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1.
The temperature dependence of water solubility in enstatite   总被引：3，自引：0，他引：3  
The solubility of water in pure enstatite was measured on samples synthesized under water-saturated conditions at 15 kbar and temperatures ranging from 700 to 1,100°C. Polarized FTIR measurements on millimetre-sized, clear crystals showed that water solubility increases strongly with temperature, from 101 ppm by weight at 700°C to 269 ppm by weight at 1,100°C. The position and shape of the infrared bands hardly changes with temperature, with one notable exception: a band close to 3,380 cm–1 is present in samples synthesized between 700 and 1,000°C, while this band is absent from samples synthesized at 1,100°C. This effect appears to be very reproducible and points towards a slight change in the crystal structure of enstatite between 1,000 and 1,100°C at 15 kbar. The water solubility data of this study as well as those of Rauch and Keppler (Contrib Mineral Petrol 143:525–536, 2002) can be reproduced by the equation where K is water solubility, is water fugacity, A is 0.01354 ppm/bar, Vsolid=12.1 cm3/mol is the volume change of enstatite during incorporation of water, and H1 bar=-4,563 J/mol is the reaction enthalpy at 1 bar. This equation predicts the following behaviour of water solubility in enstatite as a function of pressure and temperature: (1) water solubility increases with pressure up to a maximum around 80 kbar; (2) water solubility decreases with temperature at 1 bar; and (3) water solubility increases with temperature between 10 and 100 kbar. If the observed temperature dependence for enstatite were representative for other upper mantle minerals as well, it would have the following implications: (1) Lateral temperature gradients in the upper mantle could cause major variations in water contents at the same depth; in particular, hot mantle plumes may scavenge water from the surrounding shallow upper mantle. (2) The scavenging of water by hot plumes could be a major factor in increasing the mobility of plumes. (3) The predicted temperature dependence of water solubility at the base of the upper mantle may allow plumes to bypass the transition zone water filter postulated by Bercovici and Karato (Nature 425:39–44, 2003).  相似文献   

2.
The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H2O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al2O3 in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.  相似文献   

3.
The effect of alumina and water solubility on the development of fabric in orthopyroxene in response to simple shear deformation has been investigated at a pressure of 1.5 GPa and a temperature of 1,100 °C using the D-DIA apparatus. The microstructure observations at these conditions indicate that dislocation glide is the dominant deformation mechanism. In MgSiO3 enstatite and hydrous aluminous enstatite, partial dislocations bounding the stacking faults in [001] glide parallel to the (100) (or) the (100) [001] slip system. Electron backscattered diffraction analysis of anhydrous aluminous enstatite, however, indicates operation of the (010) [001] slip system, and microstructure analysis indicates dislocation movement involving [001] on both (100) and {210} planes. The strong covalent bonding induced by the occupation of M1 and T2 sites by Al could have restricted the glide on (100), activating slip on {210}. The resulting seismic anisotropies (~2 %) in orthopyroxene are weaker compared to olivine (~9.5 %), and reduced anisotropy can be expected if orthopyroxene coexists with olivine. Weak anisotropy observed in stable cratonic regions can be explained by the relatively high abundance of orthopyroxene in these rocks.  相似文献   

4.
Samples of enstatite and forsterite were crystallized in the presence of a hydrous fluid at 15 kbar and 1100 °C. Water contents in quenched samples were measured by 1H MAS NMR and by FTIR. If the samples were prepared in the same way, similar water concentrations were obtained by both methods. There is no evidence that one or the other method would severely over or underestimate water contents in nominally anhydrous minerals. However, measured water contents vary by orders of magnitude depending on sample preparation. The lowest water contents are measured by polarized FTIR spectroscopy on clear, inclusion-free single crystals. These water contents probably reflect the real point defect solubility in the crystals. Polycrystalline material shows much higher total water concentrations, presumably due to hydrous species on grain boundaries, growth defects, and in submicroscopic fluid inclusions. Grinding the sample in air further increases water concentration. This effect is even more pronounced if the sample is ground in water and subsequently dried at 150 °C. Polarized FTIR measurements on clear single crystals of enstatite saturated at 15 kbar and 1100 °C give 199 ± 25 ppm by weight of water. The spectra show sharp and strongly polarized bands. These bands are also present in spectra measured through turbid, polycrystalline aggregates of enstatite. However, in these spectra, they are superimposed on much broader, nearly isotropic bands resulting from hydrous species in grain boundaries, growth defects, and submicroscopic fluid or melt inclusions. Total water contents for these polycrystalline aggregates are between 2000 and 4000 ppm. Water contents measured by FTIR on enstatite powders are 5300 ppm after grinding in air and 12 600 ppm after grinding under water und subsequent drying at 150 °C. Received: 25 June 1999 / Revised, accepted: 4 October 1999  相似文献   

