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1.
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   

2.
Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al2O3–SiO2 and subsystem CaO–MgO–SiO2. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al2O3–SiO2 and subsystem CaO–MgO–SiO2. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg2Si2O6) and ferrosilite (Fe2Si2O6). Calculated solution energies show that R2+ cations are more soluble in Opx than R3+ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R3+ cations by coupled substitution with Li+ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r 0, maximum partition coefficients D 0, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r 0 values for R3+ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r 0 = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r 0 values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.  相似文献   

3.
Diffusion profiles in minerals are increasingly used to determine the duration of geological events. For this purpose, the distinction between growth and diffusion zoning is critical; it requires the understanding of complex features associated with multicomponent diffusion. Seed-overgrowth interdiffusion experiments carried out in the range 1,050–1,250°C at 1.3 GPa have been designed to quantify and better understand Fe–Mg–Ca interdiffusion in garnet. Some of the diffusion profiles measured by analytical transmission electron microscope show characteristic features of multicomponent diffusion such as uphill diffusion, chemical solitary waves, zero-flux planes and complex diffusion paths. We implemented three different methods to calculate the interdiffusion coefficients of the D matrix from the experimental penetration curves and determined that with Ca as the dependent component, the crossed coefficients of the D matrix are negative. Experiments and numerical simulations indicate that: (1) uphill diffusion in garnet can be observed indifferently on the three components Fe, Mg and Ca, (2) it takes the form of complementary depletion/repletion waves and (3) chemical waves occur preferentially on initially flat concentration profiles. Derived D matrices are used to simulate the fate of chemical waves in time, in finite crystals. These examples show that the flow of atoms in multicomponent systems is not necessarily unidirectional for all components; it can change both in space along the diffusion profile and in time. Moving zero-flux planes in finite crystals are transitory features that allow flux reversals of atoms in the diffusion zone. Interdiffusion coefficients of the D matrices are also analyzed in terms of eigenvalues and eigenvectors. This analysis and the experimental results show that depending on the composition of the diffusion couple, (1) the shape of chemical waves and diffusion paths changes; (2) the width of the diffusion zone for each component may or may not be identical; and (3) the width of diffusion calculated at a given D and duration may greatly vary. D matrices were retrieved from thirteen sets of diffusion profiles. Data were cast in Arrhenius relations. Linear regressions of the data yield activation energies equal to 368, 148, 394, 152 kJ mol−1 at 1 bar and frequency factors Do equal to 2.37 × 10−6, −4.46 × 10−16, −1.31 × 10−5, 9.85 × 10−15 m2 s−1 for [(D)\tilde]FeFeCa \tilde{D}_{FeFe}^{Ca} , [(D)\tilde]FeMgCa \tilde{D}_{FeMg}^{Ca} , [(D)\tilde]MgFeCa \tilde{D}_{MgFe}^{Ca} , [(D)\tilde]MgMgCa \tilde{D}_{MgMg}^{Ca} , respectively. These values can be used to calculate interdiffusion coefficients in Fe–Mg–Ca garnets and determine the duration of geological events in high temperature metamorphic or magmatic garnets.  相似文献   

4.
Regularly oriented orthopyroxene (opx) and forsterite (fo) inclusions occur as opx + rutile (rt) or fo + rt inclusion domains in garnet (grt) from Otrøy peridotite. Electron diffraction characterization shows that forsterite inclusions do not have any specific crystallographic orientation relationships (COR) with the garnet host. In contrast, orthopyroxene inclusions have two sets of COR, that is, COR‐I: <111>grt//<001>opx and {110}grt～//～{100}opx (～13° off) and COR‐II: <111>grt//<011>opx and {110}grt～//～{100}opx (～14° off), in four garnet grains analysed. Both variants of orthopyroxene have a blade‐like habit with one pair of broad crystal faces parallel/sub‐parallel to {110}grt plane and the long axis of the crystal, <001>opx for COR‐I and <011>opx for COR‐II, along <111>grt direction. Whereas the lack of specific COR between forsterite and garnet, along with the presence of abundant infiltrating trails/veinlets decorated by fo + rt at garnet edges, provide compelling evidence for the formation of forsterite inclusions in garnet through the sequential cleaving–infiltrating–precipitating–healing process at low temperatures, the origin of the epitaxial orthopyroxene inclusions in garnet is not so obvious. In this connection, the reported COR, the crystal habit and the crystal growth energetics of the exsolved orthopyroxene in relict majoritic garnet were reviewed/clarified. The exsolved orthopyroxene in a relict majoritic garnet follows COR‐III: {112}grt//{100}opx and <111>grt//<001>opx. Based on the detailed trace analysis on published SEM images, these exsolved orthopyroxene inclusions are shown to have the crystal habit with one pair of broad crystal faces parallel to {112}grt//{100}opx and the long crystal axis along <111>grt//<001>opx. Such a crystal habit can be rationalized by the differences in oxygen sub‐lattices of both structures and represents the energetically favoured crystal shape of orthopyroxene inclusions in garnet formed by solid‐state exsolution mechanism. Considering the very different COR, crystal habit, as well as crystal growth direction, the orthopyroxene inclusions in garnet of the present sample most likely had been formed by mechanism(s) other than solid‐state exsolution, regardless of their regularly oriented appearance in garnet and the COR specification between orthopyroxene and garnet. In fact, the crystallographic characteristics of orthopyroxene and the similar chemical compositions of garnet at opx + rt inclusion domains, fo + rt inclusion domains/trails and garnet rim suggest that the orthopyroxene inclusions in the garnet are most likely formed by similar cleaving‐infiltration process as forsterite inclusions, though probably at an earlier stage of metamorphism. This work demonstrates that the oriented inclusions in host minerals, with or without specific COR, can arise from mechanism(s) other than solid‐state exsolution. Caution is thus needed in the interpretation of such COR, so that an erroneous identification of exhumation from UHP depths would not be made.  相似文献   

