade: 7253 mole % Al2FeEp (low grade greenschists, 400° C) 6355 mole % Al2FeEp (higher grade greenschists, 500° C), and 6055 mole % Al2FeEp (garnet amphibolites, 500–550° C). At the temperature conditions of the highest grade garnet amphibolites and eclogites (550° C) the compositional gap closes at a composition of 58 mole % Al2FeEp.The data presented thus confirm clearly the existence of an asymmetric miscibility gap in the monoclinic Al-Fe(III)-epidote solid solution series, which, for the first time, has been assumed by Strens (1964, 1965).A model is proposed that describes the prograde compositional evolution of the epidotes studied through the competing mechanisms of growth and diffusional Al-Fe3+ exchange and their dependence on metamorphic grade and oxidation state.  相似文献   

2.
In the gneisses from the drillhole ZK2304 of the Donghai area, there have been preserved high- and ultrahigh-pressure metamorphic mineral assemblages, a series of complicated retrogressive textures and relevant metamorphic reactions. In addition to garnet, jadeititic-clinopyroxene and rutile, other peak stage (M2) minerals in some gneisses include phengite, aragonite and coesite or quartz pseudomorphs after coesite. The typical peak-stage mineral assemblages in gneisses are characterized by garnet + jadeitic-clinopyroxene + rutile + coesite, garnet + jadeitic-clinopyroxene + phengite + rutile ± coesite and garnet + jadeitic-clinopyroxene + aragonite + rutile ± coesite. The grossular content (Gro) in garnet is high and may reach 50.1 mol%. The SiO2 content of phengite ranges from 54.37% to 54.84% with 3.54–3.57 p.f.u. Quartz pseudomorphs after coesite occur as inclusions in garnet. The gneisses of the Donghai area have been subjected to multistage recrystallization and exhibit a closewise P-T evolutional path characterized by the near-isothermal decompression. The inclusion assemblage (Hb+Ep+Bi+Pl+Qz) within garnet and other minerals has recorded a pre-peak stage (M1) epidote amphibole fades metamorphic event. High- and ultrahigh-pressure peak metamorphism (M2) took place at T=750–860°C and P>2.7 GPa. The symplectitic assemblages after garnet, jadeitic-clinopyroxene and rutile imply a near-isothermal decompression metamorphism (M3, M4) during the rapid exhumation. Several lines of evidence of petrography and metamorphic reactions indicate that both gneisses and eclogites have experienced ultrahigh-pressure metamorphism in the Donghai area. This research may be of great significance for an in-depth study of the metamorphism and tectonic evolution in the Su-Lu ultrahigh-pressure metamorphic belt.  相似文献   

3.
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   

4.
The Cazadero blueschist allochthon lies within the Central MelangeBelt of the Franciscan assemblage in the northern Coast Rangeof California. Mineral compositions and assemblages of morethan 200 blueschists from Ward Creek were investigated. Theresults delineate lawsonite-, pumpellyite-, and epidote-zones.The lawsonite and pumpellyite zones are equivalent to the TypeII metabasites of Coleman & Lee (1963) and are characterizedby well-preserved igneous textures, relict augite, and pillowstructures, whereas epidote zone rocks are equivalent to theType III strongly deformed and schistose metabasites. Chlorite,phengite, aragonite, sphene, and minor quartz and albite areubiquitous. The lawsonite zone metabasites contain lawsonite ( < 3 wt.per cent Fe2O3), riebeckite-crossite, chlorite, and Ca-Na-pyroxene;some rocks have two distinct clinopyroxenes separated by a compositionalgap. The clinopyroxene of the lowest grade metabasites containsvery low Xjd. In pumpellyite zone metabasites, the most commonassemblages contain Pm + Cpx + Gl + Chl and some samples withhigher Al2O3 and/or Fe2O3 have Pm + Lw + Cpx + Chl, Actinolitejoins the above assemblage in the upper pumpellyite zone wherethe actinolite-glaucophane compositional gap is well defined.The epidote zone metabasites are characterized by the assemblagesEp + Cpx + two amphiboles + Chl, Lw + Pm + Act + Chl, and Ep+ Pm + two amphiboles + Chl depending on the Fe2O3 content ofthe rock. In the upper epidote zone, winchite appears, Fe-freelawsonite is stable, pumpellyite disappears and omphacite containsvery low Ac component. Therefore, the common assemblages areEp + winchite + Lw, and Lw + Omp + winchite. With further increasein metamorphic grade, epidote becomes Al-rich and lawsoniteis no longer stable. Hence Ep + winchite + omphacite ? garnetis characteristic. Mineral assemblages and paragenetic sequences delineate threediscontinuous reactions: (1) pumpellyite-in; (2) actinolite-in;and (3) epidote-in reactions. Using the temperatures estimatedby Taylor & Coleman (1968) and phase equilibria for Ca-Na-pyroxenes,the P–T positions of these reactions and the metamorphicgradient are located. All three metabasite zones occur withinthe aragonite stability field and are bounded by the maximumpressure curve of Ab = Jd + Qz and the maximum stabilities ofpumpellyite and lawsonite. The lawsonite zone appears to bestable at T below 200?C with a pressure range of 4–6?5kb; the pumpellyite zone between 200 and 290?C and the epidotezone above 290?C with pressure variation between 6?5 and 9 kb.The metamorphic field gradient appears to have a convex naturetowards higher pressure. A speculative model of underplatingseamounts is used to explain such feature.  相似文献   

