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1.
A thermodynamic formulation of hydrous Mg-cordierite (Mg2Al4Si5O18·nH2O) has been obtained by application of calorimetric and X-ray diffraction data for hydrous cordierite to the results of hydrothermal syntheses. The data include measurements of the molar heat capacity and enthalpy of hydration and the molar volume. The synthesis data are consistent with a thermodynamic formulation in which H2O mixes ideally on a single crystallographic site in hydrous cordierite. The standard molar Gibbs free energy of hydration is-9.5±1.0 kJ/mol (an average of 61 syntheses). The standard molar entropy of hydration derived from this value is-108±3 J/mol-K. An equation providing the H2O content of cordierite as a function of temperature and fugacity of H2O is as follows (n moles of H2O per formula unit, n<1): $$\begin{gathered}n = {{f_{{\text{ H}}_{\text{2}} O}^{\text{V}} } \mathord{\left/{\vphantom {{f_{{\text{ H}}_{\text{2}} O}^{\text{V}} } {\left( {f_{{\text{ H}}_{\text{2}} O}^{\text{V}} + {\text{exp}}\left[ { - {\text{3}}{\text{.8389}} - 5025.2\left( {\frac{1}{T} - \frac{1}{{298.15}}} \right)} \right.} \right.}}} \right.\kern-\nulldelimiterspace} {\left( {f_{{\text{ H}}_{\text{2}} O}^{\text{V}} + {\text{exp}}\left[ { - {\text{3}}{\text{.8389}} - 5025.2\left( {\frac{1}{T} - \frac{1}{{298.15}}} \right)} \right.} \right.}} \hfill \\{\text{ }}\left. {\left. { - {\text{ln}}\left( {\frac{T}{{{\text{298}}{\text{.15}}}}} \right) - \left( {\frac{{298.15}}{T} - 1} \right)} \right]} \right) \hfill \\\end{gathered}$$ Application of this formulation to the breakdown reaction of Mg-cordierite to an assemblage of pyrope-sillimanite-quartz±H2O shows that cordierite is stabilized by 3 to 3.5 kbar under H2O-saturated conditions. The thermodynamic properties of H2O in cordierite are similar to those of liquid water, with a standard molar enthalpy and Gibbs free energy of hydration that are the same (within experimental uncertainty) as the enthalpy and Gibbs free energy of vaporization. By contrast, most zeolites have Gibbs free energies of hydration two to four times more negative than the corresponding value for the vaporization of water.  相似文献   