5.
The system Ca2Al3Si3O11(O/OH)-Ca2Al2FeSi3O11(O/OH), with emphasis on the Al-rich portion, was investigated by synthesis experiments at 0.5 and 2.0 GPa, 500-800 °C, using the technique of producing overgrowths on natural seed crystals. Electron microprobe analyses of overgrowths up to >100 µm wide have located the phase transition from clinozoisite to zoisite as a function of P-T-Xps and a miscibility gap in the clinozoisite solid solution. The experiments confirm a narrow, steep zoisite-clinozoisite two-phase loop in T-Xps section. Maximum and minimum iron contents in coexisting zoisite and clinozoisite are given by Xpszo (max) = 1.9*10 - 4 T+ 3.1*10 - 2 P - 5.36*10 - 2{\rm X}_{{\rm ps}}^{{\rm zo}} {\rm (max) = 1}{\rm .9*10}^{ - 4} T{\rm + 3}{\rm .1*10}^{ - 2} P - {\rm 5}{\rm .36*10}^{ - 2} and Xpsczo (min) = (4.6 * 10 - 4 - 4 * 10 - 5 P)T + 3.82 * 10 - 2 P - 8.76 * 10 - 2{\rm X}_{{\rm ps}}^{{\rm czo}} {\rm (min)} = {\rm (4}{\rm .6} * {\rm 10}^{ - {\rm 4}} - 4 * {\rm 10}^{ - {\rm 5}} P{\rm )}T + {\rm 3}{\rm .82} * {\rm 10}^{ - {\rm 2}} P - {\rm 8}{\rm .76} * {\rm 10}^{ - {\rm 2}} (P in GPa, T in °C). The iron-free end member reaction clinozoisite = zoisite has equilibrium temperatures of 185ᇆ °C at 0.5 GPa and 0ᇆ °C at 2.0 GPa, with (Hr0=2.8ǃ.3 kJ/mol and (Sr0=4.5ǃ.4 J/mol2K. At 0.5 GPa, two clinozoisite modifications exist, which have compositions of clinozoisite I ~0.15 to 0.25 Xps and clinozoisite II >0.55 Xps. The upper thermal stability of clinozoisite I at 0.5 GPa lies slightly above 600 °C, whereas Fe-rich clinozoisite II is stable at 650 °C. The schematic phase relations between epidote minerals, grossular-andradite solid solutions and other phases in the system CaO-Al2O3-Fe2O3-SiO2-H2O are shown.  相似文献   

