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1.
Manganese-rich rocks from the island of Andros (Cyclades/Greece) contain cymrite (BaAl2Si2O8·H2O) and celsian. The textural relationships indicate replacement of celsian by cymrite. Several microprobe analyses of cymrites show a solid solution of 0.7–6.1 mole% KAlSi3O8·H2O. The relic celsians have similar K contents. Thus the described rocks from Andros represent the first natural example for the reaction celsian+water= cymrite. The rocks from Andros underwent an Eocene high pressure metamorphism. Lateron, the high pressure parageneses were nearly effaced by a Late Oligocene Barrovian type metamorphism. It is assumed that both cymrite and celsian were formed at conditions near the reaction curve celsianss+water= cymritess during the Barrovian type event.  相似文献   

2.
High-pressure, low-temperature metamorphic Mn-rich quartzites from Andros and Evvia (Euboea) islands, Greece, situated in the Eocene blueschist belt of the Hellenides, reveal different Mn-Al-Ca-Mg-silicate assemblages in response to variable metamorphic grade. On Evvia, piemontite- and/or braunite-rich quartzites which are associated with low-grade blueschists (T<400° C, P> 8 kbar) show the principle mineral assemblage quartz + montite + sursassite + braunite + Mg-chlorite + hematite + rutile + titanite. The Mn-Al-silicate sursassite, basically (Mn2+, Ca)4 Al2(Al, Fe3+, Mn3+, Mg)4Si6O21(OH)7, thus far reported as a rare mineral, locally occurs as a rockforming mineral in cm- to m-thick layers. On Andros, higher-grade quartzites (T450–500° C, P>10 kbar) of similar composition contain the assemblage quartz + piemontite + spessartine + braunite + Mg-chlorite+hematite + phengite+ phlogopite + rutile. Rare sursassite is present only as a relict phase. Additional, mostly accessory minerals in quartzites from Evvia and Andros are ardennite, Na-amphibole, acmitic clinopyroxene, albite, apatite, and tourmaline. The chemical composition of the main phases is characterized in detail.Disequilibrium textures and mineral compositions in some samples from Andros and Evvia imply the reactions sursassite + braunite + quartz = spessartine+clinochlore±hematite + H2O + O2 (1) sursassite + braunite + phengite + quartz = spessartine + phlogopite±hematite + H2O + O2 (2) and in braunite-free assemblages sursassite + Mn3+Fe –1 3+ [hematite, piemontite] + hematite + quartz = spessartine + clinochlore + H2O+O2 (3) Reactions (1) to (3) have positive P-T slopes. They are considered to account for the breakdown of sursassite and the formation of spessartine during prograde metamorphism of the piemontite quartzites and related rocks. P-T data from Andros and Evvia and geological data from few other occurrences reported suggest sursassite+ quartz±braunite to be stable at T<400–450° C over a considerable pressure interval at least up to 10 kbar. Theoretical phase relations among Mn3+-Mn2+-silicates in the pseudoquaternary system Al-Mn-Ca-Mg with excess quartz, H2O, and O2 indicate that low-grade assemblages containing sursassite (±braunite±pumpellyite±viridine±piemontite + quartz) are likely precursors of higher-grade assemblages including spessartine, Mg-chlorite, braunite, viridine, and piemontite reported from greenschist-, amphibolite-, and high-grade blueschist-facies rocks of appropriate composition.  相似文献   

3.
Cymrite, BaAl2Si2O8 · nH2O, is a rare mineral formed during low-grade dynamothermal metamorphism (T = 250–300°C, P = 1–3 kbar). Cymrite has been described from many metasedimentary ores and hydrothermal rocks. In carbonatites, it has been found for the first time. Cymrite has been identified in the Kovdor and Seblyavr massifs, Kola Peninsula. In Kovdor, this mineral has been described from one of the hydrothermal veins cutting the pyroxenite-melilitite-ijolite complex at the Phlogopite deposit; cymrite is associated with thomsonite, calcite, and stivensite. In the Seblyavr pluton, cymrite occurs in thin veins of calcite carbonatite that cut pyroxenite contacting with ijolite. Cymrite from the Seblyavr pluton is associated with calcite, natrolite, pyrite, and chalcopyrite. The mineral is optically negative and uniaxial, with extinction parallel to elongation; ω ～ 1.607(1). According to X-ray diffraction data, cymrite from Seblyavr is monoclinic, space group P1m1; unit-cell dimensions are: a = 5.33, b = 36.96, c = 7.66 Å, β = 90°, V = 1510.55 Å3. According to the results of IR spectroscopy, in the series of samples from different massifs (in the running order Kovdor-Voishor-Seblyavr), the double-layer deformation is enhanced and accompanied by a decrease in the Si-O-Si angle and weakening of hydrogen bonds of interlayer water. The empirical formulas of cymrite calculated from electron microprobe analyses are Ba0.93–0.95Ca0.01–0.02K0.00–0.05Na0.02–0.04Al1.97–2.01Si1.99–2.03O8(H2O) and Ba1.00–1.02Ca0.00–0.01Sr0.00–0.01Fe0.00–0.01Al1.94–2.00Si1.98–2.03O8(H2O) at Seblyavr and Kovdor, respectively. Cymrite from the carbonatite massifs of the Kola Peninsula was formed under hydrothermal conditions at low temperature (200–300°C), high activity of Ba and Si, and high water pressure. At Kovdor, the mineral crystallized directly from the residual solution enriched in Ba. The sequence of mineral deposition is as follows: thomsonite-cymrite-calcite-stevensite. Cymrite from the Seblyavr pluton is a product of hydrothermal alteration of primary Na-K-Ba silicates of ijolite: nepheline, feldspar, and probably celsian. Natrolite replaces cymrite indicating high alkalinity of late hydrothermal fluids.  相似文献   