5.
GREEN  D. H. 《Journal of Petrology》1964,5(1):134-188
The Lizard peridotite produced a high-temperature metamorphicaureole during diapirie emplacement in a period of amphibolitefacies regional metamorphism. The peridotite preserves a coarse-grainedprimary core within a cataclastic, finely foliated and recrystallizedmarginal shell. Chemical analyses demonstrate the constancyof rock composition in the primary and recrystallized mineralassemblages. The primary mineral assemblage of the peridotiteconsists of olivine (Fo89), aluminous enstatite, aluminous diopside,and green aluminous spinel. In contrast the mineral assemblageon recrystallization is olivine, enstatite (normal Al2O3 content),diopside (normal Al2O3 content), plagioclase, and brown chromite.A third assemblage of olivine, pargasite, and brown chromianspinel is developed locally from the plagioclase-bearing assemblage,particularly in contact areas. Major and trace element analyses of twenty minerals and eightrocks are given. These are compared in detail with peridotitesand minerals occurring as accumulates from basaltic magma, asperidotite nodules in basalts and as ’intrusive' peridotitesin orogenic areas. It is concluded that the primary mineralsof the Lizard peridotite have not crystallized and accumulatedfrom a basaltic magma but have crystallized in a similar environmentto that of peridotite nodules in basalts. It is further concludedthat the cause of the differences between the primary and recrystallizedassemblages of the peridotite is primarily a difference in loadpressure at crystallization. In particular the high aluminacontent of both enstatite and diopside and the coexistence ofpyroxenes+ aluminous spinel instead of olivine+anorthite areconsidered to be a direct consequence of the high load pressureat the initial crystallization of the peridotite.  相似文献   

6.
Experiments were conducted to determine the solubilities ofH2O and CO2 and the nature of their mixing behavior in basalticliquid at pressures and temperature relevant to seqfloor eruption.Mid-ocean ridge basaltic (MORB) liquid was equilibrated at 1200°Cwith pure H2O at pressures of 176–717 bar and H2O—CO2vapor at pressures up to 980 bar. Concentrations and speciationof H2O and CO2 dissolved in the quenched glasses were measuredusing IR spectroscopy. Molar absorptivities for the 4500 cm–1band of hydroxyl groups and the 5200 and 1630 cm–1 bandsof molecular water are 0•67±0•03, 0•62±0•07,and 25±3 l/mol-cm, respectively. These and previouslydetermined molar absorptivities for a range of silicate meltcompositions correlate positively and linearly with the concentrationof tetrahedral cations (Si+Al). The speciation of water in glass quenched from vapor-saturatedbasaltic melt is similar to that determined by Silver &Stolper (Journal of Petrology 30, 667–709, 1989) in albiticglass and can be fitted by their regular ternary solution modelusing the coefficients for albitic glasses. Concentrations ofmolecular water measured in the quenched basaltic glasses areproportional to f H2O in all samples regardless of the compositionof the vapor, demonstrating that the activity of molecular waterin basaltic melts follows Henry's law at these pressures. Abest fit to our data and existing higher-pressure water solubilitydata (Khitarov et al., Geochemistry 5, 479–492, 1959;Hamilton et al., Journal of Petrology 5, 21–39, 1964),assuming Henrian behavior for molecular water and that the dependenceof molecular water content on total water content can be describedby the regular solution model, gives estimates for the Vo, mH2Oof 12±1 cm3/mol and for the 1-bar water solubility of0•11 wt%. Concentrations of CO2 dissolved as carbonate in the melt forpure CO2-saturated and mixed H2O-CO2-saturated experiments area simple function of fCO2 These results suggest Henrian behaviorfor the activity of carbonate in basaltic melt and do not supportthe widely held view that water significantly enhances the solutionof carbon dioxide in basaltic melts. Using a Vo, mr of 23 cm3/mol(Pan et al., Geochimica et Cosmochimica Acta 55, 1587–1595,1991), the solubility of carbonate in the melt at 1 bar and1200°C is 0•5 p.p.m. Our revised determination of CO2solubility is 20% higher than that reported by Stolper &Holloway (Earth and Planetary Science Letters 87, 397–408,1988). KEY WORDS: mid-ocean ridge basalts; water and carbon dioxide solubility; experimental petrology  相似文献   