6.
Diffusion of Zr and zircon solubility in hydrous, containing approximately 4.5 wt% H2O, metaluminous granitic melts with halogens, either 0.35 wt% Cl (LCl) or 1.2 wt% F (MRF), and in a halogen-free melt (LCO) were measured at 1.0 GPa and temperatures between 1,050 and 1,400 °C in a piston-cylinder apparatus using the zircon dissolution technique. Arrhenius equations for Zr diffusion in each hydrous melt composition are, for LCO with 4.4ǂ.4 wt% H2O: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacqWGebarcqGH9aqpcq % aIYaGmcqGGUaGlcqaI4aaocqaI4aaocqGHXcqScqaIWaamcqGGUaGl % cqaIWaamcqaIZaWmcqWG4baEcqaIXaqmcqaIWaamdaahaaWcbeqaai % abgkHiTiabiIda4aaakiGbcwgaLjabcIha4jabcchaWnaabmaabaWa % aSaaaeaacqGHsislcqaIXaqmcqaI0aancqaIWaamcqGGUaGlcqaIXa % qmcqGHXcqScqaIZaWmcqaIZaWmcqGGUaGlcqaI5aqoaeaacqWGsbGu % cqWGubavaaaacaGLOaGaayzkaaaaaa!571F! D = 2.88 ±0.03x10 - 8 exp( [( - 140.1 ±33.9)/(RT)] )D = 2.88 \pm 0.03x10^{ - 8} \exp \left( {{{ - 140.1 \pm 33.9} \over {RT}}} \right) , for LCl with 4.5ǂ.5 wt% H2O: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacqWGebarcqGH9aqpcq % aIYaGmcqGGUaGlcqaIZaWmcqaIZaWmcqGHXcqScqaIWaamcqGGUaGl % cqaIWaamcqaI1aqncqWG4baEcqaIXaqmcqaIWaamdaahaaWcbeqaai % abgkHiTiabisda0aaakiGbcwgaLjabcIha4jabcchaWnaabmaabaWa % aSaaaeaacqGHsislcqaIYaGmcqaI1aqncqaI0aancqGGUaGlcqaI4a % aocqGHXcqScqaI2aGncqaI0aancqGGUaGlcqaIXaqmaeaacqWGsbGu % cqWGubavaaaacaGLOaGaayzkaaaaaa!5719! D = 2.33 ±0.05x10 - 4 exp( [( - 254.8 ±64.1)/(RT)] )D = 2.33 \pm 0.05x10^{ - 4} \exp \left( {{{ - 254.8 \pm 64.1} \over {RT}}} \right) and for MRF with 4.9ǂ.3 wt% H2O: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacqWGebarcqGH9aqpcq % aIYaGmcqGGUaGlcqaI1aqncqaI0aancqGHXcqScqaIWaamcqGGUaGl % cqaIWaamcqaIZaWmcqWG4baEcqaIXaqmcqaIWaamdaahaaWcbeqaai % abgkHiTiabiwda1aaakiGbcwgaLjabcIha4jabcchaWnaabmaabaWa % aSaaaeaacqGHsislcqaIYaGmcqaIYaGmcqaIZaWmcqGGUaGlcqaI4a % aocqGHXcqScqaIXaqmcqaI1aqncqGGUaGlcqaI1aqnaeaacqWGsbGu % cqWGubavaaaacaGLOaGaayzkaaaaaa!5715! D = 2.54 ±0.03x10 - 5 exp( [( - 223.8 ±15.5)/(RT)] )D = 2.54 \pm 0.03x10^{ - 5} \exp \left( {{{ - 223.8 \pm 15.5} \over {RT}}} \right) . Solubilities determined by the dissolution technique were reversed for LCO +4.5ǂ.5 wt% H2O by crystallization of a Zr-enriched glass of LCO composition at 1,200 and 1,050 °C at 1.0 GPa. The solubility data were used to calculate partition coefficients of Zr between zircon and hydrous melt, which are given by the following expressions: for LCO % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacyGGSbaBcqGGUbGBcq % WGebardaqhaaWcbaGaemOwaOLaemOCaihabaGaemOEaONaemyAaKMa % emOCaiNaem4yamMaem4Ba8MaemOBa4Maei4la8IaemyBa0Maemyzau % MaemiBaWMaemiDaqhaaOGaeyypa0JaeGymaeJaeiOla4IaeGOnayJa % eG4mamZaaeWaaeaadaWcaaqaaiabigdaXiabicdaWiabicdaWiabic % daWiabicdaWaqaaiabdsfaubaaaiaawIcacaGLPaaacqGHsislcqaI % 1aqncqGGUaGlcqaI4aaocqaI3aWnaaa!5924! lnDZrzircon/melt = 1.63( [10000/(T)] ) - 5.87\ln D_{Zr}^{zircon/melt} = 1.63\left( {{{10000} \over T}} \right) - 5.87 , for LCl % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacyGGSbaBcqGGUbGBcq % WGebardaqhaaWcbaGaemOwaOLaemOCaihabaGaemOEaONaemyAaKMa % emOCaiNaem4yamMaem4Ba8MaemOBa4Maei4la8IaemyBa0Maemyzau % MaemiBaWMaemiDaqhaaOGaeyypa0JaeGymaeJaeiOla4IaeGinaqJa % eG4naCZaaeWaaeaadaWcaaqaaiabigdaXiabicdaWiabicdaWiabic % daWiabicdaWaqaaiabdsfaubaaaiaawIcacaGLPaaacqGHsislcqaI % 0aancqGGUaGlcqaI3aWncqaI1aqnaaa!5920! lnDZrzircon/melt = 1.47( [10000/(T)] ) - 4.75\ln D_{Zr}^{zircon/melt} = 1.47\left( {{{10000} \over T}} \right) - 4.75 and, for MRF by % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacyGGSbaBcqGGUbGBcq % WGebardaqhaaWcbaGaemOwaOLaemOCaihabaGaemOEaONaemyAaKMa % emOCaiNaem4yamMaem4Ba8MaemOBa4Maei4la8IaemyBa0Maemyzau % MaemiBaWMaemiDaqhaaOGaeyypa0JaeGymaeJaeiOla4IaeGinaqJa % eG4naCZaaeWaaeaadaWcaaqaaiabigdaXiabicdaWiabicdaWiabic % daWiabicdaWaqaaiabdsfaubaaaiaawIcacaGLPaaacqGHsislcqaI % 0aancqGGUaGlcqaI5aqocqaIXaqmaaa!591C! lnDZrzircon/melt = 1.47( [10000/(T)] ) - 4.91\ln D_{Zr}^{zircon/melt} = 1.47\left( {{{10000} \over T}} \right) - 4.91 . Experiments on the same compositions, but with water contents down to 0.5 wt%, demonstrated reductions in both the diffusion coefficient of Zr and zircon solubility in the melt. The addition of halogens at the concentration levels studied to metaluminous melts has a small effect on either the diffusion of Zr in the melt, or the solubility of zircon at all water concentrations and temperatures investigated. At 800 °C, the calculated diffusion coefficient of Zr is lowest in LCl, 9᎒-17 m2 s-1, and is highest in LCO, 4᎒-15 m2 s-1. Extrapolation of the halogen-free solubility data to a magmatic temperature of 800 °C yields solubilities of approximately one-third of those directly measured in similar compositions, predicted by earlier studies of zircon dissolution and based upon analyses of natural rocks. This discrepancy is attributed to the higher oxygen fugacity of the experiments of this study compared with previous studies and nature, and the effect of oxygen fugacity on the structural role of iron in the melt, which, in turn, affects zircon solubility, but does not significantly affect Zr diffusion.  相似文献   

7.
The partitioning of Mg and Fe2+ between coexisting olivines and orthopyroxenes in the system MgO-FeO-SiO2 has been investigated experimentally at 1173, 1273, 1423 K and 1.6 GPa over the whole range of Mg/Fe ratios. The use of barium borosilicate as a flux to promote grain growth, and the identification by back-scattered electron imaging of resulting growth rims suitable for analysis by electron microprobe, results in coexisting olivine and orthopyroxenene compositions determined to a precision of±0.003 to 0.004 in molar Fe/(Mg+Fe). Quasi-reversal experiments were performed starting with Mg-rich olivine and Fe-rich orthopyroxene (low KD) and vice versa (high KD), which produced indistinguishable results. The distribution coefficient, KD, depends on composition and on temperature, but near Fe/(Mg+Fe)=0.1 (i.e. mantle compositions) these effects cancel out, and KD is insensitive to temperature. The results agree well with previous experimental investigations, and constrain the thermodynamic mixing properties of Mg-Fe olivine solid solutions to show small near-symmetric deviations from ideality, with between 2000 and 8000 J/mol. Multiple non-linear least squares regression of all data gave a best fit with (implying 5450 J/mol at 1 bar) and , but the two W G parameters are so highly correlated with each other that our data are almost equally well fit with , as obtained by Wiser and Wood. This value implies , apparently independent of temperature. Our experimental results are not compatible with the assessment of olivine-orthopyroxene equilibria of Sack and Ghiorso.  相似文献   