4.
The univariant reaction governing the upper stability of heulandite (CaAl2Si7O18·6H2O), heulandite=laumontite+3 quartz+2H2O (1), has been bracketed through reversal experiments at: 155±6° C, 1000 bar; 175±6° C, 1500 bar; and 180±8° C, 2000 bar. Reversals were established by determining the growth of one assemblage at the expense of the other, using both XRD and SEM studies. The standard molal entropy of heulandite is estimated to be 783.7±16 J mol–1 K–1 from the experimental brackets. Predicted standard molal Gibbs free energy and enthalpy of formation of heulandite are –9722.3±6.3 kJ mol–1 and –10524.3±9.6 kJ mol–1, respectively. The reaction (1), together with the reaction, stilbite=laumontite+3 quartz+3 H2O, defines an invariant point at which a third reaction, stilbite=heulandite+ H2O, meets. By combining the present experimental data with past work, this invariant point is located at approximately 600 bar and 140° C. Heulandite, which is stable between the stability fields of stilbite and laumontite, can occur only at pressures higher than that of the invariant point, for = P total.These results are consistent with natural parageneses in low-grade metamorphic rocks recrystallized in equilibrium with an aqueous phase in which is very close to unity.  相似文献   

5.
Dumortierite, generally simplified as Al7BSi3O18, was synthesized in the pure system Al2O3–B2O3–SiO2–H2O (ABSH) using gels with variable Al/Si ratios mixed with H3BO3 and H2O in known proportions as starting materials. Synthesis conditions ranged from 3 to 5 and 15 to 20 kbar fluid pressure at 650° to 880°C. On the basis of analyses, synthetic dumortierite shows relatively narrow homogeneity ranges with regard to Al/Si which, however, vary as a function of pressure: at low pressures (3–5 kbar) Al/Si is 2.77–2.94 versus 2.33–2.55 at high pressures (15–20 kbar). Outside of these homogeneity limits, dumortierite was found to coexist with quartz or corundum, depending on the starting composition. Whereas synthetic dumortierite invaribly contains 1.0 boron atom per formula unit (p.f.u.) based on 18 oxygens, the water contents vary drastically as a function of pressure and temperature (1.32–2.30 wt.% H2O or 0.85–1.47 H p.f.u.). H2O is an essential component in dumortierite. Structural formulae based on complete chemical analyses of the dumortierites synthesized reveal that there is invariably an Si-deficiency against the ideal number of 3.0 p.f.u. In the calculation procedure used here, this deficiency is balanced by assuming tetrahedral Al. The remaining Al, taken to occupy the octahedral sites, is always below the ideal number of 7.0 p.f.u. Charge-balancing the structure with the hydrogen found analytically leads to two different mechanisms of H incorporation: (1) 3H+ + octahedral vacancy for Al[6]; (2) H+ + tetrahedral Al for Si[4]. Dumortierite synthesized at high fluid pressure contains little Al[4] and, thus, little H+ of type 2; its hydrogen is predominantly present as type 1. Conversely, dumortierite formed at low fluid pressures is high in Al[4] and hydrogen type 2. The amounts of hydrogen type 1 in low-pressure dumortierites decrease with rising temperatures of synthesis. Typical structural formulae are: (Al6.670.33)[Al0.49Si2.51–O13.53(OH)1.47](BO3) for a low-pressure product, and (Al6.680.32)[Al0.09Si2.91O13.94(OH)1.06](BO3) for a high-pressure product. Independently of the synthesis conditions, dumortierite was found always to be orthorhombic, with b0/a0 deviating slightly, but significantly from the valid for hexagonal lattice geometry. As a function of increasing Al/Si in the synthetic crystals, their a0, c0, and V0 rise, whereas b0 decreases. Thus b0/a0 decreases most sensitively with rising Al/Si and also with growing Al[4]. More experimentation is required before the compositional variations of dumortierite found here can be applied successfully to geothermobarometry of natural rocks.  相似文献   