5.
Zusammenfassung In einem Profil ansteigender Metamorphose werden im Stavanger-Gebiet/SW-Norwegen zwei Gesteinstypen, repräsentiert durch 17 Meta-Arkosen und Quarz-Feldspat-Gneise, sowie 19 metamorphe Tuffe und Tuffite, modellhaft auf ihre Saussuritparagenesen hin analysiert.Mikroskopische und mikroanalytische Untersuchungen zeigen eine weitestgehende Eduktabhängigkeit der Saussuritparagenesen. In calcitarmen granitoiden Edukten bilden sich schon im sehr schwach-metamorphen Stadium folgende mit Ab-reichem Plagioklas koexistierende Saussuritmineralien: 4 An-reicher Plagioklas+K-Feldspat+4 Eisenhydroxid + H2O 2 Fe(III)Al2-Epidot+Muskovit+Hämatit+2 Quarz. In calcitführenden Meta-Arkosen gewinnt die Mineralreaktion: An-Plagioklas+K-Feldspat+2 Eisenhydroxid+CO2Calcit+Muskovit+ Hämatit+Quarz an Bedeutung. Im reduzierenden geochemischen Milieu der Meta-Tuffe und -Tuffite tritt in diesem metamorphen Bereich als charakteristische Neubildung Biotit neben Muskovit auf. Auch in den calcitreichen tuffitischen Proben koexistieren die Saussuritkomponenten Calcit, Muskovit, Hämatit, Quarz und Biotit.Die mikroanalytisch untersuchten Saussuritmineralien Plagioklas und Epidot zeigen anhand von annähernd 800 chemischen Vollanalysen in der Entwicklung ihrer Chemismen während der Metamorphose für beide Sedimente gleiche Trends. Im niedrigtemperierten Bildungsstadium der Saussurite können die An-Gehalte der Feldspäte in Abhängigkeit vom Edukt und aufgrund unterschiedlich intensiver Rekristallisation der Sedimente relativ stark schwanken. Die Epidote sind je nach primärem Fe(III)-Angebot mehr oder weniger eisenreich. In Richtung ansteigender Metamorphose stellen sich in den Epidoten beim Übergang zu oligoklasführenden Paragenesen maximale Fe(III)-Gehalte ein, die in Form eines rhythmischen Zonarbaus die wechselnden -Bedingungen im Verlauf der Metamorphose widerspiegeln. Bereits hier setzt der retrograde Saussuritisierungsprozeß ein: es reagieren Fe(III)Al2-Epidot, Muskovit, Quarz, Hämatit und Albit/Oligoklas zu anorthitreicherem Plagioklas, Biotit und Wasser. Zusätzlich bildet sich durch die Zersetzung des Al-reichen Epidots Mikroklin.Die Untersuchung zur Wechselbeziehung zwischen dem Eisengehalt des Eduktes und dem der Epidote ergibt, daß die Fe(III)-Einbaurate der Epidote in keiner Weise von den Fe(III)-Konzentrationen der Meta-Sedimente beeinflußt wird, vielmehr können eduktspezifische Intervalle für die Eisenanreicherung der Epidote nachgewiesen werden.
Electron microprobe investigations of saussurites dependent on metamorphic stage and geochemical environment
In a profile of ascending metamorphism, the saussuritic parageneses of two characteristic rock types, 17 acid meta-arkoses and 19 basic meta-tuffs and meta-tuffites, were investigated by microscopical and microanalytical methods.Microscopic studies reveal that the specific saussurite mineral association is dependent on the petrographic substratum. In very low stage metamorphism, granitic rocks show the following saussurite minerals coexisting with albite-rich plagioclase: 4 An-rich plagioclase+K-feldspar +4 ironhydroxide+H2O2 Fe (III) Al2-epidote + muscovite + hematite + 2 quartz. Phyllitic and calciferous meta-arkoses exhibit predominantly the following saussurite reaction: An-plagioclase + K-feldspar + 2 ironhydroxide + CO2 calcite + muscovite + hematite + quartz. In the reducing environment of the meta-tuffs and meta-tuffites, biotite is formed in addition to muscovite.The changing chemical composition of the saussurite minerals (plagioclase and epidote) at different stages of metamorphism was determined by 800 quantitative electron microprobe analyses. The changes found in both rock types are nearly the same. During low metamorphic stage, the An-content of the plagioclases depends on the substratum and the variable intensity of recrystallization. The Fe-content of the epidotes is dependent on the amount of iron available.The epidotes are enriched in Fe toward the transition to oligoclase-bearing parageneses. These Fe-contents cause rhythmical zoning, representing varying conditions during metamorphism. With increasing metamorphic grade the retrograde process of saussuritization is initiated. The reactants are Fe (III) Al2-epidote, muscovite, quartz, hematite, and albite/ oligoclase. The decomposition of these minerals leads to An-rich plagioclase, biotite, microcline, and H2O.

Herrn Prof. Dr. G. Müller, Clausthal, danke ich für viele anregende Diskussionen sowie für die kritische Durchsicht des Manuskriptes.

Mein Dank gilt auch Herrn Dr. A. Schneider, Geochemisches Institut der Universität Göttingen, der mir freundlicherweise das Rucklidge-Korrekturprogramm für Silikatanalysen zur Verfügung stellte. Zu danken habe ich auch Herrn Dr. F. Wurm, Geologisches Landesamt Baden-Württemberg, für sein großzügiges Entgegenkommen und die tatkräftige Unterstützung bei der ergänzenden Probennahme im Gebiet der nordwestlichen Inseln des Boknfjords.