8.
Calorimetric and experimental data on AlF-bearing titanite are presented that yield thermodynamic properties of CaAlFSiO4, as well as activity-composition relations of binary titanite CaTiOSiO4-CaAlFSiO4. The heat capacity of synthetic CaAlFSiO4 was measured with differential scanning calorimetry between 170 and 850 K: CP=689.96-0.38647T+2911300T-2-8356.1T-0.5+0.00016179T2 Based on low-temperature heat capacity calculations with lattice vibrational theory (Debye model), the calorimetric entropy of CaAlFSiO4 can be expected to lie between 104.7 and 118.1 J mol-1 K-1. The temperature of the P21/a to A2/a phase change was determined calorimetrically for a titanite with XAl=0.09 (Ttransition=390 K). The decrease of the transition temperature at a rate of about 11 K per mol% CaAlFSiO4 is in good agreement with previous TEM investigations. The displacement of the reaction anorthite + fluorite = CaAlFSiO4 in the presence of CaTiOSiO4 was studied with high P-T experiments. Titanite behaves as a non-ideal, symmetrical solid-solution. The thermodynamic properties of CaAlFSiO4 consistent with a multi-site mixing model are: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBam % XvP5wqSXMqHnxAJn0BKvguHDwzZbqegm0B1jxALjhiov2Daebbnrfi % fHhDYfgasaacH8srps0lbbf9q8WrFfeuY-Hhbbf9v8qqaqFr0xc9pk % 0xbba9q8WqFfea0-yr0RYxir-Jbba9q8aq0-yq-He9q8qqQ8frFve9 % Fve9Ff0dmeaabaqaciaacaGaaeqabaWaaeaaeaaakeaafaqaaiWaca % aabaGaeeyrauKaeeOBa4MaeeiDaqNaeeiAaGMaeeyyaeMaeeiBaWMa % eeiCaaNaeeyEaKNaeeiiaaIaee4Ba8MaeeOzayMaeeiiaaIaeeOzay % Maee4Ba8MaeeOCaiNaeeyBa0MaeeyyaeMaeeiDaqNaeeyAaKMaee4B % a8MaeeOBa4MaeeiiaaIaeeikaGIaeeyzauMaeeiBaWMaeeyzauMaee % yBa0MaeeyzauMaeeOBa4MaeeiDaqNaee4CamNaeeykaKIaeeiiaaIa % emizaq2aaSbaaSqaaiabdAgaMbqabaGccqWGibasdaahaaWcbeqaai % abicdaWaaaaOqaaiabg2da9iabgkHiTiabikdaYiabiEda3iabisda % 0iabicdaWiabc6caUiabiIda4iabgglaXkabiodaZiabc6caUiabic % daWiabbccaGiabbUgaRjabbQeakjabb2gaTjabb+gaVjabbYgaSnaa % CaaaleqabaGaeyOeI0IaeGymaedaaaGcbaGaee4uamLaeeiDaqNaee % yyaeMaeeOBa4MaeeizaqMaeeyyaeMaeeOCaiNaeeizaqMaeeiiaaIa % ee4CamNaeeiDaqNaeeyyaeMaeeiDaqNaeeyzauMaeeiiaaIaeeyzau % MaeeOBa4MaeeiDaqNaeeOCaiNaee4Ba8MaeeiCaaNaeeyEaKNaeeii % aaIaee4uam1aaWbaaSqabeaacqqGWaamaaaakeaacqqG9aqpcqqGXa % qmcqqGWaamcqqG0aancqqGUaGlcqqG5aqocqGHXcqScqqGXaqmcqqG % UaGlcqqGXaqmcqqGGaaicqqGkbGscqqGTbqBcqqGVbWBcqqGSbaBda % ahaaWcbeqaaiabgkHiTiabigdaXaaakiabbUealnaaCaaaleqabaGa % eyOeI0IaeGymaedaaaGcbaGaeeyta0KaeeyyaeMaeeOCaiNaee4zaC % MaeeyDauNaeeiBaWMaeeyzauMaee4CamNaeeiiaaIaeeiCaaNaeeyy % aeMaeeOCaiNaeeyyaeMaeeyBa0MaeeyzauMaeeiDaqNaeeyzauMaee % OCaiNaeeiiaaYaamWaaeaacqWGxbWvdaWgaaWcbaGaemisaG0aaWba % aWqabeaacqGHsislaaaaleqaaOGaeeivaqLaem4vaC1aaSbaaSqaai % abdohaZbqabaaakiaawUfacaGLDbaaaeaacqGH9aqpcqaIXaqmcqaI % ZaWmcqGGUaGlcqaI2aGncqGHXcqScqaIWaamcqGGUaGlcqaI0aanca % aMe8UaeeOsaOKaeeyBa0Maee4Ba8MaeeiBaW2aaWbaaSqabeaacqGH % sislcqaIXaqmaaaaaaaa!E403!
Enthalpy of formation (elements) df H0
amp; = - 2740.8 ±3.0kJmol - 1
Standard state entropy S0
amp; = 104.9 ±1.1 Jmol - 1 K - 1
WV) was determined from the excess volume of mixing based on XRD measurements (214ᆦ J mol-1 kbar-1), as well as refined from the piston-cylinder experimental results (198뀺 J mol-1 kbar-1), demonstrating consistency between crystal structure data and thermodynamic properties. The stability of AlF-bearing titanite Ca(Ti,Al)(O,F)SiO4 was investigated by thermodynamic modelling in the system Ca-Al-Si-Ti-O-F-H-C and subsystems. The petrogenetic grids are in good agreement with natural mineral assemblages, in that very Al-rich titanite (XAl>0.65ǂ.15) is generally absent because it is either unstable with respect to other phases, or its stability field lies outside the P-T conditions realised on Earth. The grids explain both the predominant occurrence of natural Al-rich titanite at high metamorphic grade such as eclogite facies conditions, as well as its scarcity in blueschist facies rocks. Wide spacing of the Al-isopleths for titanite of many high-grade assemblages prevents their use as geobarometers or thermometers. The instability of end-member CaAlFSiO4 with respect to other phases in most assemblages modelled here is consistent with the hypothesis that the presence of structural stresses in the crystal lattice of CaAlFSiO4 influences its thermodynamic stability. The titanite structure is not well suited to accommodate Al and F instead of Ti and O, causing the relatively high Gibbs free energy of CaAlFSiO4, manifested in its standard state properties. Thus, the increasing amount of CaAlFSiO4 along the binary join is the reason why titanite with XAl>0.65ǂ.15 becomes unstable in most petrogenetic grids presented here. The compositional limit of natural titanite (XAlƸ.54) probably reflects the point beyond which the less stable end member begins to dominate the solid-solution, affecting both crystal structure and thermodynamic stability.  相似文献   