6.
Calc-alkaline granitoid rocks of the Oligocene-Pliocene Chilliwack batholith, North Cascades, range from quartz diorites to granites (57–78% SiO2), and are coeval with small gabbroic stocks. Modeling of major element, trace element, and isotopic data for granitoid and mafic rocks suggests that: (1) the granitoids were derived from amphibolitic lower crust having REE (rare-earth-element) and Sr-Nd isotopic characteristics of the exposed gabbros; (2) lithologic diversity among the granitoids is primarily the result of variable water fugacity during melting. The main effect of fH 2 O variation is to change the relative proportions of plagioclase and amphibole in the residuum. The REE data for intermediate granitoids (quartz diorite-granodiorite; Eu/Eu*=0.84–0.50) are modeled by melting with fH 2 O<1 kbar, leaving a plagioclase + pyroxene residuum. In contrast, data for leucocratic granitoids (leuco-granodiorites and granites; Eu/Eu* =1.0–0.54) require residual amphibole in the source and are modeled by melting with fH 2 O=2–3 kbar. Consistent with this model, isotopic data for the granitoids show no systematic variation with rock type (87Sr/86Sri =0.7033–0.7043; Nd(0)=+3.3 to +5.5) and overlap significantly with data for the gabbroic rocks (87Sr/86Sri =0.7034–0.7040; Nd(0)=+3.3 to +6.9). The fH 2 O variations during melting may reflect additions of H2O to the lower crust from crystallizing basaltic magmas having a range of H2O contents; Chillwack gabbros document the existence of such basalts. One-dimensional conductive heat transfer calculations indicate that underplating of basaltic magmas can provide the heat required for large-scale melting of amphibolitic lower crust, provided that ambient wallrock temperatures exceed 800°C. Based on lithologic and geochemical similarities, this model may be applicable to other Cordilleran batholiths.  相似文献   

7.
We conducted melting experiments on a low-alkali tholeiite (SiO2 ~52 wt%, MgO ~6.5 wt%, CaO/Na2O~4.4, Al2O3/SiO2 ~0.33) under both H2O-undersaturated and H2O-saturated conditions to investigate the effect of H2O on the Ca–Na partitioning between plagioclase and melt. Experiments were performed in the temperature and pressure ranges of 1,000–1,300°C and 1–5 kbar, respectively, with varying H2O contents of 0–12wt%. Redox condition was 0–2 log unit above NNO (nickel–nickel oxide) buffer. Temperature-bulk H2O diagrams for the low-alkali tholeiite are constructed at 1, 2, and 5 kbar, and compositions of near-liquidus plagioclase and coexisting melt are determined. To exclude the effect of melt composition (CaO/Na2O and Al2O3/SiO2 ratios) on plagioclase composition and to reveal the effect of H2O on An (=100×Ca/(Ca+Na)) content and (=(Ca/Na)pl/(Ca/Na)melt), we focused on the composition of near-liquidus plagioclases which crystallized from melts with nearly constant CaO/Na2O and Al2O3/SiO2 ratios. Our experimental results show that, at each experimental pressure, An content of the near-liquidus plagioclase and the KDCa-Na almost linearly increases as H2O content in melt increases. Each of the An content and the variations in a low-alkali tholeiitic system (CaO/Na2O~4.0–4.5, Al2O3/SiO2 ~0.27–0.33) can be described by one equation using temperature, pressure, and melt H2O content as parameters. An content and of liquidus plagioclase increases with increasing melt H2O and with decreasing pressure, elucidating that nearly H2O-saturated conditions of 2–3 kbar is optimal for the crystallization of the most An-rich plagioclase (>An88). We suggest this pressure condition of 2–3 kbar, corresponding to depth of 7–11 km, plays an important role for the origin of An-rich plagioclase in H2O-rich low-alkali tholeiite. At pressures more than ca. 4 kbar, crystallization of liquidus Ca-rich clinopyroxene decreases the CaO/Na2O ratio of liquid, thus prohibiting the crystallization of high-An plagioclase from hydrous tholeiite.  相似文献   