Der Deutschen Forschungsgemeinschaft schulde ich Dank für die finanzielle Unterstützung dieser Arbeit.  相似文献   

6.
The 6km-thick Karmutsen metabasites, exposed over much of Vancouver Island, were thermally metamorphosed by intrusions of Jurassic granodiorite and granite. Observation of about 800 thin sections shows that the metabasites provide a complete succession of mineral assemblages ranging from the zeolite to pyroxene hornfels facies around the intrusion. The reaction leading to the appearance of actinolite, which is the facies boundary between prehnite-pumpellyite and prehnite-actinolite facies, was examined using calcite-free Karmutsen metabasites collected from the route along the Elk river. In the prehnite-pumpellyite facies, X Fe3+[Fe3+/(Fe3++Al)] in prehnite, pumpellyite and epidote buffered by the four-phase assemblage prehnite+pumpellyite+epidote+chlorite systematically decreases with increasing metamorphic grade. Such a trend is the reverse of that proposed by Cho et al. (1986); this may be related to the higher in the Mt. Menzies area. The actinolite-forming reaction depends on the value of X Fe3+ in pumpellyite. If using a low value of Fe3+, 3.89 Pr(0.06)+0.48 Ep(0.26)+0.60 Chl+H2O=2.10 Pm (0.08)+0.17 Act+0.88 Qz is delineated. The number in parentheses stands for the X Fe3+value in Ca-Al silicates. On the other hand, replacing the X Fe3+ of 0.08 in pumpellyite with a higher X Fe3+ value (0.24) changes the reaction to 0.41 Pm+0.02 Chl+0.42 Qz=0.11 Pr+0.62 Ep+0.10 Act+H2O. The first (hydration) reaction forms pumpellyite and actinolite on the high-temperature side, whereas the second (dehydration) reaction consumes pumpellyite to form prehnite, epidote and actinolite. The former reaction seems to explain the textural relationship of Ca-Al silicates in the study area. However, actinolite-forming reaction changes to a different reaction depending on the compositions of the participating minerals, although in the other area even physical conditions may be similar to those in the study area. Chemographic analysis of phase relations in the PrA facies indicates that the appearance of prehnite depends strongly on the bulk FeO/MgO ratio: this may explain the rarity of prehnite in common metabasites in spite of the expected dominant occurrence in the conventional pseudo-quaternary (Ca-Al-Fe3+-FM) system. An increasing FeO/MgO ratio stabilizes the Pr+Act assemblage and reduces the stability of the Pm+Act one. Therefore, the definition of pumpellyite-actinolite facies should include not only Pm+Act but also the absence of Pr+Act assemblages. In addition to the possible role of high (Cho and Liou 1987) and/or high to mask the appearance of prehnite, the effect of the FeO/MgO ratio is emphasized.  相似文献   

7.
Phase relations and mineral chemistry involving the phases garnet (Gt), spinel (Sp), hypersthene (Hy), sapphirine (Sa), cordierite (Cd), sillimanite (Sil) and quartz (Qz) have been experimentally determined in the system FMAS (FeO−MgO−Al2O2−SiO2) under low fO2 and for various H2O/CO2 conditions. Several compositions were studied with 100 (Mg/Mg+Fe) ratio ranging from 64 to 87 with excess quartz and sillimanite. Our data do not show any differences in Gt−Cd stability and composition as a function of H2O, CO2 and H2O−CO2 (±CH4) content, in good agreement with a previous experimental study at lower temperature (Aranovich and Podlesskii 1983). At 1,000° C and 11 kbar, under CO2-saturated conditions, cordierite grew from a crystalline mix unseeded with cordierite. Thus, under water-absent conditions, cordierite will have a high-P stability field in the presence of CO2. If water has a pressure stabilizing effect on cordierite, then our results would indicate that the effects of H2O and CO2 are of the same magnitude at high temperature. Our data support the theoretical P-T grid proposed by Hensen (1986) for high-T metapelites and are largely consistent with the high-temperature experimental data of Hensen and Green (1973). The univariant boundary Gt+Cd=Hy+Sil+Qz, which marks the disappearance of Hy−Sil−Qz assemblages, has a negative dP/dT slope above 1,000° C and a positive one below this temperature. Extrapolation of our data to iron-free systems shows that the high-P breakdown limit of Mg-cordierite has a negative slope in the range 1,025–1,300° C and probably positive below 1,000° C. This indicates a maximum of stability for Mg-cordierite at around 1,000° C and 13 kbar. Because of the curvature of the univariant reactions En+Sil=Py+Qz, Mg−Cd=En+Sil+Qz and Gt+Cd=Hy+Sil+Qz, the iron-free invariant point involving the phases Py, En, Cd, Sil and Qz probably does not exist. Sapphirine—Qz-bearing assemblages are stable only at temperatures above 1,050° C. At 1,075° C, the joint Gt−Sa is stable up to 11 kbar. At higher pressure, garnet, sapphirine and quartz react according to the reaction Gt+Sa+Qz=Hy+Sil. Reequilibrated sapphirines are more aluminous than the theoretical endmember Mg2Al4SiO10 due to AlAl=MgSi substitutions [100(Al2O3/Al2O3+FeO+MgO) in experimental sapphirines ranges from 50.5 to 52.2]. Sapphirine in the assemblage Sa−Cd−Sil−Qz shows a decrease in Al content with decreasing temperature and pressure, such that the alumina isopleths for sapphirine have a slight negative dP/dT slope. A similar decrease in Al content of sapphirine with temperature is also observed in Sa−Sil−Qz assemblages.  相似文献   

