Heat capacity and phase equilibria of wadeite-type K2Si4O9     

Wenjun Yong  E. Dachs  A. C. Withers  E. J. Essene 《Contributions to Mineralogy and Petrology》2008,155(2):137-146

The low-temperature heat capacity (C _p) of Si-wadeite (K₂Si₄O₉) synthesized with a piston cylinder device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system. The entropy of Si-wadeite at standard temperature and pressure calculated from the measured heat capacity data is 253.8 ± 0.6 J mol⁻¹ K⁻¹, which is considerably larger than some of the previous estimated values. The calculated phase transition boundaries in the system K₂O–Al₂O₃–SiO₂ are generally consistent with previous experimental results. Together with our calculated phase boundaries, seven multi-anvil experiments at 1,400 K and 6.0–7.7 GPa suggest that no equilibrium stability field of kalsilite + coesite intervenes between the stability field of sanidine and that of coesite + kyanite + Si-wadeite, in contrast to previous predictions. First-order approximations were undertaken to calculate the phase diagram in the system K₂Si₄O₉ at lower pressure and temperature. Large discrepancies were shown between the calculated diagram compared with previously published versions, suggesting that further experimental or/and calorimetric work is needed to better constrain the low-pressure phase relations of the K₂Si₄O₉ polymorphs. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

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

Jodie L. Hayob  Steven R. Bohlen  Eric J. Essene 《Contributions to Mineralogy and Petrology》1993,115(1):18-35

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

Differential unroofing within the central metasedimentary Belt of the Grenville Orogen: constraints from 40Ar/39Ar thermochronology     

Michael A. Cosca  Eric J. Essene  Michael J. Kunk  John F. Sutter 《Contributions to Mineralogy and Petrology》1992,110(2-3):211-225

An ⁴⁰Ar/³⁹Ar thermochronological investigation of upper greenschist to granulite facies gneiss, amphibolite and marble was conducted in the Central Metasedimentary Belt (CMB), Ontario, to constrain its cooling history. Incremental ⁴⁰Ar/³⁹Ar release spectra indicate that substantial differential unroofing occurred in the CMB between 1000 and 600 Ma. A consistent pattern of significantly older hornblende and phlogopite ⁴⁰Ar/³Ar cooling ages on the southeast sides of major northeast striking shear zones is interpreted to reflect late displacement due to extensional deformation. Variations in hornblende ⁴⁰Ar/³⁹Ar age plateaus exceeding 200 Ma occur over distances less than 50 km with major age discontinuities occurring across the Robertson Lake shear zone and the Sharbot Lake mylonite zone which separate the Sharbot Lake terrane from the Elzevir and Frontenac terranes. Extensional displacements of up to 14 km are inferred between the Frontenac and Elzevir terranes of the CMB. No evidence for significant post argon-closure vertical displacement is indicated in the vicinity of the Perth Road mylonite within the Frontenac terrane. Variations of nearly 100 Ma in phlogopite ⁴⁰Ar/³⁹Ar plateau ages occur in undeformed marble on either side of the Bancroft Shear Zone. Phlogopites from sheared and mylonitized marble within the shear zone yield ⁴⁰Ar/³⁹Ar diffusional loss profiles, but have older geologically meaningless ages thought to reflect incorporation of excess argon. By 900 Ma, southeast directed extension was occurring throughout the CMB, possibly initiated along previous zones of compressional shearing. An easterly migration of active zones of extension is inferred, possibly related to an earlier, overall easterly migration of active zones of regional thrusting and easterly migration of an ancient subduction zone. The duration of extensional shearing is not well constrained, but must have ceased before 600 Ma as required by the deposition of overlying undeformed Cambrian and/or Ordovician sedimentary rocks.Contribution No. 481 from the Mineralogical Laboratory, University of Michigan  相似文献   

Temporal and tectonic evolution of the granulite-eclogite association from the Bergen Arcs, western Norway   总被引：2，自引：0，他引：2  