8.
Summary Potassium-fluor-richterite is reported from wollastonite-rimmed metachert bands embedded in marbles of the Bufa del Diente aureole, NE-Mexico. K-F-richterites were generated via reaction of previously formed contact-metamorphic diopside with infiltrated hypersaline brines of magmatic origin that used the metachert bands as metamorphic aquifers. Their formation occurred at peak metamorphic conditions of 500 to 600 °C at 1 kbar according to the generalised reaction 10 CaMgSi2O6 + 8 SiO2 + 2 KClaq + 6 NaClaaq + 4 H2O + 4 HF diopside + quartz = 2 KNaCaMg5Si8O22(F)2 + 4 Ca2NaH(SiO3)3 + 8 HClaq K-F-richterite + pectolite Compositional ranges in two samples are K-Ri58–69Ri16–25Tri12–21 and K-Ri58–66Ri32–40Tr0–5. Mg/(Mg + Fe2+) ranges from 0.81 to 0.95, F/(F + OH) from 0.55 to 0.85, and the K-F-richterites are Cl-free.Microthermometrically determined K/(K + Na)-ratios of hypersaline brines trapped at 500°C to 600°C range from 0.50 to 0.64, resulting in distribution coefficients K DK-Na Amph-F1 = X K(in A) Amph /X N(in A) Amph · X Na F1 /X K F1 of 0.85 to 1.3 for the Na-K amphibole-fluid exchange reaction. Very low Ca-contents in bulk fluid leachates indicate that Cacontaining fluids cannot coexist with richterite and that Ca is incorporated into amphibole as a tremolite component. Amphibole compositions in Al-free systems can predict Na-K-Ca-ratios of metasomatic brines that equilibrated with them. Despite the hypersaline nature of the brines, Cl is not incorporated into the Mg-rich K-F-richterites because of the Mg-Cl and Fe-F avoidance rules in amphiboles.
Kalium-Fluor-Richterit in kontaktmetamorphem Quarziten der Bufa del Diente Aureole, NO-México
Zusammenfassung In die Marmore der Kontaktaureole des Bufa del Diente-Alkalisyenits sind 5-15 cm mächtige Quarzitbänder eingeschaltet, die mehrere cm-dicke Wollastonitsäume aufweisen. Die Metaquarzite enthalten Kalium- und Fluor-reiche Richterite. Die K-FRichterite bildeten sich durch Reaktion von zuvor gebildetem, kontaktmetamorphem Diopsid mit infiltrierenden hochsalinaren Fluiden magmatischen Ursprungs. Die Metaquarzite dienten als metamorphe Aquifere für diese Fluide.Die K-F-Richterite wurden bei den Maximaltemperaturen der Kontaktmetamorphose von 500-600°C bei 1 kbar nach der folgenden schematischen Reaktion gebildet: 10 CaM9Si2O6 + 8 SiO2 + 2 KClaq + 6 NaClaq + 4 H2O + 4 HF Diopsid + Quarz = 2 KNaCaMg5Si8O22(F)2 + 4 Ca2NaH(SiO3)3 + 8 HClaq K-F-Richterit + Pektolit Der Zusammensetzungsbereich von zwei Proben aus unterschiedlichen Metaquarzitbändern liegt bei K-Ri58–69Ri16–25Tr12–21 und K-Ri58–66Ri32–40Tr0–5. K-FRichterite in beiden Proben haben F/(F + OH)-Verhältnisse von 0.55 bis 0.85 und enthalten kein Cl.Mikrothermometrisch bestimmte K/(K + Na)-Verhältnisse der bei 500°-600°C in Flüssigkeitseinschlüssen okkludierten, hochsalinaren Fluide betragen 0.50–0.64. Daraus lassen sich Verteilungskoeffizienten K DK-Na Amph-Fi = X K(in A) Amph /X N(in A) Amph · X Na F1 /X K F1 von 0.85-1.3 für die Amphibol-Fluid Austauschreaktion in tremolitfreien Amphibolen ableiten. Wässrige Extrakte der Gesamtfluidpopulationen enthalten sehr geringe Ca-Konzentrationen im Vergleich zu K und Na. Dies zeigt, daß Fluide mit signifikanten Ca-Konzentrationen nicht mit Richteriten koexistieren können und Ca bevorzugt als Tremolitkomponente eingebaut wird. Amphibolzusammensetzungen in Al-freien Systemen eignen sich als Indikatoren für K-Na-Ca-Verhältnisse von koexistierenden metasomatischen Fluiden. Die K-F-Richterite sind Cl-frei, obwohl sie mit hochsalinaren Fluiden koexistiert haben. Mg-reiche Amphibole können kein CI einbauen und Fe-reiche Amphibole kein F.

With 4 Figures  相似文献   

9.
Orthorhombic amphiboles with excess OH, which can be schematically deduced from anthophyllite by the combined substitutions Mg2+ + O2–Li++OH– and Mg2+2 Li+, were synthesized at 750–875° C/1 kbar in the system Li2O-MgO-SiO2-H2O. Their phase relations are presented for 800° C/1 kbar . An amphibole with the analytical composition 2.70 wt% Li2O, 31.1 wt% MgO, 63.0 wt% SiO2, and 3.29 wt% H2O has lattice constants a 0 18.588 (11), b 0 17.966 (10), c 0 5.262 (3) Å, V 0 1,757.2 (1.5) Å3 (referred to Space Group Pnma). The OH-valence vibrational spectrum of this amphibole showed v OH bands at 3,667, 3,708, and 3,725 (shoulder) cm–1, which are ascribed to OH in the configurations (MgMgMg)-OH, (MgMgMg)-OH-Li (Li in the A-site) of the pseudotrigonal (M1M1M3)-OH arrangement in the amphibole structure, and to Si-OH, respectively. No explanation can at present be offered for an additional shoulder at 3,695 cm–1. The proposed structural formula is (Li0.27 0.73)(Li1.11 Mg0.89)· (Mg5)(Si8.01O21.20(OH)0.80)(OH)2.00.  相似文献   

10.
The solubility of calcite in NaCl-H2O and in HCl-H2O fluids was measured using an extraction-quench hydrothermal apparatus. Experiments were conducted at 2 kbar, between 400° C and 600° C. Measurements in NaCl-H2O were conducted in two ways: 1) at constant pressure and NaCl concentration, as a function of temperature; and 2) at constant pressure and temperature, as a function of NaCl concentration. In both the NaCl-H2O and the HCl-H2O systems, the solubility of calcite increases with increasing chlorine concentrations. For example, the log calcium molality in equilibrium with calcite increases from –3.75 at 2 kbar and 500° C, in pure H2O to –3.10 at 2 kbar and 500° C at log NaCl molality=–1.67. At fixed pressure and NaCl molality, the solubility of calcite is almost constant from 400° C to 550° C, but increases somewhat at higher temperatures. The results can be used to determine the dominant calcium species in the experimental solutions as a function of NaCl concentration and to obtain values for the second dissociation constant of CaCl2(aq). At 2 kbar, 400° C, 500° C, and 600° C, we calculate values for the log of the dissociation constant of CaCl+ of –2.1, –3.2, and –4.3, respectively. The 400° C and 500° C values are consistent with those obtained by Frantz and Marshall (1982) using electrical conductance techniques. However, our 600° C value is 0.8 log units higher than that reported by Frantz and Marshall. The calcite solubilities in the NaCl-H2O and HCl-H2O systems are inconsistent with the solubilities of calcite in pure H2O reported by Walther and Long (1986). They are, however, consistent with the measurements of calcite solubilities in pure H2O presented in this study. These results allow for the calculation of the solubilities of calcium silicates and carbonates in fluids that contain CO2 and NaCl.  相似文献   