7.
Al- and F-rich titanite (3.862O3 <9.33 wt%, 0.931(F, OH)1Ti-1O-1 substitution within single crystals, particularly at grain boundaries with omphacite and/or phengite. In-situ ion microprobe U-Pb analysis of titanite domains that have various Al and F contents yielded apparent 206Pb/238U ages scattering between 283 and 153 Ma. Chemical and petrological data are indispensable to interpret this complex age distribution, and the good correlation between 206Pb/238U ratios and Al content indicates that the Al- and F-rich titanite was formed during pre-Alpine metamorphism (𔕑ᆟ Ma). Progressively younger ages are obtained in domains with decreasing Al and F content, suggesting that partial chemical re-equilibration was responsible for the incomplete isotopic resetting during Alpine metamorphism. Petrological and U-Pb data show that Al- and F-rich titanite should be used with caution to infer high-pressure conditions in polymetamorphic carbonate systems.  相似文献   

8.
Crystallization of Chromite and Chromium Solubility in Basaltic Melts   总被引：6，自引：3，他引：6  
The equilibrium between chromite and melt has been determinedon four basalts at temperatures of 1200–1400?C over arange of oxygen fugacity (fo2) and pressures of 1 atm and 10kb. The Cr content of chromite-saturated melts at 1300?C and1 atm ranges from 0?05 wt.% Cr2O3 at a log fo2= –3 to1?4 wt.% at a log fo2=–12?8. The Cr2+/Cr3+ of melt increaseswith decreasing fo2 and is estimated by assuming a constantpartitioning of Cr3+ between chromite and melt at constant temperature.The estimated values of Cr2+/Cr3+ in the melt are at fo2 valuesof 4–5 orders of magnitude lower than the equivalent Fe2+/Fe3+values. The Cr/(Cr+Al) of chromite coexisting with melt at constanttemperature changes little with variation of fo2 below log fo2=–6.Five experiments at 10 kb indicate that Cr2O3 dissolved in themelt is slightly higher and the Cr/(Cr + Al) of coexisting chromiteis slightly lower than experiments at 1 atm pressure. Thus variationin total pressure cannot explain the large variations of Cr/(Cr+ Al) that are common to mid-ocean ridge basalt (MORB) chromite. Experiments on a MORB at 1 atm at fo2 values close to fayalite-magnetite-quartz(FMQ) buffer showed that the Al2O3 content of melt is highlysensitive to the crystallization or melting of plagioclase,and consequently coexisting chromite shows a large change inCr/(Cr + Al). It would appear, therefore, that mixing of a MORBmagma containing plagioclase with a hotter MORB magma undersaturatedin plagioclase may give rise to the large range of Cr/(Cr +Al) observed in some MORB chromite.  相似文献   

9.
The Bixiling mafic-ultramafic metamorphic complex is a 1•5km2 tectonic block within biotite gneiss in the southern Dabieultrahigh-pressure terrane, central China. The complex consistsof banded eclogites that contain thin layers of garnet-bearingcumulate ultramafic rock. Except for common eclogitic phases(garnet, omphacite, kyanite, phengite, zoisite and rutilc),banded eclogites contain additional talc and abundant coesiteinclusions in omphacite, zoisite, kyanite and garnet. Some metaultramaficrocks contain magnesite and Ti-clinohumite. Both eclogites andmeta-ultramafic rocks have undergone multi-stage metamorphism.Eclogite facies metamorphisrn occurred at 610–700C andP>27 kbar, whereas amphibolite facies retrograde metamorphismis characterized by symplectites of plagioclase and hornblendeafter omphacite and replacement of tremolite after talc at P<6–15kbar and T <600C. The meta-ultramafic assemblages such asolivine + enstatite + diopside + garnet and Ti-clinohumite +diopside + enstatite + garnet + magnesite olivine formed at700–800C and 47–67 kbar. Investigation of the phaserelations for the system CaO-MgO-SiO2-H2O-CO2 and the experimentallydetermined stabilities of talc, magnesite and Ti-clinohumiteindicate that (1) UHP talc assemblages are restricted to Mg-Algabbro composition and cannot be an important water-bearingphase in the ultramafic mantle, and (2) Ti-clinohumite and magnesiteare stable H2O-bearing and CO2-bearing phases at depths >100km. The mafic-ultramafic cumulates were initially emplaced atcrustal levels, then subducted to great depths during the Triassiccollision of the Sine-Korean and Yangtze cratons. KEY WORDS: eclogite; magnesite; meta-ultramafics; talc; ultrahigh-P metamorphism *Corresponding author  相似文献   