T. M. Boundy  K. Mezger  E. J. Essene   《Lithos》1997,39(3-4):159-178

The U-Pb and Sm-Nd dating of deep crustal rocks from the Bergen Arcs system helps resolve enigmatic aspects of the tectonic evolution of the Caledonian Orogen in western Norway and yields insights into the arrested stages of eclogite development within the granulites of the area. The U-Pb dating of zircon from one of the eclogite facies shear zones yields an upper intercept age of 945 ± 5 Ma [all errors two standard deviations (2σ)], which is similar to other zircon ages from the granulite facies protolith. The age is interpreted to represent the time of late Proterozoic (Sveconorwegian) granulite metamorphism. The U-Pb ages of sphene and epidote show that the eclogites formed early in the evolution of the Caledonian Orogen (pre-Scandian phase) at about 460 Ma. An eclogite facies quartz vein yields a Sm-Nd whole rock-garnet isochron of 440 ± 12 Ma that may reflect the onset of cooling immediately after peak eclogite facies conditions, although the Sm-Nd systematics reveal some isotopic disequilibrium within the sample. In tandem with previous ⁴⁰Ar/³⁹Ar age determinations from, an adjacent eclogite of 450 Ma for hornblende and 430 Ma for muscovite, these data indicate that < 30 Ma elapsed between formation of the eclogites and the initial stages of cooling and exhumation to at least mid-crustal levels. This corresponds to minimum cooling rates of 14 °C/m.y. The timing relations suggest that the formation and exhumation of these eclogites from the overlying Caledonian Nappe wedge in western Norway are related to an early phase of crustal subduction during or somewhat before the major phase of continent-continent collision.

The short period of time between the formation of the eclogites and the initial stages of exhumation and rapid cooling is consistent with the only partial and localized transformation of the granulite to eclogite. Isolated occurrences of eclogite within the granulite, the formation of eclogite along metasomatic fronts and the formation of hydrous eclogite facies minerals within the “dry” granulite all point to the importance of fluids in the transformation and re-equilibration of the granulite to eclogite. Together, field and isotopic data demonstrate that both the localized and limited access of fluids and the rapid cycling of continental crust through the deepest portions of the orogen to upper crustal levels resulted in the preservation of the arrested stages of eclogite formation and survival of the granulites metastably through eclogite facies conditions.  相似文献   

Complete chemical analyses of metamorphic hornblendes: implications for normalizations,calculated H2O activities,and thermobarometry   总被引：1，自引：0，他引：1  

Michael A. Cosca  Eric J. Essene  Johns R. Bowman 《Contributions to Mineralogy and Petrology》1991,108(4):472-484

Twenty-two hornblendes separated from amphibolites and granulites of the Grenville Orogen of Ontario have been quantitatively analyzed for major and minor elements by electron microprobe, for FeO/Fe₂O₃ by wet chemistry, and for H₂O by manometric measurement as H₂. Hornblende formulae were calculated on the basis of 24O+OH+Cl+F. Most samples are magnesio-hornblendes, ferroan pargasitic hornblendes and ferroan hastingsitic hornblendes, with weight fractions of Fe³⁺/(Fe²⁺+Fe³⁺) ranging from 0.15 to 0.50. An oxy-amphibole component of 0–25 mol%, with an average value of 17 mol%, is obtained for these complete analyses. When compared with structural formulae determined solely from microprobe data, normalization based on 13=Si+Ti+Al+Fe+Mn+Mg cations provides the best approximation to hornblende formulae calculated from the complete analyses. Less satisfactory agreement is obtained from a normalization scheme based on 15=Si+Ti+Al+Fe+Mn+Mg+Ca, while worst agreement is obtained from normalization to 23 oxygens assuming all Fe is Fe²⁺. No normalization scheme based on microprobe data alone consistently replicates the measured FeO, Fe₂O₃, and H₂O; accurate determination of these values requires complete chemical analysies. Ionic solution models previously have been proposed to evaluate the activity of Ca₂Mg₅Si₈ O₂₂(OH)₂(a _Trem) in hornblende for use in equilibria that constrain the activity of H₂O (a _{H 2}O) in igneous and metamorphic rocks. Application of ionic models to typical hornblendes produces low a _Trem (usually<0.01), consequetly yielding extremely low a _{H 2}O. If an oxy-amphibole component is present, the calculated a _Trem and H₂O is further reduced. An oxy-amphibole component of 25% reduces the calculated H₂O activity and that of any hydroxyl-amphibole component by 50% below that calculated with simplified assumptions regarding X _OH in the hydroxyl site (i.e., X _OH=1, or X _OH=1–X _Cl–X _f). Thus, methods of amphibole normalizations appear to have a substantial effect on calculated amphibole and H₂O activites. Before quantitative hornblende thermobarometry can be calibrated and applied, the amounts of FeO, Fe₂O₃ and H₂O must be measured in order to fully characterize hornblende solid solutions.Contribution No. 478 from the Mineralogical Laboratory, University of Michigan  相似文献   

Genesis and solvus relations of submicroscopically intergrown paragonite and phengite in a blueschist from northern California     

Yen-Hong Shau  Melanie E. Feather  Eric J. Essene  Donald R. Peacor 《Contributions to Mineralogy and Petrology》1991,106(3):367-378