11.
The solubility of calcite in H2O was measured at 6–16 kbar, 500–800 °C, using a piston-cylinder apparatus. The solubility was determined by the weight loss of a single crystal and by direct analysis of the quench fluid. Calcite dissolves congruently in the pressure (P) and temperature (T) range of this study. At 10 kbar, calcite solubility increases with increasing temperature from 0.016±0.005 molal at 500 °C to 0.057±0.022 molal at 750 °C. The experiments reveal evidence for hydrous melting of calcite between 750 and 800 °C. Solubilities show only a slight increase with increasing P over the range investigated. Comparison with work at low P demonstrates that the P dependence of calcite solubility is large between 1 and 6 kbar, increasing at 500 °C from 1.8×10–5 molal at 1 kbar to 6.4×10–3 molal at 6 kbar. The experimental results are described by:
where T is in Kelvin and H2O is the density of pure water in g/cm3. The equation is applicable at 1–20 kbar and 400–800 °C, where calcite and H2O stably coexist. Extrapolated thermodynamic data for indicates that the dominant dissolved carbon species is CO2,aq at all experimental conditions. The results require that equilibrium constant for the reaction:
increases by several orders of magnitude between 1 and 6 kbar, and also rises with isobaric T increase. Published thermodynamic data for aqueous species fail to predict this behavior. The increase in calcite solubility with P and T demonstrates that there is a strong potential for calcite precipitation during cooling and decompression of water-rich metamorphic fluids sourced in the middle to lower crust.Editorial responsibility: T.L. Grove  相似文献   

12.
Dynamics of Na in sodium aluminosilicate glasses and liquids   总被引：1，自引：0，他引：1  
23Na NMR measurements on Na2Si3O7, Na3AlSi6O15, and NaAlSi3O8 glasses from room temperature to 1200°C show that the dynamics and local structure of sodium in silicate/aluminosilicate glasses and melts vary with composition and temperature.The peak positions decrease in frequency between room temperature and 200°C indicating that the Na sees a larger average site as temperature is increased. Between 200°–300° and 700°C, line widths, nutation frequencies and peak positions are consistent with motional averaging of quadrupolar satellites. Above 700°C there is little or no change in the peak positions with temperature. Chemical shifts of the materials at 1000°C (Na2Si3O7: 3.6; Na3AlSi6O15:-1.3; NaAlSi3O8:-6.4 ppm) indicate a slight change in the average Na coordination number from 6–7 for the silicate to 7–8 for the aluminosilicates.  相似文献   

13.
Glassy orthopyroxene granodiorite-tonalite (named pincinite after type locality) was described from basaltic lapilli tuffs of the Pliocene maar near Pinciná village in the Slovakian part of the Pannonian Basin. Two pincinite types exhibit a qualitatively similar mineral composition (quartz, An20–55 plagioclase, intergranular silicic glass with orthopyroxene and ilmenite, ±K-feldspar), but strongly different redox potential and formation PT conditions. Peraluminous pincinite is reduced (6–7% of total iron as Fe3+ in corundum-normative intergranular dacitic glass) and contains ilmenite with 8–10 mol% Fe2O3 and orthopyroxene dominated by ferrosilite. High-density (up to 0.85 g/cm3) primary CO2 inclusions with minor H2, CH4, H2S, CO and N2 (<2 mol% total) are present in Qtz and Plg. Equilibrium PT conditions inferred from the intergranular Opx–Ilm–Glass assemblage and fluid density correspond to 1,170±50°C, 5.6±0.4 kbar, respectively. Metaluminous pincinite is more oxidised (25–27% of total iron as Fe3+ in diopside-normative intergranular glass of rhyolite–trachyte–dacite composition) and contains Fe2O3-rich ilmenite (17–29 mol%) associated with enstatite. Fluid inclusions are composed of CO2–H2O mixtures with up to 38 mol% H2O. Raman spectroscopy revealed H2S along with dominant CO2 in the carbonic phase. Equilibrium PT parameters for the intergranular Opx–Ilm–Glass assemblage correspond to 740±15°C, 2.8±0.1 kbar, respectively. Reducing gas species (<2 mol% total) in the CO2-inclusions of the peraluminous pincinite resulted from hydrogen diffusion due to fH2 gradient imposed during decrease of redox potential from the log fO2 values near QFM during Qtz + Plg growth, to QFM-2 incidental to the superimposed Opx + Ilm assemblage in the intergranular melt. The decrease in oxygen fugacity was recorded also in the metaluminous pincinite, where log fO2 values changed from ~QFM + 2.6 to QFM + 0.4, but hydrogen diffusion did not occur. Absence of OH-bearing minerals, major and trace element abundances (e.g. REE 300–320, Nb 55–57, Th 4–31, Zr 240–300 ppm, FeOtot/MgO up to 11), and Sr–O isotope ratios in the pincinites are diagnostic of high-temperature anorogenic magmas originated by dehydration melting of biotite in quartz-feldspathoid crust (87Sr/86Sr>0.705–0.706, 18O>9 V-SMOW) around alkali basalt reservoir in depths between 17 and 20 km, and around late stage derivatives of the basalt fractionation, intruding the crust up to depths of 10–11 km. Low water activity in the pincinite parental melt was caused by CO2-flux from the Tertiary basaltic reservoirs and intrusions. The anatexis leads to generation of a melt-depleted granulitic crust beneath the Pannonian Basin, and the pincinites are interpreted as equivalents of igneous charnockites and enderbites quenched at temperatures above solidus and unaffected by sub-solidus re-equilibration and metamorphic overprint.  相似文献   