2.
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3.
The high-grade assemblage Cd-Ga-Si-Qz can be thermodynamically modelled from available calorimetric data on the metastable reaction: (I) $$3 MgCd \rightleftarrows 2 Py + 4 Si + 5 Qz$$ naturalK D Fe-Mg between garnet and cordierite and experimental results on cordierite hydration. In the system SiO2-Al2O3-MgO-H2O, reaction (I) becomes (II) $$3 MgCd \cdot nH_2 O \rightleftarrows 2 Py + 4 Si + 5 Qz + 3 nH_2 O$$ . However, hydrous cordierite is neither a hydrate nor a solid solution between water and anhydrous cordierite and when nH2O (number of moles of H2O in Cd) is plotted against \(P_{H_2 O} \) , the resulting isotherms are similar to adsorption isotherms characteristic of zeolitic minerals. Reaction (II) can thus be considered as a combination of reaction (I) with a physical equilibrium of the type nH2O (in Cd)?nH2O (in vapor phase). Starting from a point on equilibrium (I), introduction of H2O into anhydrous Mg-cordierite lowers the chemical potential of MgCd and hence stabilizes this mineral to higher pressure relative to the right-hand assemblage in reaction (I). The pressure increment of stabilization,ΔP, above the pressure limit of anhydrous cordierite stability at constantT, has been calculated using the standard thermodynamics of adsorption isotherms. Cordierite is regarded as a mixture of Mg2Al4Si5O18 and H2O. The activity of H2O in the cordierite is evaluated relative to an hypothetical standard state extrapolated from infinite H2O dilution, by using measured hydration data. The activity of Mg2Al4Si5O18 in the cordierite is then obtained by integration of the Gibbs-Duhem equation, and the pressure stabilization increment,ΔP, computed by means of the relation: $$\Delta V_s \Delta P \cong - RT\ln a_{MgCd}^{MgCd \cdot nH2O} \left( {\Delta V indepentdent of P and T} \right)$$ . Thus, one may contour theP-T plane in isopleths of nH2O=constant within the area of Mg-cordierite stability allowed by the hydration data for \(P_{H_2 O} = P_{total} \) . The present model indicates greater stabilization of cordierite by H2O than the model of Newton and Wood (1979) and the calculated curve for metastable breakdown of hydrous MgCd is consistent with experimental data on cordierite breakdown at \(P_{H_2 O} = P_{total} \) . Mg/(Mg+Fe) isopleths have been derived for cordierites of varying nH2O in the SiO2-Al2O3-MgO-FeO-H2O system using the additional assumptions that (Fe, Mg) cordierite and (Fe, Mg) garnet behave as ideal solutions, and that typical values of the distribution coefficient of Fe and Mg between coexisting garnet and cordierite observed in natural parageneses can be applied to the calculations. The calculated stable breakdown curve of Fe-cordierite under conditions of \(P_{H_2 O} = P_{total} \) to almandine, sillimanite, quartz and vapor has a positive slope (dP/dT) apparently in contrast to the experimental negative slope. This may be explained by hydration kinetics, which could have allowed systematic breakdown of cordierites of metastable hydration states in the experiments. The bivariant Cd-Ga fields calibrated from the present model are, potentially, good petrogenetic indicators, as, given the iron-magnesium ratio of garnet and cordierite and the hydration number of cordierite, the temperature, pressure and water fugacity are uniquely determined. As this geothermobarometer is in part based on the water content of cordierite, it can be used only if there is some assurance that the actual hydration is inherited from high-grade metamorphic conditions. Such conditions could be realised if the slope of unloading-cooling retrograde metamorphism is more or less parallel to a cordierite isohydron.  相似文献   

4.
The high-temperature and high-pressure experiment on natural block rock indicates that dehydration-melting of hydrous biotite (Bi) and partial melting of felsic minerals in garnet-biotite-plagioclase gneiss are mainly controlled by temperature, while mineral phase transformation is not only controlled by temperature-pressure conditions but also genetically associated with hydrous mineral dehydration-melting and partial melting of felsic minerals. According to the characteristics of biotite dehydration-melting and garnet transformation reaction, three stages may be distinguished: (1) when the experimental temperature is 700℃, biotite transforms to ilmenite (Ilm) + magnetite (Mt) + H2O and garnet to magnetite (Mt); (2) when the temperature is 730-760℃, biotite is dehydrated and melted and transformed into K2O-rich melt + Ilm + Mt, and garnet, into hypersthene (Hy) + cordierite (Crd); (3) when the temperature is up to or higher than 790℃, biotite is dehydrated and melted and transformed into melt + Hy +  相似文献   