9.
Rare earth element diffusion in a natural pyrope single crystal at 2.8 GPa   总被引：1，自引：0，他引：1  
Volume diffusion rates of Ce, Sm, Dy, and Yb have been measured in a natural pyrope-rich garnet single crystal (Py71Alm16Gr13) at a pressure of 2.8 GPa and temperatures of 1,200-1,450 °C. Pieces of a single gem-quality pyrope megacryst were polished, coated with a thin layer of polycrystalline REE oxide, then annealed in a piston cylinder device for times between 2.6 and 90 h. Diffusion profiles in the annealed samples were measured by SIMS depth profiling. The dependence of diffusion rates on temperature can be described by the following Arrhenius equations (diffusion coefficients in m2/s): % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBam % XvP5wqSXMqHnxAJn0BKvguHDwzZbqegm0B1jxALjhiov2DaeHbuLwB % Lnhiov2DGi1BTfMBaebbfv3ySLgzGueE0jxyaibaieYlf9irVeeu0d % Xdh9vqqj-hEeeu0xXdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9 % pgea0dXdar-Jb9hs0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaaca % qabeaadaabauaaaOqaauaabeqaeeaaaaqaaiGbcYgaSjabc+gaVjab % cEgaNnaaBaaaleaacqaIXaqmcqaIWaamaeqaaOGaemiraq0aaSbaaS % qaaiabbMfazjabbkgaIbqabaGccqGH9aqpcqGGOaakcqGHsislcqaI % 3aWncqGGUaGlcqaI3aWncqaIZaWmcqGHXcqScqaIWaamcqGGUaGlcq % aI5aqocqaI3aWncqGGPaqkcqGHsisldaqadaqaaiabiodaZiabisda % 0iabiodaZiabgglaXkabiodaZiabicdaWiaaysW7cqqGRbWAcqqGkb % GscaaMe8UaeeyBa0Maee4Ba8MaeeiBaW2aaWbaaSqabeaacqqGTaql % cqqGXaqmaaGccqGGVaWlcqaIYaGmcqGGUaGlcqaIZaWmcqaIWaamcq % aIZaWmcqWGsbGucqWGubavaiaawIcacaGLPaaaaeaacyGGSbaBcqGG % VbWBcqGGNbWzdaWgaaWcbaGaeGymaeJaeGimaadabeaakiabdseaen % aaBaaaleaacqqGebarcqqG5bqEaeqaaOGaeyypa0JaeiikaGIaeyOe % I0IaeGyoaKJaeiOla4IaeGimaaJaeGinaqJaeyySaeRaeGimaaJaei % Ola4IaeGyoaKJaeG4naCJaeiykaKIaeyOeI0YaaeWaaeaacqaIZaWm % cqaIWaamcqaIYaGmcqGHXcqScqaIZaWmcqaIWaamcaaMe8Uaee4AaS % MaeeOsaOKaaGjbVlabb2gaTjabb+gaVjabbYgaSnaaCaaaleqabaGa % eeyla0IaeeymaedaaOGaei4la8IaeGOmaiJaeiOla4IaeG4mamJaeG % imaaJaeG4mamJaemOuaiLaemivaqfacaGLOaGaayzkaaaabaGagiiB % aWMaei4Ba8Maei4zaC2aaSbaaSqaaiabigdaXiabicdaWaqabaGccq % WGebardaWgaaWcbaGaee4uamLaeeyBa0gabeaakiabg2da9iabcIca % OiabgkHiTiabiMda5iabc6caUiabikdaYiabigdaXiabgglaXkabic % daWiabc6caUiabiMda5iabiEda3iabcMcaPiabgkHiTmaabmaabaGa % eG4mamJaeGimaaJaeGimaaJaeyySaeRaeG4mamJaeGimaaJaaGjbVl % abbUgaRjabbQeakjaaysW7cqqGTbqBcqqGVbWBcqqGSbaBdaahaaWc % beqaaiabb2caTiabbgdaXaaakiabc+caViabikdaYiabc6caUiabio % daZiabicdaWiabiodaZiabdkfasjabdsfaubGaayjkaiaawMcaaaqa % aiGbcYgaSjabc+gaVjabcEgaNnaaBaaaleaacqaIXaqmcqaIWaamae % qaaOGaemiraq0aaSbaaSqaaiabboeadjabbwgaLbqabaGccqGH9aqp % cqGGOaakcqGHsislcqaI5aqocqGGUaGlcqaI3aWncqaI0aancqGHXc % qScqaIYaGmcqGGUaGlcqaI4aaocqaI0aancqGGPaqkcqGHsisldaqa % daqaaiabikdaYiabiIda4iabisda0iabgglaXkabiMda5iabigdaXi % aaysW7cqqGRbWAcqqGkbGscaaMe8UaeeyBa0Maee4Ba8MaeeiBaW2a % aWbaaSqabeaacqqGTaqlcqqGXaqmaaGccqGGVaWlcqaIYaGmcqGGUa % GlcqaIZaWmcqaIWaamcqaIZaWmcqWGsbGucqWGubavaiaawIcacaGL % Paaaaaaaaa!0C76!
Margules parameter [ WH- TWs ]
log10 DYb = ( - 7.73 ±0.97) - ( 343 ±30  kJ  mol- 1 /2.303RT )
log10 DDy = ( - 9.04 ±0.97) - ( 302 ±30  kJ  mol- 1 /2.303RT )
log10 DSm = ( - 9.21 ±0.97) - ( 300 ±30  kJ  mol- 1 /2.303RT )
log10 DCe = ( - 9.74 ±2.84) - ( 284 ±91 &nbs\matrix{ {\log _{10} D_{{\rm Yb}} = ( - 7.73 \pm 0.97) - \left( {343 \pm 30\;{\rm kJ}\;{\rm mol}^{{\rm - 1}} /2.303RT} \right)} \cr {\log _{10} D_{{\rm Dy}} = ( - 9.04 \pm 0.97) - \left( {302 \pm 30\;{\rm kJ}\;{\rm mol}^{{\rm - 1}} /2.303RT} \right)} \cr {\log _{10} D_{{\rm Sm}} = ( - 9.21 \pm 0.97) - \left( {300 \pm 30\;{\rm kJ}\;{\rm mol}^{{\rm - 1}} /2.303RT} \right)} \cr {\log _{10} D_{{\rm Ce}} = ( - 9.74 \pm 2.84) - \left( {284 \pm 91\;{\rm kJ}\;{\rm mol}^{{\rm - 1}} /2.303RT} \right)} \cr } . There is no significant influence of ionic radius on diffusion rates; at each temperature the diffusion coefficients for Ce, Sm, Dy, and Yb are indistinguishable from each other within the measurement uncertainty. However, comparison with other diffusion data suggests that there is a strong influence of ionic charge on diffusion rates in garnet, with REE3+ diffusion rates more than two orders of magnitude slower than divalent cation diffusion rates. This implies that the Sm-Nd isotopic chronometer may close at significantly higher temperatures than thermometers based on divalent cation exchange, such as the garnet-biotite thermometer. REE diffusion rates in pyrope are similar to Yb and Dy diffusion rates in diopside at temperatures near the solidus of garnet lherzolite (~1,450 °C at 2.8 GPa), and are an order of magnitude faster than Nd, Ce, and La in high-Ca pyroxene at these conditions. At lower temperatures relevant to the lithospheric mantle and crust, REE diffusion rates in garnet are much faster than in high-Ca pyroxene, and closure temperatures for Nd isotopes in slowly-cooled garnets are ~200 °C lower than in high-Ca pyroxene.  相似文献   