14.
The mineral paragonite, NaAl2[AlSi3O10 (OH)]2, has been synthesized on its own composition starting from a variety of different materials. Indexed powder data and refined cell parameters are given for both the 1M and 2M1 polymorphs obtained. The upper stability limit of paragonite is marked by its breakdown to albite + corundum + vapour. The univariant equilibria pertaining to this reaction have been established by reversing the reaction at six different pressures, the equilibrium curve running through the following intervals: 1 kb: 530°–550° C 2 kb: 555°–575° C 3 kb: 580°–600° C 5kb: 625°–640° C 6 kb: 620°–650° C 7 kb: 650°–670° C.Comparison with the upper stability limit of muscovite (Velde, 1966) shows that paragonite has a notably lower thermal stability thus explaining the field observation that paragonite is absent in many higher grade metamorphic rocks in which muscovite is still stable.The enthalpy and entropy of the paragonite breakdown reaction have been estimated. Since intermediate albites of varying structural states are in equilibrium with paragonite, corundum and H2O along the univariant equilibrium curve, two sets of data pertaining to the entropy of paragonite (S 298 0 ) as well as the enthalpy ( H f,298 0 ) and Gibbs free energy ( G f,298 0 ) of its formation were computed, assuming (1) high albite and (2) low albite as the equilibrium phase. The values are: (1) (2) S 298 0 67.8±3.9 cal deg–1 gfw–1 63.7±3.9 cal deg–1 gfw–1 H f,298 0 –1417.9±2.7 kcal gfw–1 –1420.2±2.6 kcal gfw–1 G f,298 0 –1327.4±4.0 kcal gfw–1 –1328.5±4.0 kcal gfw–1.Adapted from a part of the author's Habilitationsschrift accepted by the Ruhr University, Bochum (Chatterjee, 1968).  相似文献   

15.
Summary Synthesis of Mn-bearing ilvaites, CaFe 2–x 2+ MnxFe3+ [Si2O7/O/(OH)], with 0 x 0.19, have been performed under hydrothermal conditions at 2 and 3 kbars, T = 300 -400°C and at oxygen fugacities defined by the Fe2O3/Fe3O4 - and the Ni/NiO -buffer. As shown by X-ray diffraction, the substitution of Fe2+ by Mn2+ decreases the monoclinic angle and causes a phase transition from monoclinic to orthorhombic at x = 0.19. The Fe-distribution has been determined by Mössbauer spectroscopy.
Synthese und Charakterisierung von Mn-haltigem Ilvait CaFe 2–x 2+ MnxFe3+ [Si2O7/O/(OH)]
Zusammenfassung Mn-haltiger Ilvait CaFe 2–x 2+ Mnx Fe3+ [Si2O7/O/(OH)] wurde unter hydrothermalen Bedingungen bei Drucken von 2 und 3 kbar, Temperaturen zwischen 300 und 400°C und bei Sauerstoff Fugazitäten, die durch Festkörperpuffer (Fe2O3/Fe3O4 und Ni/NiO) kontrolliert wurden, hergestellt. Röntgenbeugungsuntersuchungen zeigen, daß mit steigendem Mn-Einbau der monokline Winkel kleiner wird, und daß bei x = 0.19 ein Phasenübergang von der monoklinen zur orthorhombischen Struktur erfolgt. Die Fe-Verteilung wurde mit Mössbauer-Spektroskopie bestimmt.