5.
Cordierite H2O and CO2 volatile saturation surfaces derived from recent experimental studies are presented for P–T conditions relevant to high‐grade metamorphism and used to evaluate fluid conditions attending partial melting and granulite formation. The volatile saturation surfaces and saturation isopleths for both H2O and CO2 in cordierite are strongly pressure dependent. In contrast, the uptake of H2O by cordierite in equilibrium with melts formed through biotite dehydration melting, controlled by the distribution of H2O between granitic melt and cordierite, Dw[Dw = wt% H2O (melt)/wt% H2O(Crd)], is mainly temperature dependent. Dw = 2.5–6.0 for the H2O contents (0.4–1.6 wt percentage) typical of cordierite formed through biotite dehydration melting at 3–7 kbar and 725–900 °C. This range in Dw causes a 15–30% relative decrease in the total wt% of melt produced from pelites. Cordierite in S‐type granites are H2O‐rich (1.3–1.9 wt%) and close to or saturated in total volatiles, signifying equilibration with crystallizing melts that achieved saturation in H2O. In contrast, the lower H2O contents (0.6–1.2 wt percentage) preserved in cordierite from many granulite and contact migmatite terranes are consistent with fluid‐absent conditions during anatexis. In several cases, including the Cooma migmatites and Broken Hill granulites, the cordierite volatile compositions yield aH2O values (0.15–0.4) and melt H2O contents (2.2–4.4 wt%) compatible with model dehydration melting reactions. In contrast, H2O leakage is indicated for cordierite from Prydz Bay, Antarctica that preserve H2O contents (0.5–0.3 wt%) which are significantly less than those required (1.0–0.8 wt%) for equilibrium with melt at conditions of 6 kbar and 860 °C. The CO2 contents of cordierite in migmatites range from negligible (< 0.1 wt%) to high (0.5–1.0 wt%), and bear no simple relationship to preserved cordierite H2O contents and aH2O. In most cases the cordierite volatile contents yield total calculated fluid activities (aH2O + aCO2) that are significantly less than those required for fluid saturation at the P–T conditions of their formation. Whether this reflects fluid absence, dilution of H2O and CO2 by other components, or leakage of H2O from cordierite is an issue that must be evaluated on a case‐by‐case basis.  相似文献   

6.
The heat capacity of synthetic anhydrous Mg and Fe cordierite was measured by differential scanning calorimetry (DSC). Mg cordierite was synthesized from a glass at high temperatures and shows an ordered structural state. Fe cordierite was synthesized hydrothermally and dehydrated under reducing conditions to obtain H2O-free material. IR spectroscopy was used to ascertain the lack of H2O in both phases. The molar volume of both phases was measured using powder X-ray diffraction giving 23.316 (7) J/bar for Mg cordierite and 23.672 (6) J/bar for Fe cordierite. DSC measurements between 300 and 950 K were made following the procedure of Bosenick et al. (1996). The data show a precision of about 1% in the case of Mg cordierite and 1.5% for Fe cordierite. Fitted Cp polynomials in J/mol/K are:
and
for Mg and Fe cordierite, respectively. The Cp values determined for Mg cordierite are slightly larger (1–3%) than those measured by drop calorimetry by Pankratz and Kelley (1963). The Cp data for Fe cordierite permit the calculation of its standard third-law entropy, So 298 K from the reaction 3Fe cordierite=2 almandine + 4 sillimanite + 5 quartz giving 465 J/mol/K, which is in good agreement with recent model estimates. Received: 18 June 1999 / Accepted: 30 August 1999  相似文献   

7.
 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H2O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)2Al4Si5O18+H2O ⇄ (Fe,Mg)2Al4Si5O18.H2O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ° r =–37141±3520 J and ΔS °  r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n H2O=1/[1+1/(K ⋅ f H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H2O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996  相似文献   

8.
Two natural CO2-rich cordierite samples (1.00 wt% CO2, 0.38 wt% H2O, and 1.65 wt% CO2, 0.15 wt% H2O, respectively) were investigated by means of Raman spectroscopy and single-crystal X-ray diffraction at ambient and high pressures. The effect of heavy-ion irradiation (Au 2.2 GeV, fluence of 1 × 1012 ions cm?2) on the crystal structure was investigated to characterize the structural alterations complementary to results reported on hydrous cordierite. The linear CO2 molecules sustained irradiation-induced breakdown with small CO2-to-CO conversion rates in contrast to the distinct loss of channel H2O. The maximum CO2 depletion rate corresponds to ~12 ± 5 % (i.e. ~0.87 and ~1.49 wt% CO2 according to the two samples, respectively). The elastic properties of CO2-rich cordierite reveal stiffening due to the CO2 molecules (non-irradiated: isothermal bulk modulus K 0 = 120.3 ± 3.7 GPa, irradiated: K 0 = 109.7 ± 3.7 GPa), but show the equivalent effect of hydrous cordierite to get softer when irradiated. The degree of anisotropy of axial compressibilities and the anomalous elastic softening at increasing pressure agrees with those reported for hydrous cordierite. Nevertheless, the experimental high-pressure measurements using ethanol–methanol reveal a small hysteresis between compression and decompression, together with the noticeable effect of pressure-induced over-hydration at pressures between 4 and 5 GPa.  相似文献   