8.
Samples of micaschists, gneisses, and migmatites from a sequence of metamorphic subfacies of the Gévennes Médianes (Dép. Ardèche, France) are characterized chemically by
  1. a high and only slightly varying Al2O3 content (m.v.=17.57 wt.-%, stand, dev.=1.804, var. coeff.=0.103).
  2. a negligible variation of the molar MgO/MgO+FeO ratio (m.v.=0.504, stand. dev.= 0.066, var. coeff.=0.130), and
  3. an insignificant variation of the molar CaO/CaO + Na2O ratio (m.v.=0.360, stand. dev.=0.014, var. coeff.=0.039).
The Na2O and K2O values of the migmatite samples are respectively 14 and 30% higher than those of the samples of the neighbouring gneisses and schists. The concentrations of all other major elements of the migmatites are within the variation limits determined for the gneisses and schists. Samples displaying initial migmatization have the following petrography:
  1. The light-coloured portions of the migmatites (leueosome) contain alkalifeldspar, plagioclase, and quartz, the dark-coloured ones (melanosome) are always free of alkalifeldspar and contain, besides ferromagnesian constituents, both plagioclase and quartz.
  2. The plagioclase of the melanosome has a remarkably higher An-content (An30–40mol.-%) than that one of the leueosome (An 9–14 mol.-%).
These observations seem to represent petrographic evidence that leueosome and melanosome have been in a restite-melt-relation at a temperature that just reached or slightly exceeded the value necessary to produce the beginning of melting. In addition, major element analyses of separated leueosome portions of samples displaying the petrography mentioned above have been undertaken. Normative Qz ∶ Ab: Or-ratios calculated from these analyses vary within very narrow limits about the average value of Qz ∶ Ab ∶ Or=36 ∶ 31 ∶ 33. Using the diagrams of von Platen (1965) concerning the crystallization of granitic melts the petrographic findings can be verified from analytical results, i.e. the migmatites of the Beaume valley are considered to be products of minimum temperature melting of the gneisses which still occur unaltered in adjoining areas of lower metamorphic grade.  相似文献   

9.
The aluminous enclaves occur in gedrite-cordierite-gneissesof the Middle Ordovician Ammonoosuc Volcanics, and are composedof combinations of the aluminous minerals sillimanite (Sill),kyanite, corundum (Cor), staurolite (St), sapphirine (Sa), andspinel (Sp), which are set in a matrix of cordierite (Crd) orplagioclase (Plag). Generally, where plagioclase is present,both it and the aluminous minerals are separated from gedrite(Ged) and rare hornblende (Hbl) by cordierite. The enclavesarc interpreted to have formed near the peak of Acadian (Devonian)metamorphism at sillimanite-staurolite-muscovite grade by reactionsthat were encountered during the pressure decrease which accompaniedthe rise of gneiss domes in the region. The enclaves are divided into two main types: (1) enclaves ofcordierite surrounding aluminous minerals; and (2) enclavesof cordierite and plagioclase surrounding aluminuous minerals.Sapphirine grains contain between 9?2 and 9?3 Al atoms per formulacalculated to 14 cations. Staurolites from the enclaves areMg-rich and have (Fe2++ Mn)/(Fe2++Mn+Mg) ratios of 0-59–0?64. The textures and mineralogy of the enclaves suggest that theserocks originally consisted of Ged+Sill?Qz?Hbl?Sp?Plag. Theseminerals reacted to form Crd+Aluminous Minerals?Plag. The mineralogyof both main types of enclaves can be explained by two analogoussets of continuous Fe-Mg reactions:The structure of the enclavessuggests that the mineral growth by the above reactions wasdiffusion controlled, which would have resulted from oversteppingthe above reactions (i.e. the P change exceeded the reactionrate). Therefore, chemical potential gradients (relative mobilityof diffusing components) between gedrite and sillimanite controlledthe location of mineral growth. The Fe-Mg ratio of the bulkcomposition and the proportions of non-Fe-Mg minerals (quartzand sillimanite) appear to determine which continuous Fe-Mgreactions were encountered. Examples of mineral sequences in the cordierite enclaves are:Sill (core)/St+Crd/Ged (matrix); Cor+Crd (core)/Ged (matrix),and Sill (core)/St+Crd/Sa+Crd/Ged (matrix). Examples of themineral sequences in the cordierite-plagioclase enclaves are:Sill (core)/St+Plag/Plag+Crd/Hbl+Ged (matrix); Cor+Plag (core)/St+Plag/Sa+Plag/Ged+ Hbl (matrix); and St+Plag (core)/Plag+Crd/Ged+Hbl (matrix). P–µFeMg–1 diagrams proved to be an importanttool for understanding and illustrating the development of theenclaves. These diagrams allow one to view simultaneously allthe discontinuous and continuous Fe-Mg reactions along a P–µH2O(or T) rock path. With this information it is possible to determinequalitatively which reactions and what sequence of reactionsmight be encountered by bulk compositions with variable Fe-Mgratios and modal proportions of phases.  相似文献   