10.
We determined experimentally the Nernst distribution coefficient between orthopyroxene and anhydrous silicate melt for trace elements i in the system Na2O–CaO–MgO–Al2O3–SiO2 (NCMAS) along the dry model lherzolite solidus from 1.1 GPa/1,230°C up to 3.2 GPa/1,535°C in a piston cylinder apparatus. Major and trace element composition of melt and orthopyroxene were determined with a combination of electron microprobe and ion probe analyses. We provide partitioning data for trace elements Li, Be, B, K, Sc, Ti, V, Cr, Co, Ni, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Sm, Nd, Yb, Lu, Hf, Ta, Pb, U, and Th. The melts were chosen to be boninitic at 1.1 and 2.0 GPa, picritic at 2.3 GPa and komatiitic at 2.7 and 3.2 GPa. Orthopyroxene is Tschermakitic with 8 mol% Mg-Tschermaks MgAl[AlSiO6] at 1.1 GPa while at higher pressure it has 18–20 mol%. The rare earth elements show a continuous, significant increase in compatibility with decreasing ionic radius from D Laopx−melt ∼ 0.0008 to D Luopx−melt ∼ 0.15. For the high-field-strength elements compatibility increases from D Thopx−melt ∼ 0.001 through D Nbopx−melt ∼ 0.0015, D Uopx−melt ∼ 0.002, D Taopx−melt ∼ 0.005, D Zropx−melt ∼ 0.02 and D Hfopx−melt ∼ 0.04 to D Tiopx−melt ∼ 0.14. From mathematical and graphical fits we determined best-fit values for D 0M1, D 0M2, r 0M1, r 0M2, E 0M1, and E 0M2 for the two different M sites in orthopyroxene according to the lattice strain model and calculated the intracrystalline distribution between M1 and M2. Our data indicate extreme intracrystalline fractionation for most elements in orthopyroxene; for the divalent cations D i M2−M1 varies by three orders of magnitude between D CoM2−M1 = 0.00098–0.00919 and D BaM2−M1 = 2.3–28. Trivalent cations Al and Cr almost exclusively substitute on M1 while the other trivalent cations substitute on M2; D LaM2−M1 reaches extreme values between 6.5 × 107 and 1.4 × 1016. Tetravalent cations Ti, Hf, and Zr almost exclusively substitute on M1 while U and Th exclusively substitute on M2. Our new comprehensive data set can be used for polybaric-polythermal melting models along the Earth’s mantle solidus. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

11.
Oxygen diffusion in albite has been determined by the integrating (bulk 18O) method between 750° and 450° C, for a P H2O of 2 kb. The original material has a low dislocation density (<106 cm?2), and its lattice diffusion coefficient (D 1), given below, agrees well with previous determinations. A sample was deformed at high temperature and pressure to produce a uniform dislocation density of 5 × 109 cm?2. The diffusion coefficient (D a) for this deformed material, given below, is about 0.5 and 0.7 orders of magnitude larger than D 1 at 700° and 450° C, respectively. This enhancement is believed due to faster diffusion along the cores of dislocations. Assuming a dislocation core radius of 4 Å, the calculated pipe diffusion coefficient (D p), given below, is about 5 orders of magnitude larger than D 1. These results suggest that volume diffusion at metamorphic conditions may be only slightly enhanced by the presence of dislocations. $$\begin{gathered} D_1 = 9.8 \pm 6.9 \times 10^{ - 6} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 33.4 \pm 0.6(kcal/mole)/RT] \hfill \\ \end{gathered} $$ $$\begin{gathered} D_a = 7.6 \pm 4.0 \times 10^{ - 6} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 30.9 \pm 1.1(kcal/mole)/RT] \hfill \\ \end{gathered} $$ $$\begin{gathered} D_p \approx 1.2 \times 10^{ - 1} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 29.8(kcal/mole)/RT]. \hfill \\ \end{gathered} $$   相似文献   