9.
The H2O and CO2 content of cordierite was analysed in 34 samples from successive contact metamorphic zones of the Etive thermal aureole, Scotland, using Fourier‐transform infrared spectroscopy (FTIR). The measured volatile contents were used to calculate peak metamorphic H2O and CO2 activities. Total volatile contents are compared with recently modelled cordierite volatile saturation surfaces in order to assess the extent of fluid‐present v. fluid‐absent conditions across the thermal aureole. In the middle aureole, prior to the onset of partial melting, calculated aH2O values are high, close to unity, and measured volatile contents intersect modelled H2O–CO2 saturation curves at the temperature of interest, suggesting that fluid‐present conditions prevailed. Total volatile contents and aH2O steadily decrease beyond the onset of partial melting, consistent with the notion of aH2O being buffered to lower values as melting progresses once free hydrous fluid is exhausted. All sillimanite zone samples record total volatile contents that are significantly lower than modelled H2O–CO2 saturation surfaces, implying that fluid‐absent conditions prevailed. The lowest recorded aH2O values lie entirely within part of the section where fluid‐absent melting reactions are thought to have dominated. Samples within 30 m of the igneous contact appear to be re‐saturated, possibly via a magmatically derived fluid. In fluid‐absent parts of the aureole, cordierite H2O contents yield melt–H2O contents that are compatible with independently determined melt–H2O contents. The internally consistent cordierite volatile data and melt–H2O data support the conclusion that the independent P–T estimates applied to the Etive rocks were valid and that measured cordierite volatile contents are representative of peak metamorphic values. The Etive thermal aureole provides the most compelling evidence, suggesting that the cordierite fluid monitor can be used to accurately assess the fluid conditions during metamorphism and partial melting in a thermal aureole.  相似文献   

10.
Near-infrared (NIR) absorption bands related to total water (4000 and 7050 cm−1), OH groups (4500 cm−1) and molecular H2O (5200 cm−1) were studied in two polymerised glasses, a synthetic albitic composition and a natural obsidian. The water contents of the glasses were determined using Karl Fischer titration. Molar absorption coefficients were calculated for each of the bands using albitic glasses containing between 0.54 and 9.16 wt.% H2O and rhyolitic glasses containing between 0.97 and 9.20 wt.% H2O. Different combinations of baseline type and intensity measure (peak height/area) for the combination bands at 4500 and 5200 cm−1 were used to investigate the effect of evaluation procedure on calculated hydrous species concentrations. Total water contents calculated using each of the baseline/molar absorption coefficient combinations agree to within 5.8% relative for rhyolitic and 6.5% relative for albitic glasses (maximum absolute differences of 0.08 and 0.15 wt.% H2O, respectively). In glasses with water contents >1 wt.%, calculated hydrous species concentrations vary by up to 17% relative for OH and 11% relative for H2O (maximum absolute differences of 0.33 and 0.43 wt.% H2O, respectively). This variation in calculated species concentrations is typically greater in rhyolitic glasses than albitic. In situ, micro-FTIR analysis at 300 and 100 K was used to investigate the effect of varying temperature on the NIR spectra of the glasses. The linear and integral molar absorption coefficients for each of the bands were recalculated from the 100 K spectra, and were found to vary systematically from the 300 K values. Linear molar absorption coefficients for the 4000 and 7050 cm−1 bands decrease by 16–20% and integral molar absorption coefficients by up to 30%. Depending on glass composition and baseline type, the integral molar absorption coefficients for the absorption bands related to OH groups and molecular H2O change by up to −5.8 and +7.4%, respectively, while linear molar absorption coefficients show less variation, with a maximum change of ∼4%. Using the new molar absorption coefficients for the combination bands to calculate species concentrations at 100 K, the maximum change in species concentration is 0.08 wt.% H2O, compared with 0.39 wt.% which would be calculated if constant values were assumed for the combination band molar absorption coefficients. Almost all the changes in the spectra can therefore be interpreted in terms of changing molar absorption coefficient, rather than interconversion between hydrous species. Received: 17 December 1998 / Revised, accepted 8 July 1999  相似文献   