10.
The Southern Vanoise is localized in the internal part of the Western Alps, in the Briançonnais zone. In Vanoise the following units can be distinguished (Fig. 1): a pre-hercynian basement (micaschists, glaucophanites, basic rocks), a permian cover (micaschists) and a mesozoic-paleocene cover (carbonate rocks). This area has been affected by the alpine metamorphic event characterized here by high and intermediate pressure facies. The rocks paragenesis are often unbalanced.The paleozoic rocks (Table 1) contain mainly: quartz, albite, paragonite, phengite, blue amphibole, chlorite, green biotite, garnet (Table 2). These minerals were analysed by an electron microprobe (Tables 3, 4 and 5). Mineral composition is highly variable: glaucophane is zoned (Table 5), white micas are more or less substituted with phengite (3.22O3/FeO + MgO)<0.53] whereas the Al rich chlorites [(Al2O3/FeO + MgO)>0.6] are associated with the less substituted white micas (Si=3.2) (Tables 3 and 4). The phengites with a Si content 3.2 occur in rocks where the retromorphic evolution is the most pronounced and penetrative. A metamorphic evolution is characterized by the disappearance of glaucophane which corresponds to the appearance of Al rich chlorite and to the decrease of phengitic substitution.The samples analysis are plotted in the tetraedric diagram: K2O-Al2O3-Na2O, Al2O3-FeO, MgO, on which a special mathematical treatment was applied. This method calculates the location of rocks composition in the four minerals space. This location is internal when the per cent amounts of all four relevant minerals are positive, if any of them is negative, the point is external (Tables 6–9).In Southern Vanoise micaschists, 2 subfacies are successively present (Fig. 3):Subfacies I: glaucophane-chlorite-phengite (Si4+ 3.5)-paragonite. Then subfacies II: chlorite-albite-phengite (Si4+ 3.2)-paragonite.In basic rocks is found essentially: Subfacies III: glaucophane-garnet-phengite-paragonite or IV: glaucophane-garnet-phengite-albite. Then subfacies V: green biotite-chlorite-albite-paragonite.The assemblages I and II proceed through reaction: 2 glaucophane +1 paragonite+2 H2O4.2 albite + 1 chlorite.The assemblage V appears with reactions: 1.8 glaucophane +2 phengite0.4 chlorite+2 green biotite + 3.6 albite +0.4 H2O or 2 glaucophane +2 phengite +0.5 garnet+ 6 H2O2 green biotite +1 chlorite+4 albiteThese reactions are controlled by hydratation: the composition variation of phengite and associated chlorite during the metamorphic evolution determines the stability of some minerals (particularly the glaucophane in Na2O poor rocks).In same rocks the results of mathematical treatment is not consistent with the data (Tables 2, 6–9). This discrepancy corresponds to a desequilibrium between chlorite and phengite.These results imply a continuous metamorphic evolution between two stages (Fig. 6): a first stage (1) at 8 kb, 350 ° C; a second stage (2) at 2 to 3 kb, 400–450 ° C.  相似文献   

11.
Abstract Textural evolution and compositional variation of clinopyroxenes in Ward Creek metabasites are described. Pyroxenes change, with increasing grade, from finegrained aggregates through fan-shaped medium-grained prisms to blocky coarse crystals. Characteristic features of metamorphic pyroxenes include: (1) the occurrence of coexisting pyroxene pairs, the compositions of which are used to delineate compositional gaps; (2) the existence of large compositional variations of pyroxenes, within a single specimen, which record a considerable span of P and/or T for crystallization; and, (3) the development of compositional trends in single specimens and in three metamorphic zones which are progressive in nature. The first formed clinopyroxene (Jd20Aug65Ac15) in the lower lawsonite zone mimics the composition of relict igneous augite. It changes continuously, with increasing grade, at nearly constant low XJd content towards acmite. At a composition around Jd20Aug30Ac50, the trend turns towards jadeite and intersects a solvus to form two coexisting clinopyroxenes in the middle lawsonite zone. At higher grade, the compositional gap becomes restricted towards the jadeite-omphacite join and clinopyroxene increases in XJd toward jadeite. A reversed compositional trend occurs at higher grade; clinopyroxenes decrease in jadeite component at nearly constant Aug/Ac ratio of 50/50 and finally become omphacite in the uppermost pumpellyite and epidote zones. The Na–Ca pyroxenes, close to the binary join Jd–Ac, occur in the lawsonite- and pumpellyite-zones, ranging from XJd= 1.0–0.30 together with Ab and Qz. The ubiquitous occurrence of aragonite at temperature estimates of 170–240° C by Taylor & Coleman (1968) for these zones does not support the low-temperature extrapolation of the Jd–Ab–Qz curve by Holland (1980). The estimated metamorphic field gradient indicates an inflection point at 7 kbar, 200° C. Below this, blueschist facies metamorphism proceeded under dominant pressure-increase from 4 to 7 kbar at nearly constant temperature, about 150–200° C, whereas at higher grade recrystallization, above the inflection point, the metamorphic temperature increased from 200 to 350° C at nearly constant pressure, about 7–8 kbar. Such an inflection point suggests the depth of underplating of either seamounts or accretionary packages in a subduction zone.  相似文献   

12.
Oxidation of As(III) by natural manganese (hydr)oxides is an important geochemical reaction mediating the transformation of highly concentrated As(III) in the acidic environment such as acid mine drainage (AMD) and industrial As-contaminated wastewater, however, little is known regarding the presence of dissolved Fe(II) on the oxidation process. In this study, oxidation of As(III) in the absence and presence of Fe(II) by MnO2 under acidic conditions was investigated. Kinetic results showed that the presence of Fe(II) significantly inhibited the removal of As(III) (including oxidation and sorption) by MnO2 in As(III)-Fe(II) simultaneous oxidation system even at the molar ratio of Fe(II):As(III) = 1/64:1, and the inhibitory effects increased with the increasing ratios of Fe(II):As(III). Such an inhibition could be attributed to the formation of Fe(III) compounds covering the surface of MnO2 and thus preventing the oxidizing sites available to As(III). On the other hand, the produced Fe(III) compounds adsorbed more As(III) and the oxidized As(V) on the MnO2 surface with an increasing ratio of Fe(II):As(III) as demonstrated in kinetic and XPS results. TEM and EDX results confirmed the formation of Fe compounds around MnO2 particles or separated in solution in Fe(II) individual oxidation system, Fe(II) pre-treated and simultaneous oxidation processes, and schwertmannite was detected in Fe(II) individual and Fe pre-treated oxidation processes, while a new kind of mineral, probably amorphous FeOHAs or FeAsO4 particles were detected in Fe(II)-As(III) simultaneous oxidation process. This suggests that the mechanisms are different in Fe pre-treated and simultaneous oxidation processes. In the Fe pre-treated and MnO2-mediated oxidation pathway, As(III) diffused through a schwertmannite coating formed around MnO2 particles to be oxidized. The newly formed As(V) was adsorbed onto the schwertmannite coating until its sorption capacity was exceeded. Arsenic(V) then diffused out of the coating and was released into the bulk solution. The diffusion into the schwertmannite coating and the oxidation of As(III) and sorption of both As(V) and As(III) onto the coating contributed to the removal of total As from the solution phase. In the simultaneous oxidation pathway, the competitive oxidation of Fe(II) and As(III) on MnO2 occurred first, followed by the formation of FeOHAs or FeAsO4 around MnO2 particles, and these poorly crystalline particles of FeOHAs and FeAsO4 remained suspended in the bulk solution to adsorb As(III) and As(V). The present study reveals that the formation of Fe(III) compounds on mineral surfaces play an important role in the sorption and oxidation of As(III) by MnO2 under acidic conditions in natural environments, and the mechanisms involved in the oxidation of As(III) depend upon how Fe(II) is introduced into the As(III)-MnO2 system.  相似文献   