10.
Hydrogen solubility and hydroxyl substitution mechanism in olivineat upper-mantle conditions are not only a function of pressure,temperature, water fugacity and hydrogen fugacity, but are alsoinfluenced by silica activity. Olivine synthesized in equilibriumwith magnesiowüstite displays hydroxyl stretching bandsin the wavenumber range from 3640 to 3430 cm–1. In contrast,olivine in equilibrium with orthopyroxene shows absorption bandsin a narrower wavenumber range from 3380 to 3285 cm–1.The two fundamentally different spectra are assigned to hydroxylin tetrahedral and octahedral sublattices, respectively. Olivinein equilibrium with orthopyroxene is also less capable of incorporatinghydroxyl, relative to olivines in equilibrium with magnesiowüstite,by about a factor of ten. A comparison of spectra obtained aspart of this study with hydroxyl spectra of natural mantle olivinesshows that the latter display hydroxyl stretching patterns reminiscentof equilibrium with magnesiowüstite, although undoubtedlyolivine in the Earth’s mantle coexists with orthopyroxene.This may be attributed to a metasomatic overprint by a low-silicafluid and/or melt that was in reaction relationship with orthopyroxene.A likely metasomatic agent is a carbonatitic melt. When carbonatiticmelts decompose to oxides and CO2, they may temporarily imposea low-aSiO2 environment inherited by the olivine structure.If this suggestion proves true, Fourier transform IR spectroscopymay be used to fingerprint metasomatic episodes in the lithosphericmantle. KEY WORDS: FTIR spectrometry; olivine; mantle; metasomatism; water  相似文献   

11.
The solubility of U and Th in aqueous solutions at P-T-conditions relevant for subduction zones was studied by trapping uraninite or thorite saturated fluids as synthetic fluid inclusions in quartz and analyzing their composition by Laser Ablation-ICPMS. Uranium is virtually insoluble in aqueous fluids at Fe-FeO buffer conditions, whereas its solubility increases both with oxygen fugacity and with salinity to 960 ppm at 26.1 kbar, Re-ReO2 buffer conditions and 14.1 wt% NaCl in the fluid. At 26.1 kbar and 800°C, uranium solubility can be reproduced by the equation: log\textU = 2.681 + 0.1433logf\textO2 + 0.594\textCl, \log {\text{U}} = 2.681 + 0.1433\log f{\text{O}}_{2} + 0.594{\text{Cl,}} where fO2 is the oxygen fugacity, and Cl is the chlorine content of the fluid in molality. In contrast, Th solubility is generally low (<10 ppm) and independent of oxygen fugacity or fluid salinity. The solubility of U and Th in clinopyroxene in equilibrium with uraninite and thorite was found to be in the order of 10 ppm. Calculated fluid/cpx partition coefficients of Th are close to unity for all conditions. In contrast, Dfluid/cpx for uranium increases strongly both with oxygen fugacity and with salinity. We show that reducing or NaCl-free fluids cannot produce primitive arc magmas with U/Th ratio higher than MORB. However, the dissolution of several wt% of oxidized, saline fluids in arc melts can produce U/Th ratios several times higher than in MORB. We suggest that observed U/Th ratios in arc magmas provide tight constraints on both the salinity and the oxidation state of subduction zone fluids.  相似文献   

12.
The solubility of sulfur as S2– has been experimentallydetermined for 19 silicate melt compositions in the system CaO–MgO–Al2O3–SiO2(CMAS)± TiO2 ± FeO, at 1400°C and 1 bar, using CO–CO2–SO2gas mixtures to vary oxygen fugacity (fO2) and sulfur fugacity(fS2). For all compositions, the S solubility is confirmed tobe proportional to (fS2/fO2)1/2, allowing the definition ofthe sulfide capacity (CS) of a silicate melt as CS = [S](fO2/fS2)1/2.Additional experiments covering over 150 melt compositions,including some with Na and K, were then used to determine CSas a function of melt composition at 1400°C. The resultswere fitted to the equation  相似文献   