With 4 Figures  相似文献   

16.
Phase relations for the magnesio-hornblende bulk composition, 2 CaO·4 MgO·Al2O3·7 SiO2+ excess H2O, have been investigated to 10 kb employing hydrothermal and piston-cylinder techniques. The low-temperature limit of amphibole in this system lies at 519° C, 1,000 bars, 541° C, 2,000 bars, and 718° C, 10 kb. The low-T assemblage consists of an+chl+di+tc(+f), and is related to the adjacent high-T equilibrium assemblage, amph+an+chl+f, by the solid-solid reaction (A): 2 di+tc=tr. Small amounts of aluminum, hypothesized to be preferentially dissolved in the cpx (and in the tc) relative to amph, may account for the broad P-T stability range of the di+tc assemblage in the synthetic work relative to systems involving stoichiometric tr, Ca2Mg5Si8O22(OH)2, such as are common in natural, Al-poor calc-silicate parageneses. Alternatively, the low-temperature assemblage produced in the experiments may be metastable. For the investigated bulk composition, synthetic tremolitic-cummingtonitic amphibole contains relatively modest amounts of ts, Ca2Mg3Al2 IVSi6-Al2 IVO22(OH)2; at pressures of 1,000–3,000 bars, solid solution extends from near tremolite only to about cu11tr69ts20, analogous to most analyzed natural magnesio-hornblendic specimens. At 10 kb fluid pressure, the solid solution reaches approximately cu06tr53ts41 for the investigated bulk composition, and appears to be virtually independent of temperature. Amphibole and 14 Å chl react within the amphibole stability field, along curve (B), at about 704° C and 2,000 bars, to produce an, en, fo and f (H=40.9 kcal/ mole); at pressures greater than approximately 7kb, due to the incompatibility of an and fo, the higher temperature assemblage consists of amph, an, en, sp and f. Above P fluid– T curve (B), the amphibole coexists with an+en+fo+f at low pressures; at higher pressures, the amphibole, which is in equilibrium with an+en+sp+f, is relatively more aluminous. The high-T stability limit of aluminous tr+fo lies approximately 20–25° C below the dehydration curve for stoichiometric tremolite on its own bulk composition. Reaction (C), tr+fo=2 di+5 en+f (H = 39.4 kcal/mole), produces an+di+en+f, the highest temperature subsolidus assemblage investigated for the tr50ts50 bulk composition. Hydrous melt is encountered at temperatures at least as low as 900° C at 10 kb, and at that fluid pressure coexists with amphibole over an interval of more than 60° C. Limited solid solution observed between tr and ts in nature (tr100-70) is accounted for by the restricted range of amphibole compositions produced in the present study. Such amphiboles, moreover, appear to have both high- and low-temperature stability limits, as demonstrated by the experimental results.Institute of Geophysics and Planetary Physics Publication No. 2811  相似文献   

17.
The effect of the Si/Al distribution in the tetrahedral sheets of the vermiculite mineral has been investigated employing density functional theory. The structures of six models for vermiculite with the structural formula (Mg4)(Mg12)(Si8Al8)O40(OH)8·24(H2O) per unit cell were fully optimized. The models differ by the T···Mg2+···T coordination of the interlayer Mg2+ cations by two central cations from the adjacent tetrahedral sheets of the 2:1 vermiculite layers (T,T=Si,Al). We observed the formation of very strong hydrogen bonds between water molecules solvating the interlayer Mg2+ cations and the surface basal oxygen atoms of the 2:1 layers. The directionality of hydrogen bonds is the major factor determining the layer stacking in the vermiculite structure. Results showed that the most stable model is that where only silicon atoms in the tetrahedral sheets coordinate all interlayer Mg2+ cations.  相似文献   

18.
The partitioning of samarium and thulium between garnets and melts in the systems Mg3Al2-Si3O12-H2O and Ca3Al2Si3O12-H2O has been studied as a function of REE concentration in the garnets at 30 kbar pressure. Synthesis experiments of variable time under constant P, T conditions indicate that garnet initially crystallizes rapidly to produce apparent values of D Sm (D Sm=concentration of Sm in garnet/concentration of Sm in liquid) which are too large in the case of pyrope and too small in the case of grossular. As the experiment proceeds, Sm diffuses out of or into the garnet and the equilibrium value of D Sm is approached. Approximate values of diffusion coefficients for Sm in pyrope garnet obtained by this method are 6 × 10–13 cm2 s–1 at 1,300 ° C and 2 × 10–12 cm2 s–1 at 1,500 ° C, and for grossular, 8.3 × 10–12 cm2 s–1 at 1,200 ° C and 4.6 × 10–11 cm2 s–1 at 1,300 ° C. The equilibrium values of D Sm have been reversed by experiments with Sm-free pyrope and Sm-bearing glass, and with Sm-bearing grossular and Sm-free glass.Between 12 ppm and 1,000 ppm Sm in pyrope at 1,300 ° C and between 80 ppm and >2 wt.% Tm in pyrope at 1,500 ° C, partition coefficients are constant and independent of REE concentration. Above 100 ppm of Sm in garnet at 1,500 ° C, partition coefficients are independent of Sm concentration. At lower concentrations, however, D Sm is dependent upon the Sm content of the garnet. The two regions may be interpreted in terms of charge-balanced substitution of Sm3Al5O12 in the garnet at high Sm concentrations and defect equilibria involving cation vacancies at low concentrations. At very low REE concentrations (< 1 ppm Tm in grossular at 1,300 ° C) DREE garnet/liquid again becomes constant with an apparent Henry's Law value greater than that at high concentrations. This may be interpreted in terms of a large abundance of cation vacancies relative to the number of REE ions.The importance of defects in the low concentration region has been confirmed by adding other REE (at 80 ppm level) to the system Mg3Al2Si3O12-H2O at low Sm concentrations. These change D Sm in the defect region, demonstrating their role in the production of vacancies.Experiments on a natural pyropic garnet indicate that defect equilibria are of importance to REE partitioning within the concentration ranges found in nature.  相似文献   