12.
The enstatite-diopside solvus presents certain interesting thermodynamic and crystal-structural problems. The solvus may be considered as parts of two solvi one with the ortho-structure and the other with clino-structure. By assuming the standard free energy change for the two reactions (MgMgSi2O6)opx ? (MgMgSi2O6)cpx and (CaMgSi2O6) opx ? (CaMgSi2O6) cpx as 500 and 1 000 to 3 000 cal/mol respectively, it is possible to calculate the regular solution parameter W for orthopyroxene and clinopyroxene. These W's essentially refer to mixing on M2 sites. The expression for the equilibrium constant by assuming ideal mixing for Fe-Mg, Fe-Ca and non-ideal mixing for Ca-Mg on binary M1 and ternary M2 sites is given by 1 $$K_a = \frac{{X_{{\text{Mg - cpx}}}^{{\text{M1}}} X_{{\text{Mg - cpx}}}^{{\text{M2}}} \exp \left[ {\frac{{W_{{\text{cpx}}} }}{{RT}}\left\{ {X_{{\text{Ca - cpx}}}^{{\text{M2}}} \left( {X_{{\text{Ca - cpx}}}^{{\text{M2}}} + X_{{\text{Fe - cpx}}}^{{\text{M2}}} } \right)} \right\}} \right]}}{{X_{{\text{Mg - cpx}}}^{{\text{M1}}} X_{{\text{Mg - opx}}}^{{\text{M2}}} \exp \left[ {\frac{{W_{{\text{cpx}}} }}{{RT}}\left\{ {X_{{\text{Ca - opx}}}^{{\text{M2}}} \left( {X_{{\text{Ca - opx}}}^{{\text{M2}}} + X_{{\text{Fe - opx}}}^{{\text{M2}}} } \right)} \right\}} \right]}}$$ where X's are site occupancies, R is 1.987 and T is temperature in oK. Temperature of pyroxene crystallization may be estimated by substituting for T in the above equation until the equation ?RT In K a=500 is satisfied. The shortcomings of this method are the incomplete standard free energy data on the end member components and the absence of site occupancy data in pyroxenes at high temperatures. The assumed free energy data do, however, show the possible extent of inaccuracy in temperature estimates resulting from the neglect of Mg-Ca non ideality.  相似文献   

13.
The effect of temperature, pressure, and dissolved H2O in the melt on the Fe2+–Mg exchange coefficient between orthopyroxene and rhyolite melt was investigated with a series of H2O fluid-saturated phase-equilibrium experiments. Experiments were conducted in a rapid-quench cold-seal pressure vessel over a temperature and pressure range of 785–850 °C and 80–185 MPa, respectively. Oxygen fugacity was buffered with the solid Ni–NiO assemblage in a double-capsule assembly. These experiments, when combined with H2O-undersaturated experiments in the literature, show that \( ^{{{\text{Fe}}^{2 + } {-}{\text{Mg}}}} K_{\text{D}} \) between orthopyroxene and rhyolite liquid increases strongly (from 0.23 to 0.54) as a function of dissolved water in the melt (from 2.7 to 5.6 wt%). There is no detectable effect of temperature or pressure over an interval of 65 °C and 100 MPa, respectively, on the Fe2+–Mg exchange coefficient values. The data show that Fe-rich orthopyroxene is favored at high water contents, whereas Mg-rich orthopyroxene crystallizes at low water contents. It is proposed that the effect of dissolved water in the melt on the composition of orthopyroxene is analogous to its effect on the composition of plagioclase. In the latter case, dissolved hydroxyl groups preferentially complex with Na+ relative to Ca2+, which reduces the activity of the albite component, leading to a more anorthite-rich (calcic) plagioclase. Similarly, it is proposed that dissolved hydroxyl groups preferentially complex with Mg2+ relative to Fe2+, thus lowering the activity of the enstatite component, leading to a more Fe-rich orthopyroxene at high water contents in the melt. The experimental results presented in this study show that reversely zoned pyroxene (i.e., Mg-rich rims) in silicic magmas may be a result of H2O degassing and not necessarily the result of mixing with a more mafic magma.  相似文献   

14.
Li diffusion in zircon   总被引：2，自引：2，他引：0  
Diffusion of Li under anhydrous conditions at 1 atm and under fluid-present elevated pressure (1.0–1.2 GPa) conditions has been measured in natural zircon. The source of diffusant for 1-atm experiments was ground natural spodumene, which was sealed under vacuum in silica glass capsules with polished slabs of zircon. An experiment using a Dy-bearing source was also conducted to evaluate possible rate-limiting effects on Li diffusion of slow-diffusing REE+3 that might provide charge balance. Diffusion experiments performed in the presence of H2O–CO2 fluid were run in a piston–cylinder apparatus, using a source consisting of a powdered mixture of spodumene, quartz and zircon with oxalic acid added to produce H2O–CO2 fluid. Nuclear reaction analysis (NRA) with the resonant nuclear reaction 7Li(p,γ)8Be was used to measure diffusion profiles for the experiments. The following Arrhenius parameters were obtained for Li diffusion normal to the c-axis over the temperature range 703–1.151°C at 1 atm for experiments run with the spodumene source:
D\textLi = 7.17 ×10 - 7 exp( - 275 ±11 \textkJmol - 1 /\textRT)\textm2 \texts - 1. D_{\text{Li}} = 7.17 \times 10^{ - 7} { \exp }( - 275 \pm 11\,{\text{kJmol}}^{ - 1} /{\text{RT}}){\text{m}}^{2} {\text{s}}^{ - 1}.  相似文献   

15.
Geothermometric equations for spinel peridotites by Fujii (1976), Gasparik and Newton (1984), and Chatterjee, and Terhart (1985) based on the reaction enstatite (en)+spinel (sp)Mg–Tschermaks (mats)+forsterite (fo) were tested using a nearly isothermal suite of mantle xenoliths from the Eifel, West Germany. In spite of using activities of MgAl2O4, en, and mats to allow for the non-ideal solution behaviour of the constituent phases, temperatures calculated from these equations systematically change as a function of Cr/(Cr+AL+Fe3+) in spinel. We propose an improved version of the empirical geothermometer for spinel peridotites of Sachtleben and Seck (1981) derived from the evaluation of the solubilities of Ca and Al in orthopyroxene from more than 100 spinel peridotites from the Rhenish Volcanic Province. A least squares regression yielded a smooth correlation between
  相似文献   