13.
Tourmaline has been synthesized hydrothermally at 200 MPa between 300 and 700 °C from oxide mixtures with Mg-Al ratios for the end members dravite NaMg3Al6(Si6O18)(BO3)3(OH)3(OH) and Mg-foitite &ding6F;(Mg2Al)Al6 (Si6O18)(BO3)3(OH)3(OH). Six different Na concentrations were investigated to determine the distribution of Na between tourmaline and fluid in the SiO2-saturated system Na2O-MgO-Al2O3-SiO2-B2O3-H2O-HCl. Synthetic tourmaline ranges from X-site vacant (&ding6F;) tourmaline (Mg-foitite) to nearly ideal dravite with Na=0.95 apfu. There are small, but significant, amounts of proton deficiency and negligible tetrahedral Al. Chemical variation is primarily caused by the substitutions Al&ding6F;Mg-1Na-1 and minor AlMg-1H-1. Varying amounts of Na and &ding6F; determine the Mg/Al ratios. Besides tourmaline and quartz, additional Mg-Al phases are chlorite and, at 700 °C, cordierite. Albite is also present at high Na concentrations in the bulk composition. The c dimension of the tourmaline crystals increases with Na in tourmaline. The amount of Na in the X-site depends strongly on the bulk concentration of Na in the system as well as on the temperature. These factors in turn control the phase assemblage and the composition of the fluid phase. For the assemblage tourmaline + quartz + chlorite/cordierite + fluid, a linear relationship exists between Na concentration in the fluid (quenched after the run) and tourmaline with temperature: T °C [ᆭ °C]=(Nafluid/Natur)앾.878-14.692 (r2=0.96). For the assemblage tourmaline + albite + quartz + fluid, it is: T °C [ᆣ °C]=(Nafluid/Natur)욝.813-6.231 (r2=0.95), where Nafluid is the concentration of Na+ in the final fluid (mol/l) and Natur is the number of Na cations in the X-site of tourmaline. The equations are valid in the temperature range of 500-715 °C. Our experiments demonstrate that the occupancy of the X-site in combination with the changing concentrations of Al and Mg can be used to monitor changes in the fluid composition in equilibrium with a growing tourmaline crystal. Currently, this relation can be applied qualitatively to natural tourmaline to explain zoning in Na- and Al/(Al+Mg).  相似文献   

14.
End member boromuscovite, with nearly the ideal composition, was synthesized as a single phase from mixtures of its own composition, or with excess boron and water, at high pressures of between 15 and 30 kbar at 700 °C. The mica synthesized consists of a mixture of 2M1 and 1M polytypes with the cell dimensions of 2M1: a=5.071(4), b=8.786(4), c=19.830(89) Å, #=95.84(12)°, V=878.5(1.4) Å3; and 1M: a=5.059(5), b=8.819(6), c=10.025(17) Å, #=101.39(57)°, V=438.4(1.3) Å. The IR spectrum shows characteristic differences relative to that of muscovite. DTA registers an endothermic peak due to dehydration breakdown above 680 °C. Seeded experiments indicate that boromuscovite is a high-pressure phase requiring minimum pressures of 3 to 10 kbar at temperatures that concomitantly increase from 300 to 750 °C. At lower pressures, the anhydrous solid assemblage K-feldspar + Al-borate (probably Al4B2O9) coexists with a vapor rich in boric acid. The conversion of this assemblage to boromuscovite is connected with increases in the coordination number of B from [3] to [4], and of Al from [4] to [6]. Above 10 kbar, the boromuscovite stability field is limited along its high-temperature side by congruent (or incongruent?) melting of the mica, starting near 750 °C and 10 kbar and increasing to about 900 °C at 50 kbar, although, at such very high pressures a supercritical fluid may be present. Because, even in the presence of excess-boron fluid, the synthetic mica shows invariable X-ray properties, it is concluded that one B atom per formula unit represents the maximum, and - contrary to olenitic tourmalines - no further substitution of Si by B linked with addition of hydrogen takes place. In contrast to muscovite, KAl2[AlSi3O10](OH)2, end member boromuscovite is not stable under normal P-T conditions of the Continental Crust along a 30 °C/km geotherm, and especially not during the intrusion of acidic igneous rocks including their pegmatites, which may explain its scarcity in nature. However, it may form in the waning hydrothermal stages of deep-seated (>10.5 km) pegmatites and - providing sufficient boron is available - in HP/LT subduction zone environments, where it may carry boron to considerable depths.  相似文献   