Electron microbeam techniques have been used to examine submicroscopically intergrown paragonite, phengite and chlorite from the South Fork Mountain Schist of the Franciscan Terrane of northern California, which was subjected to blueschist facies metamorphism. The sample also contains quartz, albite, lawsonite, and rutile. The subassemblage albite-lawsonite-rutile requires metamorphic conditions on the low-temperature side of the equilibrium albite+lawsonite+rutile=paragonite+sphene+quartz+H₂O (T<200° C and P<7.4 kbars based on thermodynamic data of Holland and Powell 1990). The white micas appear to be optically homogeneous, but back-scattered electron images can distinguish two different micas by their slight difference in contrast. Electron microprobe analyses (EMPA) of micas show Na/(Na+K) ranging from 0.2 to 0.8. The two micas are resolved by transmission electron microscopy (TEM) as packets of phengite and paragonite that range from 20 to several hundred nm in thickness. The compositions, determined by analytical electron microscopy (AEM), constrain the limbs of the phengite-paragonite solvus to values of Na/(Na+K)=<0.02 and 0.97, representing less mutual solid solution than ever reported by EMPA. The textural relations imply that the sheet silicates were derived from reactions between fluids and detrital clays and that they are in an intermediate stage of textural development. We caution that microprobe analyses of apparently homogeneous sheet silicates may yield erroneous data and lead to faulty conclusions using phengite barometry and paragonite-muscovite thermometry, especially in fine-grained rocks that formed at relatively low temperatures. Contribution no. 473 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan, USA  相似文献   

Heat capacity of γ-Fe2SiO4 between 5 and 303 K and derived thermodynamic properties     

Wenjun Yong  E. Dachs  A. C. Withers  E. J. Essene 《Physics and Chemistry of Minerals》2007,34(2):121-127

A multi-anvil device was used to synthesize 24 mg of pure γ-Fe₂SiO₄ crystals at 8.5 GPa and 1,273 K. The low-temperature heat capacity (C _p) of γ-Fe₂SiO₄ was measured between 5 and 303 K using the heat capacity option of a physical properties measurement system. The measured heat capacity data show a broad λ-transition at 11.8 K. The difference in the C _p between fayalite and γ-Fe₂SiO₄ is reduced as the temperature increases in the range of 50–300 K. The gap in C _p data between 300 and 350 K of γ-Fe₂SiO₄ is an impediment to calculation of a precise C _p equation above 298 K that can be used for phase equilibrium calculations at high temperatures and high pressures. The C _p and entropy of γ-Fe₂SiO₄ at standard temperature and pressure (S°₂₉₈) are 131.1 ± 0.6 and 140.2 ± 0.4 J mol⁻¹ K⁻¹, respectively. The Gibbs free energy at standard pressure and temperature (ΔG° _f,298) is calculated to be −1,369.3 ± 2.7 J mol⁻¹ based on the new entropy data. The phase boundary for the fayalite–γ-Fe₂SiO₄ transition at 298 K based on current thermodynamic data is located at 2.4 ± 0.6 GPa with a slope of 25.4 bars/K, consistent with extrapolated results of previous experimental studies.  相似文献   

Stability of pyrope-quartz in the system MgO-Al2O3-SiO2     

B. J. Hensen  E. J. Essene 《Contributions to Mineralogy and Petrology》1971,30(1):72-83

Pyrope and quartz are stable with respect to aluminous enstatite and sillimanite at 1400 °C, 20 kb and at 1100 °C, 16 kb. The phase boundary limiting the coexistence of pyrope and quartz towards lower pressures is probably slightly curved. A slope of 15 bars/°C at 1400° and of 10 bars/°C at 1000 °C has been estimated from the experimental data. Between 1050 and 1100 °C the curve is intersected by the kyanite-sillimanite phase boundary. The calculated slope of the reaction aluminous enstatite + kyanite pyrope + quartz is negative (ca. 18–25 bars/°C). The existence of a negative slope has been demonstrated experimentally. Experimental evidence indicates that the assemblage aluminous enstatite and sillimanite is metastable with respect to sapphirine + quartz at high temperature. The invariant point involving the phases pyrope-sapphirine-aluminous enstatite-sillimanite-quartz is estimated to occur at 1125°±25 °C and 16±1 kb. A model phase diagram for the silicasaturated part of the system MgO-Al₂O₃-SiO₂ has been constructed. The position of three invariant points in this system has been estimated on the basis of presently available data.  相似文献   