13.
Local fluid migration through a serpentine melange caused successive carbonation of a metabasite block (about 80 meter in diameter) during the uplift stage of the glaucophanitic metamorphic rocks, the Nishisonogi metamorphics, southwest Japan. The block shows a zonal sequence as follows. Zone 1: original greenschist (Am+Ep+ Chl+Ab+Sph+Qtz). Zone 2: epidote disappears by the reaction Ep+Am+CO2+H2O=Chl+Cc+Qtz. Zone 3: balc appears by the reaction Am+CO2+H2O=Ta+Cc+ Qtz. Zone 4:sphene breakdowns by the reaction Sph+ CO2=Rt+Cc+Qtz. Zone 5: amphibole disappears by the two simultaneous reactions, Am+CO2=Do+Ta+Qtz and Ta+Cc+CO2=Do+Qtz+H2O. Zone 7: albite is replaced by chlorite, calcite, dolomite and quartz, and the assemblage of Do+Cc+Chl+Rt+Qtz is stable. Analyses of phase relations indicate an introduction of CO2-rich fluid into the greenschist body during regional metamorphism. The CO2-rich fluid may have formed by devolatilization reactions between serpentinite and graphite-bearing metasediments. The fluid migrated within the melange through a channelized pathway and into the greenschist body from a deeper part of the melange.  相似文献   

14.
Rocks of the greenschist facies in eastern Otago, New Zealand, have been investigated in an area some thirteen to sixteen kilometers wide and sixty-five kilometers long extending northeastwards approximately normal to the boundary of the schist with lower grade rocks. Quartzo-feldspathic schists predominate but greenschists and metacherts occur sporadically throughout the area. At the southwestern edge of the area schists are in the chlorite zone, slightly above the high-grade limit of pumpellyite. Metamorphic grade increases toward the northeast into the biotite zone which occupies about half the terrane studied and is believed to be everywhere little advanced in metamorphic grade past that of the biotite isograd. Some 130 mineral specimens have been partially analysed with the electron probe. Results derived from these data as well as other mineralogical investigation are as follows: Albite contains a maximum of 1% anorthite plus orthoclase in epidote-bearing rocks from all parts of the area.Compositions of epidotes range from 12% to 32% Ca2Fe3(SiO4)3(OH), but most lie between 15% and 20%, a compositional field thought by Strens (1965) and Holdaway (1965) to occupy a miscibility gap in the epidote series. Zoning in some epidotes suggests a history of early growth of small, sparse iron-rich epidotes, and later growth of relatively large amounts of iron-poor epidote probably caused by breakdown of prehnite and/or pumpellyite. Muscovites vary widely in celadonite content; but the composition shows little if any dependence on metamorphic grade within the area studied. Most tend to be celadonite-rich, and in this respect are similar in composition to muscovites from rocks of the glaucophane-schist facies.Chlorites range widely in Mg/Fe; but Al/Mg+Fe is relatively uniform. Chlorites associated with actinolite tend to have higher Mg/Fe than those associated with stilpnomelane. Following the classification of Foster (1962) most chlorites are brunsvigite and some are ripidolite. Textural and chemical relations between biotite and coexisting minerals demonstrate that, contrary to some previous suggestions, biotite is not a relict mineral. An alteration product of chlorite bears strong resemblance to biotite, and previous misidentification of this mineral as biotite has caused much confusion regarding the distribution and metamorphic significance of biotite in Otago schists.An attempt to determine the reaction producing biotite is not successful. Possibly biotitebearing rocks have slightly higher biotite component than rocks of the chlorite zone. All newly formed amphibole found in eastern Otago is pale green, Al- and Na-poor actinolite. One of the chemical conditions necessary for the formation of actinolite in schists of eastern Otago is a relatively high Mg/Fe+Al ratio.Stilpnomelane is an integral part of assemblages in which it occurs, being developed under conditions of relatively low and in rocks with a high Fe/Mg + Al ratio. The present highly oxidized state of all stilpnomelane observed in this study is probably not a primary feature of the mineral but developed after metamorphism.Porphyroblastic garnets are accessory constituents in about half the quartzo-feldspathic schists collected from the biotite zone but are extremely rare in specimens of the same lithology from the chlorite zone. Either a garnet-producing reaction began in quartzo-feldspathic schists at about the biotite isograd, or rocks of biotite zone tend to have slightly higher garnet component than those of the chlorite zone. Composition of the garnets ranges widely, extremes being: 77% spess., 18% gross., 5% alm.; 25% spess., 50% gross., 25% alm.; 15% spess., 30% gross., 55% alm. Most of the variation in composition is controlled by host rock composition, but garnets at higher grade tend to have lower spessartine content. The garnets are zoned; generally Mn decreases and Fe increases from core to rim.For the most part chemical equilibrium among different grains and minerals was closely approached over distances of at least a few millimeters. However, profound disequilibrium exists within some individual grains, such as a zoned garnet which over a distance of only 15 microns ranges in spessartine content from 77% in the core to 35% on the rim.This report is a condensed version of part of the author's Ph.D. thesis (Brown, 1966), University of California, Berkeley.  相似文献   