15.
Hydrous species and the amount of water (OH? ions and crystal hydrate H2O) in structures of nominally anhydrous rock-forming minerals (olivine, ortho- and clinopyroxenes) were studied with Fourier spectroscopy in peridotite nodules (19 samples) from Cenozoic alkali basalts of the Baikal-Mongolia region (Dariganga Plateau, Taryat Depression, and Vitim Plateau). Single-crystal samples oriented relative to the crystallographic axes of minerals were examined with an FTIR spectrometer equipped with an IR microscope at the points of platelets free from fluid inclusions. FTIR spectra were measured in regions of stretching vibrations of OH? and H2O (3800–3000 cm?1) and deformation vibrations of H2O (1850–1450 cm?1). The water content in mineral structures was determined from integral intensities. To estimate the conditions of entrapment and loss of structural water in minerals, their chemical composition, including Fe2+ and Fe3+ contents, was determined with an electron microprobe analysis and Mössbauer spectroscopy. The bulk chemical composition of some nodules was determined with XRF and ICP MS. The total water content (OH? + H2O) varies from 150 to 1140 ppm in olivines, from 45 to 870 ppm in clinopyroxenes, and from 40 to 1100 ppm in orthopyroxenes. Both water species in the mineral structures are retained down to a depth of 150–160 km in wide temperature and pressure ranges (1100–1500 °C, 32–47 kbar) at the oxygen fugacity of ?1.4 to ?0.1 log units relative to that of the quartz-fayalite-magnetite buffer.  相似文献   

16.
The ultrahigh-temperature (UHT) metamorphism of the Napier Complex is characterized by the presence of dry mineral assemblages, the stability of which requires anhydrous conditions. Typically, the presence of the index mineral orthopyroxene in more than one lithology indicates that H2O activities were substantially low. In this study, we investigate a suite of UHT rocks comprising quartzo-feldspathic garnet gneiss, sapphirine granulite, garnet-orthopyroxene gneiss, and magnetite-quartz gneiss from Tonagh Island. High Al contents in orthopyroxene from sapphirine granulite, the presence of an equilibrium sapphirine-quartz assemblage, mesoperthite in quartzo-feldspathic garnet gneiss, and an inverted pigeonite-augite assemblage in magnetite-quartz gneiss indicate that the peak temperature conditions were higher than 1,000 °C. Petrology, mineral phase equilibria, and pressure-temperature computations presented in this study indicate that the Tonagh Island granulites experienced maximum P-T conditions of up to 9 kbar and 1,100 °C, which are comparable with previous P-T estimates for Tonagh and East Tonagh Islands. The textures and mineral reactions preserved by these UHT rocks are consistent with an isobaric cooling (IBC) history probably following an counterclockwise P-T path. We document the occurrence of very high-density CO2-rich fluid inclusions in the UHT rocks from Tonagh Island and characterize their nature, composition, and density from systematic petrographic and microthermometric studies. Our study shows the common presence of carbonic fluid inclusions entrapped within sapphirine, quartz, garnet and orthopyroxene. Analysed fluid inclusions in sapphirine, and some in garnet and quartz, were trapped during mineral growth at UHT conditions as 'primary' inclusions. The melting temperatures of fluids in most cases lie in the range of -56.3 to -57.2 °C, close to the triple point for pure CO2 (-56.6 °C). The only exceptions are fluid inclusions in magnetite-quartz gneiss, which show slight depression in their melting temperatures (-56.7 to -57.8 °C) suggesting traces of additional fluid species such as N2 in the dominantly CO2-rich fluid. Homogenization of pure CO2 inclusions in the quartzo-feldspathic garnet gneiss, sapphirine granulite, and garnet-orthopyroxene gneiss occurs into the liquid phase at temperatures in the range of -34.9 to +4.2 °C. This translates into very high CO2 densities in the range of 0.95-1.07 g/cm3. In the garnet-orthopyroxene gneiss, the composition and density of inclusions in the different minerals show systematic variation, with highest homogenization temperatures (lowest density) yielded by inclusions in garnet, as against inclusions with lowest homogenization (high density) in quartz. This could be a reflection of continued recrystallization of quartz with entrapment of late fluids along the IBC path. Very high-density CO2 inclusions in sapphirine associated with quartz in the Tonagh Island rocks provide potential evidence for the involvement of CO2-rich fluids during extreme crustal temperatures associated with UHT metamorphism. The estimated CO2 isochores for sapphirine granulite intersect the counterclockwise P-T trajectory of Tonagh Island rocks at around 6-9 kbar at 1,100 °C, which corresponds to the peak metamorphic conditions of this terrane derived from mineral phase equilibria, and the stability field of sapphirine + quartz. Therefore, we infer that CO2 was the dominant fluid species present during the peak metamorphism in Tonagh Island, and interpret that the fluid inclusions preserve traces of the synmetamorphic fluid from the UHT event. The stability of anhydrous minerals, such as orthopyroxene, in the study area might have been achieved by the lowering of H2O activity through the influx of CO2 at peak metamorphic conditions (>1,100 °C). Our microthermometric data support a counterclockwise P-T path for the Napier Complex.  相似文献   