11.
The effect of water on heat capacity has been determined for four series of hydrated synthetic aluminosilicate glasses and supercooled liquids close to albite, phonolite, trachyte, and leucogranite compositions. Heat capacities were measured at atmospheric pressure by differential scanning calorimetry for water contents between 0 and 4.9 wt % from 300 K to about 100 K above the glass transition temperature (Tg). The partial molar heat capacity of water in polymerized aluminosilicate glasses, which can be considered as independent of composition, is (J/mol K). In liquids containing at least 1 wt % H2O, the partial molar heat capacity of water is about 85 J/mol K. From speciation data, the effects of water as hydroxyl groups and as molecular water have tentatively been estimated, with partial molar heat capacities of 153 ± 18 and 41 ± 14 J/mol K, respectively. In all cases, water strongly increases the configurational heat capacity at Tg and exerts a marked depressing effect on Tg, in close agreement with the results of viscosity experiments on the same series of glasses. Consistent with the Adam and Gibbs theory of relaxation processes, the departure of the viscosity of hydrous melts from Arrhenian variations correlates with the magnitude of configurational heat capacities.  相似文献   

12.
Schists from the foothills of the Central Sierra Nevada contain one dominant matrix foliation and yet four phases of growth of both cordierite and andalusite porphyroblasts can be distinguished. These occurred early during four separate deformation events that formed successive steep and shallow foliations. A fifth deformation event pre-dates the growth of all porphyroblasts studied. The multiple phases of porphyroblast growth allow correlation of structures across and along the region. A repeated pattern of deformation, in terms of the curvature of earlier foliations against the overprinting one, allows samples containing porphyroblasts with simpler inclusion trail geometries to be interpreted with confidence. The large-scale fold structures in this region formed before or during the second of the five deformation events recorded by the porphyroblasts. However, the matrix foliation is predominantly a product of the fourth deformation, which has commonly reactivated or re-used older foliations, and is dominated by east-side-up shear. The intervening third deformation produced locally intense foliations and was accompanied by top-to-the-east shear. The very weak fifth deformation produced weak crenulations with subhorizontal axial planes and was coaxial. Multiple phases of episodic but synchronous growth of cordierite and andalusite were produced by the KFMASH univariant equilibrium Ms+Chl+Qtz=And+Crd+Bt+H2O. The rocks crossed this reaction at a pressure just below the intersection with the KFMASH divariant equilibrium Ms+Chl+Qtz=Crd+Bt+H2O; the latter being overstepped in favour of the former as there is no evidence for cordierite growth prior to andalusite in these rocks. Subsequent multiple episodes of synchronous growth of cordierite and andalusite indicate that the possible variation in P–T during subsequent deformations was not large. This requires the high-amplitude macroscopic fold to form prior to porphyroblast growth and then be simply tightened and modified by the younger deformations.  相似文献   

13.
The Legs Lake shear zone is a crustal‐scale thrust fault system in the western Canadian Shield that juxtaposes high‐pressure (1.0+ GPa) granulite facies rocks against shallow crustal (< 0.5 GPa) amphibolite facies rocks. Hangingwall decompression is characterized by breakdown of the peak assemblage Grt + Sil + Kfs + Pl + Qtz into the assemblage Grt + Crd + Bt ± Sil + Pl + Qtz. Similar felsic granulite occurs throughout the region, but retrograde cordierite is restricted to the immediate hangingwall of the shear zone. Textural observations, petrological analysis using P–T/P–MH2O phase diagram sections, and in situ electron microprobe monazite geochronology suggest that decompression from peak conditions of 1.1 GPa, c. 800 °C involved several distinct stages under first dry and then hydrated conditions. Retrograde re‐equilibration occurred at 0.5–0.4 GPa, 550–650 °C. Morphology, X‐ray maps, and microprobe dates indicate several distinct monazite generations. Populations 1 and 2 are relatively high yttrium (Y) monazite that grew at 2.55–2.50 Ga and correspond to an early granulite facies event. Population 3 represents episodic growth of low Y monazite between 2.50 and 2.15 Ga whose general significance is still unclear. Population 4 reflects low Y monazite growth at 1.9 Ga, which corresponds to the youngest period of high‐pressure metamorphism. Finally, population 5 is restricted to the hydrous retrograded granulite and represents high Y monazite growth at 1.85 Ga that is linked directly to the synkinematic garnet‐consuming hydration reaction (KFMASH): Grt + Kfs + H2O = Bt + Sil + Qtz. Two samples yield weighted mean microprobe dates for this population of 1853 ± 15 and 1851 ± 9 Ma, respectively. Subsequent xenotime growth correlates with the reaction: Grt + Sil + Qtz + H2O = Crd. We suggest that the shear zone acted as a channel for fluid produced by dehydration of metasediments in the underthrust domain.  相似文献   