19.
Summary Sonoraite, FeTeO3(OH)·H2O, is monoclinic,P 21/c, witha=10.984(2),b=10.268(2),c=7.917(2) Å, =108.49(2)°. For 8 formula units per cell the calculated density is 4.179(2) g/cm3; the observed value is 3.95(1) g/cm3. The Supper-Pace automated diffractometer was used to collect 1884 independent reflections which were corrected for absorption. The structure was determined by an automated symbolic addition procedure. It was refined to a residualR of 6.2% using anisotropic temperature factors for the cations and isotropic temperature factors for the oxygen atoms. Chains of octahedra about Fe extend along [101]; edge-sharing pairs of these octahedra are joined by corner sharing. The Fe–Fe distances across the shared edges are 3.05 and 3.20 Å, short enough to suggest magnetic interactions. All but one H2O are involved in the chains. The Te4+ ions have a pseudotetrahedral coordination, with three oxygen ions forming one face of the tetrahedron and the lone electron pair of Te occupying the fourth corner. The O–Te–O average bond angle is 95°. The Fe chains are tied together by Te–O bonds in all three dimensions.
Die Kristallstruktur von Sonorait, Fe3+Te4+O3(OH).H2O
Zusammenfassung Sonorait, FeTeO3(OH)·H2O, ist monoklin, P 21/c, mit den folgenden Zelldimensionen:a=10,984(2),b=10,268(2),c=7,917(2) Å, =108,49(2)°. Mit 8 Formel-Einheiten errechnet man eine Dichte von 4,179(2) g/cm3; die gemessene Dichte beträgt 3,95(1) g/cm3. Das Supper-Pace automatische Diffraktometer wurde zur Sammlung von 1884 unabhängigen Reflexen benutzt, welche für Absorption korrigiert wurden. Die Struktur wurde mit Hilfe eines vollständig automatischen Programms für symbolische Addition bestimmt. Mit anisotropen Temperaturfaktoren für die Kationen und mit isotropen Temperaturfaktoren für die Sauerstoff-Atome wurde ein Residuum von 6,2% erreicht. Ketten von Eisen-Oktaedern erstrecken sich entlang [101]; Oktaeder-Paare mit gemeinsamen Kanten sind über Eckenverknüpfung verbunden. Die Fe–Fe-Abstände über die gemeinsamen Kanten betragen 3,05 und 3,20 Å, kurz genug, um zu magnetischer Wechselwirkung führen zu können. Nur ein H2O-Molekül ist nicht Teil einer Kette. Die Te4+-Ionen befinden sich in pseudotetraedrischer Koordination; drei Sauerstoff-Ionen bilden eine Fläche des Tetraeders, die vierte Ecke wird durch das einsame Elektronenpaar von Te besetzt. Der Mittelwert des O–Te–O-Bindungswinkels beträgt 95° Die Fe-Ketten werden durch Te–O-Bindungen dreidimensional verbunden.

With 3 Figures  相似文献   

20.
The model for the thermodynamic properties of multicomponent pyroxenes (Part I) is calibrated for ortho- and clinopyroxenes in the quadrilateral subsystem defined by the end-member components Mg2Si2O6, CaMgSi2O6, CaFeSi2O6, and Fe2Si2O6. This calibration accounts for: (1) Fe-Mg partitioning relations between orthopyroxenes and augites, and between pigeonites and augites, (2) miscibility gap features along the constituent binary joins CaMgSi2O6-Mg2Si2O6 and CaFeSi2O6-Fe2Si2O6, (3) calorimetric data for CaMgSi2O6-Mg2Si2O6 pyroxenes, and (4) the P-T-X systematics of both the reaction pigeonite=orthopyroxene+augite, and miscibility gap featurs, over the temperature and pressure ranges 800–1500°C and 0–30 kbar. The calibration is achieved with the simplifying assumption that all regular-solution-type parameters are constants independent of temperature. It is predicated on the assumptions that: (1) the Ca-Mg substitution is more nonideal in Pbca pyroxenes than in C2/c pyroxenes, and (2) entropies of about 3 and 6.5 J/K-mol are associated with the change of Ca from 6- to 8-fold coordination in the M2 site in magnesian and iron C2/c pyroxenes, respectively. The model predicts that Fe2+-Mg2+ M1-M2 site preferences in C2/c pyroxenes are highly dependent on Ca and Mg contents, with Fe2+ more strongly preferring M2 sites both in Ca-rich C2/c pyroxenes with a given Fe/(Fe+Mg) ratio, and in magnesian C2/c pyroxenes with intermediate Ca/(Ca+Fe+Mg) ratios.The proposed model is internally consistent with our previous analyses of the solution properties of spinels, rhombohedral oxides, and Fe-Mg olivines and orthpyroxenes. Results of our calibration extend an existing database to include estimates for the thermodynamic properties of the C2/c and Pbca pyroxene end-members clinoenstatite, clinoferrosilite, hedenbergite, orthodiopside, and orthohedenbergite. Phase relations within the quadrilateral and its constitutent subsystems are calculated for temperatures and pressures over the range 800–1700°C and 0–50 kbar and compare favorably with experimental constraints.  相似文献   

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