15.
The metabasites within the Tokoro belt of eastern Hokkaido,Japan, suffered pervasive high–P/ Tetamorphism. Mineralassemblages and compositions of more than 400 metabasites fromthe Saroma–Tokoro district were investigated. The metabasites are divided into six metamorphic zones basedon mineral assemblages. The laumontite (Lm) zone is definedby the presence of laumontite. The prehnite–pumpellyite(Pr–Pp) zone is characterized by the association of prehnite+ pumpellyite. The lawsonite–sodic. pyroxene (Lw–Napx)zone is defined by the assemblage lawsonite + pumpellyite +sodic pyroxene + chlorite. The epidote–sodic pyroxene(Ep–Napx)(1) and (2) zones are charecterized by the assemblage epidote+ pumpellyite + sodic pyroxene + chlorite. The former is characterizedby the absence of aragonite, sodic amphibole, and winchite,as well as the presence of jadeite–poor sodic pyroxene(maxJd mol% = 13), whereas these minerals occur in the Ep–Napx(2)zone, together with jadeite–rich sodic pyroxene (max.Jd mol % = 34). In the epidote–actinolite (Ep–Act)zone, the most common assemblages contain epidote+ actionolite+ pumpellyite + chlorite. The Lm zone corresponds to the zeolite facies (150–200?Cand 1–2 kb) and the Pr–Pp zone is equivalent tothe prehnite–pumpellyite facies (200–250?C and 2–2–5kb). The Ep–Napx(I) zone appears to be stable at 200–250?C and 2? 5?3?5 kb. The pressure conditions in the Lw–Napx,Ep-Napx(2), and Ep–Act zones appear to range from 5 to6 kb, and the temperatures are estimated to be 200–230,230–270, and 270–300? C, respectively. The sequenceof the metamorphic zones is charaterized by the curved P–Tpath. The stability field of pumpellyite+ sodic+ pyroxene+ chloritein Fe3+ bearing metabasites is located in the lower–temperatureand higher–pressure part of the pumpellyite–actionolitefacies. On the basis of Schreinmaker's method, the stabilityfield of the assemblage is bounded by a high–pressurereaction Pp+ Napx+ Chl+ Ab+ Qz+ H2O= Lw+ Gl, and by a high-temperaturereaction Pp Napx+ Chl+ Ab+ Qz = Ep + Gl + H2O.  相似文献   

16.
《Geochimica et cosmochimica acta》1999,63(19-20):3171-3182
The oxidation rate of pyrite at pH 7, 25°C and at constant partial pressure of oxygen (0.21 and 0.177 atm) was measured in the presence of the Fe(III)-chelators NTA, oxalate, leucine, EDTA, citrate, IDA and the Fe(III)-reductant ascorbic acid. With the exception of leucine and EDTA, non-reducing Fe(III)-chelators increased the oxidation rate relative to the reference state of formation of the Fe(OH)2+ complex at pH 7. The rate increase was proportional to the logarithm of the conditional stability constant of the ligands for the complexation of Fe3+. No effect on the oxidation rate was observed in the presence of EDTA, which shifted the redox potential of the redox couple Fe2+/Fe3+ to a value below that in the absence of any ligand at pH 7. Ascorbic acid decreased the pyrite oxidation rate by a factor of 5 at ascorbic acid concentrations between 10−4 and 10−2 mol L−1. Comparison of the rate constants for the oxidation of ascorbic acid by surface bound Fe(III) in the absence and presence of pyrite shows that the pyrite surface accelerates this reaction by a factor of 10. The oxidation of both pyrite and ascorbic acid is of fractional order with respect to ascorbic acid (HAsc): rpy=0.55 c(HAsc)−0.35 rHAsc=3.6 c(HAsc)0.59. Both the results from experiments with Fe(III)-chelating ligands and the Fe(III)-reductant, suggest a very efficient interference in the electron cycling between Fe(II) and Fe(III) at the pyrite surface. The interference seems to be mainly related to the reductive side of the iron cycling. It is therefore concluded that the electron transfer between ferric iron and pyritic sulfur limits the pyrite oxidation rate at pH 7.  相似文献   

17.
Högbomite has generally been considered to be a rare accessory phase in metamorphic rocks. While investigating high-grade peraluminous metamorphites in the Benson Mine District, Adirondack Mountains, New York and the Manitouwadge Massive Sulfide District, Ontario, Canada, we have found several högbomite occurrences and believe that högbomite is more widespread in high-grade aluminous rocks than previously recognized. At Benson Mine, an iron-rich högbomite (Hög) occurs with K-feldspar-magnetite (Mt)-ilmenite (Ilm)-biotite-almandine (Alm)-sillimanite (Sil)-quartz (Qz)-hercynite (Hc)-corundum (Cor)-rutile (Ru). At Manitouwadge, Fe -Zn högbomite is found with gedrite-cordierite-staurolite-hercynite-magnetite±quartz ±ilmenite±rutile±biotite±cassiterite. Because composition varies with structure type, it is essential to determine the structure of högbomite utilized in specific reactions. Högbomite from Benson Mine has an 8H structure type, while that at Manitouwadge has a complex mixed structure. Both are more iron-rich than previously reported högbomites, and their composition can be approximated by the ideal formula Fe5Al16TiO30(OH)2. Proposed reactions for 8H-högbomite are Hög=Ilm+Hc+Cor+V, Hög=Ru+Hc+Cor+V, Hög+Ru=Ilm+Cor+V, and Hög+Ilm=Ru+Hc+V. These reactions can be combined with the experimentally determined reactions Alm+Sil=Hc+Qz and Ru+Alm=Ilm+Sil+Qz to derive reactions in the system FeO-Al2O3-TiO2-SiO2-H2O that limit the stability of the assemblages Hög+Alm and Hög+Sil. Oxidation-sulfidation reactions define a wedge-shaped stability field for högbomite that is closed on the high f S2 side.Contribution No. 456 from the Mineralogical Laboratory, University of Michigan, Ann Arbor, USA  相似文献   