14.
潘波  程滔  徐丹  刘松军 《岩石学报》2020,36(7):2067-2080
长白山天池火口北侧天文峰之上,一套醒目的黄色浮岩引起广泛的关注,其颜色成因问题更是讨论的热点。本文通过野外地质调查、显微形貌和地球化学分析等方法,探索了黄色浮岩的颜色成因问题,并对此次喷发活动(天文峰期喷发)有了更进一步的认识。黄色浮岩与其下部灰白色浮岩应为同一期喷发所形成,两者成分一致且特征相似。黄色浮岩初始颜色为灰白色,后期受所处环境(降水丰富)与本身气孔特征的影响,浮岩内发生了元素析出和元素沉淀的过程。首先,浮岩内Si与H2O结合形成弱硅酸(H2Si O3),而大气中CO2与H2O结合形成弱碳酸(H2CO3),在弱酸环境下火山玻璃逐渐析出Si、K、Al、Ca和Fe等阳离子,而析出的元素易溶于水的部分被流水带走,难溶于水的Fe与Al富集并粘附在火山玻璃壁上,同时由于Fe可与H2O络合形成黄色的Fe的水合物(Fe2O3·n H2O),而Al与H2O络合形成凝胶状白色水合物(Al2O3·n H2O),两者混合形成了黄色胶状物粘附在火山玻璃壁上,改变了浮岩原本的灰白色,形成了黄色浮岩。因此,天文峰期浮岩的黄色是由于后期风化淋滤作用所造成,属于次生色。本研究提高了对火山喷发堆积物风化淋滤作用过程的认识,也为其他地区相似颜色变化问题的讨论提供了借鉴。  相似文献   

15.
The Tulul Al Hammam area in central Jordan is an advantageous natural analogue site to study long-term U(VI) retention in ~?1 Ma old U-bearing combustion metamorphic marbles with clinker-like mineralogy exposed to prolonged supergene alteration for at least ~?100 kyr. The marbles contain abundant grains of high-temperature (ca. 800–850 °C) primary double Ca-U(VI) oxides (mainly Ca3UO6 and CaUO4), which are commonly replaced by hydrated calcium uranates with various impurities (Si, Fe, Al and F). A more hydrous natural analogue of X-phase (Ca2UO5·2-3H2O) occurs as a predominant secondary U compound after primary Ca-U(VI) oxides. The phase was studied by single-crystal XRD, SEM/EDX and electron microprobe (EPMA) analyses and Raman spectroscopy. It is a non-crystalline phase with a specific finger-like microtexture consisting of thin (no wider than 1–2 μm) lamellar particles. Its Raman spectrum shows a single strong band at 706–713 cm?1, sometimes coexisting with up to three weak diffuse bands (ν ~?390, ~?540 and 1355–1400 cm?1). The find of the natural X-phase (Ca2UO5·2-3H2O) is evidence of its long-term stability in a natural environment. It proves explicitly that the compound Ca2UO5·nH2O is a solubility-limiting phase in aged cements. The results have implications for geological disposal of radioactive wastes.  相似文献   