16.
We have experimentally determined the partitioning of REE (rare earth elements) between zoisite and hydrous silicate melt at 1,100 °C and 3 GPa. All REE behave moderately compatible in zoisite with respect to the melt and all show a smooth parabolic dependence on ionic radius. The partitioning parabola peaks at Nd , and the compatibility slightly decreases towards La and decreases by half an order of magnitude towards Yb . Application of the elastic strain model of Blundy and Wood (1994) to the available zoisite and allanite REE mineral/melt partitioning data and comparison with partitioning pattern calculated from a combination of structural and physical data (taken from the literature) with the elastic strain model suggest that in zoisite REE prefer the A1-site and that only La and Ce are incorporated into the A2-site in significant amounts. In contrast, in allanite, all REE are preferentially incorporated into the large and highly co-ordinated A2 site. As a result, zoisite fractionates the MREE effectively from the HREE and moderately from the LREE, while allanite fractionates the LREE very effectively from the MREE and HREE. Consequently, the presence of either zoisite or allanite during slab melting will lead to quite different REE pattern in the produced melt.Editorial responsibility: J. Hoefs  相似文献   

17.
The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H2O t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H2O t ) and water-rich (~2 wt% H2O t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H2O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al2O3 with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:
where is the water diffusivity at 1 wt% H2O t in m2/s, T is the temperature in K and P is the pressure in MPa. The above equation reproduces the experimental data (14 runs in total) with a standard fit error of 0.15 log units. It can be employed to model degassing of peralkaline melts at water contents up to 2 wt%.  相似文献   

18.
The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H2O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H2O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because simpler systems do not account for enhanced hydrous melt stability and reduced H2O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline phases have maximal H2O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C, the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation C\textH2 \textO\textolivine ( \textppm ) = 57.6( ±16 ) ×P( \textGPa ) - 169( ±18 ). C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations of D\textH2 \textO\textpyx/olivine D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} from this study and estimates of D\textH2 \textO\textgt/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} , allows for estimation of peridotite H2O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm bulk H2O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues of subducted slabs, which contain 300–1,000 ppm bulk H2O, can exceed the peridotite H2O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values of D\textH2 \textO\textpyx/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H2O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence on viscosity and other transport properties.  相似文献   

19.
Experiments at high pressure and temperature indicate that excess Ca may be dissolved in diopside. If the (Ca, Mg)2Si2O6 clinopyroxene solution extends to more Ca-rich compositions than CaMgSi2O6, macroscopic regular solution models cannot strictly be applied to this system. A nonconvergent site-disorder model, such as that proposed by Thompson (1969, 1970), may be more appropriate. We have modified Thompson's model to include asymmetric excess parameters and have used a linear least-squares technique to fit the available experimental data for Ca-Mg orthopyroxene-clinopyroxene equilibria and Fe-free pigeonite stability to this model. The model expressions for equilibrium conditions \(\mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction A) and \(\mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction B) are given by: 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Mg}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ W_{21} [2(X_{{\text{Ca}}}^{{\text{M2}}} )^3 - (X_{{\text{Ca}}}^{{\text{M2}}} ] \hfill \\ {\text{ + 2W}}_{{\text{22}}} [X_{{\text{Ca}}}^{{\text{M2}}} )^2 - (X_{{\text{Ca}}}^{{\text{M2}}} )^3 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{Wo}}}^{{\text{opx}}} )^2 \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Ca}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ 2W_{21} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^2 - (X_{{\text{Mg}}}^{{\text{M2}}} )^3 ] \hfill \\ {\text{ + W}}_{{\text{22}}} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^3 - (X_{{\text{Mg}}}^{{\text{M2}}} )^2 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{En}}}^{{\text{opx}}} )^2 \hfill \\ \hfill \\ \end{gathered} $$ where 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = 2.953 + 0.0602{\text{P}} - 0.00179{\text{T}} \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = 24.64 + 0.958{\text{P}} - (0.0286){\text{T}} \hfill \\ {\text{W}}_{{\text{21}}} = 47.12 + 0.273{\text{P}} \hfill \\ {\text{W}}_{{\text{22}}} = 66.11 + ( - 0.249){\text{P}} \hfill \\ {\text{W}}^{{\text{opx}}} = 40 \hfill \\ \Delta {\text{G}}_*^0 = 155{\text{ (all values are in kJ/gfw)}}{\text{.}} \hfill \\ \end{gathered} $$ . Site occupancies in clinopyroxene were determined from the internal equilibrium condition 1 $$\begin{gathered} \Delta G_{\text{E}}^{\text{O}} = - {\text{RT 1n}}\left[ {\frac{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}{{X_{{\text{Ca}}}^{{\text{M2}}} \cdot X_{{\text{Mg}}}^{{\text{M1}}} }}} \right] + \tfrac{1}{2}[(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} )(2{\text{X}}_{{\text{Ca}}}^{{\text{M2}}} - 1) \hfill \\ {\text{ + }}\Delta G_*^0 (X_{{\text{Ca}}}^{{\text{M1}}} - X_{{\text{Ca}}}^{{\text{M2}}} ) + \tfrac{3}{2}(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} ) \hfill \\ {\text{ (1}} - 2X_{{\text{Ca}}}^{{\text{M1}}} )(X_{{\text{Ca}}}^{{\text{M1}}} + \tfrac{1}{2})] \hfill \\ \end{gathered} $$ where δG E 0 =153+0.023T+1.2P. The predicted concentrations of Ca on the clinopyroxene Ml site are low enough to be compatible with crystallographic studies. Temperatures calculated from the model for coexisting ortho- and clinopyroxene pairs fit the experimental data to within 10° in most cases; the worst discrepancy is 30°. Phase relations for clinopyroxene, orthopyroxene and pigeonite are successfully described by this model at temperatures up to 1,600° C and pressures from 0.001 to 40 kbar. Predicted enthalpies of solution agree well with the calorimetric measurements of Newton et al. (1979). The nonconvergent site disorder model affords good approximations to both the free energy and enthalpy of clinopyroxenes, and, therefore, the configurational entropy as well. This approach may provide an example for Febearing pyroxenes in which cation site exchange has an even more profound effect on the thermodynamic properties.  相似文献   

20.
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