18.
《Applied Geochemistry》2004,19(7):995-1009
Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H2SO4, and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO4.  相似文献   

19.
Ninety-seven mineral phases consisting of ten chloritoids, fifteen epidotes, sixteen garnets, four sphenes, seven rutiles, seven pyroxenes, thirteen blue amphiboles, two green amphiboles, eleven phengites, two paragonites, a mariposite, seven chlorites, and two specimens of albite were obtained from the metamorphic rocks of Île de Groix, and their chemical, physical, optical and X-ray properties determined. The chloritoids are all optically positive, monoclinic polymorphs with large 2V, moderate refractive indices and characterized by high densities. Their fluorine contents have been used to propose a new upper limit for OHF substitution in the chloritoid structure, suggesting that partial pressure of fluorine might modify the stability of chloritoids from that determined in pure H2O. The epidotes belong to the Al-Fe epidote series and are epidote sensu stricto. The almandine-rich garnets and the chloromelanites are metastable relics in the glaucophane schists. The grossular contents of the calcareous schist garnets are believed to have become depressed under high CO2 pressure and the low Tschermak's contents of the pyroxenes are to be explained by equilibria involving epidote at high and low temperature when the Tschermak's components will break down to epidote group minerals. The sphenes contain appreciable amounts of combined water, fluorine substituting for oxygen and aluminium substituting for silicon and titanium. The presence of H3O+ is suspected in a specimen of blue amphibole. The barroisite has a composition between glaucophane and hornblende. On account of its high Fe3+ content it is believed to have formed under higher P O 2 than the blue amphiboles. The paragonites which occur in the ohloritoid veins are unstable in the potassium-rich aluminous schists. The phengites show a tendency towards sericitic composition due to post-glaucophanisation readjustments under the lower pressure conditions of the greenschist facies. Some of the Fe3+ contents of the chlorites are interpreted as due to oxidation of ferrous iron, e.g. 2 [Fe(OH)2]2FeOOH + H2. The minerals show strong chemical control of the host rock and their Mn contents are directly related to those of the minerals from which they have evolved through retrogression.Chloritoids and epidotes that are not associated with garnets contain higher amounts of manganese; similarly, the two blue amphiboles with the highest FeMg ratios were obtained from rocks in which garnet has not appeared. It is therefore believed that ottrelite and piemontite would be stable only at the lowest subfacies of the greenschist facies. Also, the ironrich amphiboles must have evolved from low-grade iron-aluminium chlorites, since on the appearance of garnet in a schist iron-aluminium chlorites react with quartz to give almandine and Mg-rich chlorites. The Fe2+Mg ratios of the blue amphiboles therefore reflect the grade of the original schist in which the minerals formed.  相似文献   

20.
We report the T-X(H2O) phase relations for the trondhjemitic Nûk gneiss which comprises the principal component of the second phase of Archean (3.0–2.8 by) igneous activity in the Godthåb region of southwestern Greenland. A pressure of 15 kbar was chosen to place constraints on possible protoliths for trondhjemitic melts at lower crustal depths. Under H2O-saturated conditions, a melting interval of 135° C separates the solidus at 610° C from the liquidus at 745° C. H2O-saturation at 15 kbar occurs at approximately 15.5 wt % H2O. The H2O-undersaturated liquidus extends along a curved path from 745° C at 15.5 wt % H2O to 1100° C at 2% H2O. Lower H2O contents were not investigated. At low H2O contents (<6%) sodic plagioclase (Pl, An32) is the liquidus phase followed at lower but still near-liquidus temperatures by quartz (Qz) and then garnet (Ga). At 6% H2O, Ga replaces Pl on the liquidus and is joined at slightly lower temperatures by Pl and hornblende (Hb). The field for liquidus Ga extends to only 7.5% H2O where it is replaced by Hb which is the liquidus phase up to 13% H2O. At all higher H2O contents, epidote (Ep) is the first phase to crystallize, followed by biotite (Bi) at slightly lower temperatures. Following the standard inverse approach, the near-liquidus phase assemblages are interpreted as potential residues from which trondhjemitic melts could be extracted. At high melt H2O contents (>7%), mafic residues consisting of some combination of Hb, Ga, Ep, and Bi are possible and could correspond to amphibolitic source rocks. At lower melt H2O contents (< 5%), possible residues consist of Na-Pl+Qz±Ga and could correspond to an earlier generation of tonalitic-trondhjemitic rocks. However, such residues would not impart the highly fractionated REE patterns characteristic of Archean trondhjemites. If a first generation of tonalitic-trondhjemitic melts was generated by higher pressure partial fusion of eclogite and emplaced at 55 km depth, it would crystallize to an assemblage consisting almost entirely of Na-Pl+Qz with highly fractionated REE patterns. These rocks in turn could be partially melted to yield a second generation of trondhjemites which would inherit the highly fractionated REE patterns because neigher Pl nor Qz is capable of significantly fractionating HREE from LREE.  相似文献   

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