Comparison of garnet-biotite, calcite-graphite, and calcite-dolomite thermometry in the Grenville Orogen; Ontario, Canada     

Mark A. Rathmell  Margaret M. Streepey  Eric J. Essene  Ben A. van der Pluijm 《Contributions to Mineralogy and Petrology》1999,134(2-3):217-231

The Elzevir Terrane of the Grenville Orogen in southern Ontario contains metapelites and abundant graphitic marbles that were regionally metamorphosed from the upper greenschist to upper amphibolite facies. Comparative thermometry was undertaken with widely used calibrations for the systems garnet-biotite, calcite-dolomite, and calcite-graphite. Temperatures that are obtained from matrix biotites paired with prograde garnet near-rim analyses are usually consistent with those determined using calcite-graphite thermometry. However, calcite-graphite thermometry occasionally yields low temperatures due to lack of equilibration of anomalously light graphite. Application of calcite-graphite and garnet-biotite systems may yield temperatures up to 70 °C higher than calcite-dolomite in amphibolite facies rocks. Calcite-dolomite temperatures most closely approach those from calcite-graphite and garnet-biotite when the samples contain a single generation of dolomite and calcite grains contain no visible dolomite exsolution lamellae. However, some of these samples yield temperatures considerably lower than temperatures calculated from calcite-graphite and garnet-biotite thermometry, indicating that the calcite-dolomite thermometer may have been partially reset during retrogression. Estimated peak metamorphic temperatures of regional metamorphism between Madoc (upper greenschist facies) and Bancroft (upper amphibolite facies) range from 500 to 650 °C. These results place the chlorite-staurolite isograd at 540 °C, the kyanite-sillimanite isograd at 590 °C, and the sillimanite-K-feldspar isograd at 650 °C. Although each thermometer may have an absolute uncertainty of as much as ±50 °C, the 50 to 60 °C temperature differences between the isograds are probably accurate to 10 to 20 °C. An incomplete picture of the thermal gradients can result from the application of only one thermometer in a given area. Simultaneous application of several systems allows one to recognize and overcome the inherent limitations of each thermometer. Received: 26 March 1997 / Accepted: 15 April 1998  相似文献   

The LaPaz Icefield 04840 meteorite: Mineralogy, metamorphism, and origin of an amphibole- and biotite-bearing R chondrite     

M.C. McCanta  A.H. Treiman  C.M.O’D. Alexander  E.J. Essene 《Geochimica et cosmochimica acta》2008,72(23):5757-5780

The R chondrite meteorite LaPaz Icefield (LAP) 04840 is unique among metamorphosed, non-carbonaceous chondrites in containing abundant OH-bearing silicate minerals: ∼13% ferri-magnesiohornblende and ∼0.4% phlogopite by volume. Other minerals include olivine (Fo₆₂), orthopyroxene (En₆₉Fs₃₀Wo₁), albite (An₈Ab₉₀Or₂), magnetite, pyrrhotite, pentlandite, and apatite. Ferromagnesian minerals are rich in Fe³⁺, as determined by Mössbauer spectrometry and electron microprobe chemical analyses. Fe³⁺/Fe_tot values are olivine ?5%, amphibole 80%, phlogopite 65%, and magnetite 42%. Mineral compositions are nearly constant across grains and the section, except for a small variability in amphibole compositions reflecting the edenite exchange couple (^ANa + ^IVAl ↔ ^A□ + Si). These mineral compositions, the absence of Fe-Ni metal, and the oxygen isotope data support its classification as an R (Rumuruti) chondrite. LAP 04840 is classified as petrologic grade 5, based on the chemical homogeneity of its minerals, and the presence of distinctly marked chondrules and chondrule fragments in a fine-grained crystalline matrix. The mineral assemblage of LAP 04840 allows calculation of physical and chemical conditions at the peak of its metamorphism: T = 670 ± 60 °C from a amphibole-plagioclase thermometer; P_H2O between 250 and 500 bars as constrained by the assemblage phlogopite + orthopyroxene + olivine + feldspar and the absence of diopside; P_CO2 unconstrained; f_O2 at QFM + 0.5 log units; . The hydrogen in LAP 04840 is very heavy, an average δD value of +3660 ± 75‰ in the magnesiohornblende. Only a few known sources of hydrogen have such high δD and are suitable sources for LAP 04840: ordinary chondrite phyllosilicates (as in the Semarkona chondrite), and insoluble organic matter (IOM) in ordinary chondrites and CR chondrites. Hydrogen from the IOM could have been released by oxidation, and then reacted with an anhydrous R chondrite (at high temperature), but it is not clear whether this scenario is correct.  相似文献