17.
The water-pressure temperature stability field of yoderite,ideally Mg2Al5.6Fe3 + 0.4Si4O18(OH)2, was determined at highoxygen fugacities by high-pressure bracketing runs on eightpossible breakdown reactions involving the phases chlorite,kyanite, talc, staurolite, pyrope, enstatite, boron-free kornerupine,cordierite, quartz, and invariably an excess of hematite. Yoderitewas found to be stable over the surprisingly large PT rangefrom 6 to 25 kbar water pressure and 590 to 795 C. It is thusa high-pressure mineral covering the upper amphibolite and portionsof the eclogite facies. In the presence of quartz its upperpressure stability is reduced to some 15 kbar, and its uppertemperature stability to 715 C. Two of the yoderite-producingreactions are anomalous as they show dehydration in the directiontowards lower temperatures. Importantly, this is also true forthe reaction kyanite + talc + hematite+H2O=yoderite+quartz whichis responsible for the only yoderite occurrence in nature atMautia Hill, Tanzania. Preliminary thermodynamic calculationsindicate that—owing to this unusual dehydration behavior—thestability field for the assemblage yoderite+quartz disappearsfor water activities lower than 0.5. The rarity of yoderitein natural rocks, which is in contrast to its large PT stabilityfield, must be explained on chemical rather than on physicalgrounds. Yoderite can only occur in whiteschist-type bulk compositionsrich in MgO, Al2O3, SiO2, and containing some iron, but poorin alkalis and CaO. Oxygen fugacities must be unusually highto keep Fe trivalent, and—at least for rocks with excessquartz—the water activity must be high as well. In anenvironment of this kind, yoderite formation in the Mautia Hillwhiteschist may have occurred even at constant total pressureand temperature simply by an influx of hydrous fluid duringthe late stages of metamorphism under amphibolite facies conditions.  相似文献   

18.
Diffusion-controlled growth rates of polycrystalline enstatite reaction rims between forsterite and quartz were determined at 1,000 °C and 1 GPa in presence of traces of water. Iron-free, pure synthetic forsterite with normal oxygen and silicon isotopic compositions and quartz extremely enriched in 18O and 29Si were used as reactants. The relative mobility of 18O and 29Si in reactants and rims were determined by SIMS step scanning. The morphology of the rim shows that enstatite grows by a direct replacement of forsterite. Rim growth is modelled within a mass-conserving reference frame that implies advancement of reaction fronts from the initial forsterite-quartz interface in both directions. The isotopic compositions at the two reaction interfaces are controlled by the partial reactions Mg2SiO4=0.5 Mg2Si2O6+MgO at the forsterite-enstatite, and MgO+SiO2=0.5 Mg2Si2O6 at the enstatite-quartz interface, implying that grain boundary diffusion of MgO is rate-controlling. Isotopic profiles show no silicon exchange across the propagating reaction interfaces. This propagation, controlled by MgO diffusion, is faster than the homogenisation of Si by self-diffusion behind the advancing fronts. From this, and using % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamiramaaDa % aaleaacaWGtbGaamyAaiaacYcacaWGfbGaamOBaaqaaiaadAfacaWG % VbGaamiBaaaaaaa!3DD2! DSi,EnVolD_{Si,En}^{Vol} at dry conditions from the literature, results a % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGabmirayaafa % Waa0baaSqaaiaadofacaWGPbGaaiilaiaadweacaWGUbaabaaaaOGa % eqiTdqgaaa!3CCD! D￠Si,En dD'_{Si,En}^{} \delta value of 3᎒-24 m3 s-1 at 1,000 °C. The isotopic profiles for oxygen are more complex. They are interpreted as an interplay between the propagation of the interfaces, the homogenisation of the isotope concentrations by grain boundary self-diffusion of O within the rim, and the isotope exchange across the enstatite-quartz interface, which was open to 18O influx from quartz. Because of overlapping diffusion processes, boundary conditions are unstable and D´Ox,En' cannot be quantified. Using measured rim growth rates, the grain boundary diffusivity D´MgO' of MgO in iron-free enstatite is 8᎒-22 m3 s-1 at 1,000 °C and 1 GPa. Experiments with San Carlos olivine (fo92) as reactant reveal lower rates by a factor of about 4. Our results show that isotope tracers in rim growth experiments allow identification of the actual interface reactions, recognition of the rate-controlling component and further calculation of D´' values for specific components.  相似文献   

19.
Anomalous geogenic arsenic occurs in drinking water from the Goose River crystalline ground-watershed in mid-coastal Maine. Isotope investigations were useful in understanding release areas of arsenic into affected water wells. The isotope composition of sulfate associated with probable arsenian pyrite oxidation is described. Correlation of '18OSO4 enrichment [+4.57 to +7.46‰ Vienna Standard Mean Ocean Water (VSMOW)] is discussed with specific and recurring areas of elevated arsenic (10-52 µg l-1). Although arsenic concentrations were highly variable over 2 years per well, '18OSO4 values were always consistent and suggested a specific and consistent risk for elevated arsenic occurrences for each well. The '18O values in the water molecule (-12.07 to -8.81‰ VSMOW) and the '18OSO4 values may serve as prospective indicators of prominent zones of aeration at depth in discrete fracture zones. The '18O values in the water molecule and sulfate ion appear to indicate that more than 60% of O2 incorporated into the SO42- ion are from dissolved oxygen and belong to distinct fractured areas. These aeration zones or oxidation fronts, as outlined by oxygen isotopes, are sentinels for high arsenic risk in groundwater.  相似文献   

20.
Volume diffusion rates for five rare earth elements (La, Ce, Nd, Dy, and Yb) have been measured in single crystals of natural diopside at pressures of 0.1 MPa to 2.5 GPa and temperatures of 1,050 to1,450 °C. Polished, pre-annealed crystals were coated with a thin film of rare earth element oxides, then held at constant temperature and pressure for times ranging from 20 to 882 h. Diffusion profiles in quenched samples were measured by SIMS (secondary ion mass spectrometry) depth profiling. At 1 atm pressure, with the oxygen fugacity controlled near the quartz-fayalite-magnetite buffer, the following Arrhenius relations were obtained for diffusion normal to (001) (diffusion coefficient D in m2/s): log10DYb=(-4.64ǂ.42)-(411ᆠ kJ/mol/2.303RT); log10DDy=(-3.31ǃ.44)-(461ᆽ kJ/mol/2.303RT); log10DNd=(-2.95DŽ.64)-(496ᇡ kJ/mol/2.303RT); log10DCe=(-4.10ǃ.08)-(463ᆳ kJ/mol/2.303RT); log10DLu=(-4.22DŽ.66)-(466ᇢ kJ/mol/2.303RT). Diffusion rates decrease significantly with increasing ionic radius, with La a factor of ~35 slower than Yb. The relationship between diffusivity and ionic radius is consistent with a model in which elastic strain plays a critical role in governing the motion of an ion through the crystal lattice. Activation volumes for Yb and Ce diffusion, at constant temperature and oxygen fugacity, are 9.0DŽ.0 cm3/mol and 8.9Dž.2 cm3/mol, respectively, corresponding to an order of magnitude decrease in diffusivity as pressure is increased from 0 to 3 GPa at 1,200 °C. Diffusion of Nd is such that grain-scale isotopic equilibrium in the mantle can be achieved in ~1 My under conditions near the peridotite solidus (~1,450 °C at 2.5 GPa). The equilibration time is much longer under P, T conditions of the lithospheric mantle or at the eclogite solidus (~1 Gy at 1.5 GPa and 1,150 °C). Because of the relatively strong decrease in diffusivity with pressure (two orders of magnitude between 2.5 and 15 GPa along an adiabatic temperature gradient), Nd transport in clinopyroxene will be effectively frozen at pressures approaching the transition zone, on time scales less than 100 My. Rare earth element diffusion rates are slow enough that significant disequilibrium uptake of REE by growing clinopyroxene phenocrysts may be preserved under natural conditions of basalt crystallization. The relative abundances and spatial distributions of REE in such crystals may provide a sensitive record of the cooling and crystallization history of the host lava.  相似文献   

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