16.
Phase relations for a natural serpentinite containing 5 wt% of magnetite have been investigated using a multi-anvil apparatus between 6.5 and 11 GPa and 400–850 °C. Post-antigorite hydrous phase assemblages comprise the dense hydrous magnesium silicates (DHMSs) phase A (11.3 wt% H2O) and the aluminous phase E (Al-PhE, 11.9 wt% H2O). In addition, a ferromagnesian hydrous silicate (11.1 wt% H2O) identified as balangeroite (Mg,Fe)42Si16O54(OH)40, typically described in low pressure natural serpentinite, was found coexisting with Al-PhE between 650 and 700 °C at 8 GPa. In the natural antigorite system, phase E stability is extended to lower pressures (8 GPa) than previously reported in simple chemical systems. The reaction Al-phase E?=?garnet?+?olivine?+?H2O is constrained between 750 and 800 °C between 8 and 11 GPa as the terminal boundary between hydrous mineral assemblages and nominally anhydrous assemblages, hence restricting water transfer into the deep mantle to the coldest slabs. The water storage capacity of the assemblage Al-PhE?+?enstatite (high-clinoenstatite)?+?olivine, relevant for realistic hydrated slab composition along a relatively cold temperature path is estimated to be ca. 2 wt% H2O. Attempts to mass balance run products emphasizes the role of magnetite in phase equilibria, and suggests the importance of ferric iron in the stabilization of hydrous phases such as balangeroite and aluminous phase E.  相似文献   

17.
Low‐pressure crystal‐liquid equilibria in pelitic compositions are important in the formation of low‐pressure, high‐temperature migmatites and in the crystallization of peraluminous leucogranites and S‐type granites and their volcanic equivalents. This paper provides data from vapour‐present melting of cordierite‐bearing pelitic assemblages and augments published data from vapour‐present and vapour‐absent melting of peraluminous compositions, much of which is at higher pressures. Starting material for the experiments was a pelitic rock from Morton Pass, Wyoming, with the major assemblage quartz‐K feldspar‐biotite‐cordierite, approximately in the system KFMASH. A greater range in starting materials was obtained by addition of quartz and sillimanite to aliquots of this rock. Sixty‐one experiments were carried out in cold‐seal apparatus at pressures of 1–3.5 kbar (particularly 2 kbar) and temperatures from 700 to 840 °C, with and without the addition of water. In the vapour‐present liquidus relations at 2 kbar near the beginning of melting, the sequence of reactions with increasing temperature is: Qtz + Kfs + Crd + Sil + Spl + V = L; Qtz + Kfs + Crd + Spl + Ilm + V = Bt + L; and Qtz + Bt + V = Crd + Opx + Ilm + L. Vapour‐absent melting starts at about 800 °C with a reaction of the form Qtz + Bt = Kfs + Crd + Opx + Ilm + L. Between approximately 1–3 kbar the congruent melting reaction is biotite‐absent, and biotite is produced by incongruent melting, in contrast to higher‐pressure equilibria. Low pressure melts from pelitic compositions are dominated by Qtz‐Kfs‐Crd. Glasses at 820–840 °C have calculated modes of approximately Qtz42Kfs46Crd12. Granites or granitic leucosomes with more than 10–15% cordierite should be suspected of containing residual cordierite. The low‐pressure glasses are quite similar to the higher‐pressure glasses from the literature. However, XMg increases from about 0.1–0.3 with increasing pressure from 1 to 10 kbar, and the low‐temperature low‐pressure glasses are the most Fe‐rich of all the experimental glasses from pelitic compositions.  相似文献   

18.
The reaction muscovite+cordierite→biotite+Al2SiO5 +quartz+H2O is of considerable importance in the low pressure metamorphism of pelitic rocks: (1) its operation is implied in the widespread assemblage Ms + Crd +And± Sil + Bt + Qtz, a common mineral assemblage in contact aureoles and low pressure regional terranes; (2) it is potentially an important equilibrium for pressure estimation in low pressure assemblages lacking garnet; and (3) it has been used to distinguish between clockwise and anticlockwise P–T paths in low pressure metamorphic settings. Experiments and thermodynamic databases provide conflicting constraints on the slope and position of the reaction, with most thermodynamic databases predicting a positive slope for the reaction. Evidence from mineral assemblages and microtextures from a large number of natural prograde sequences, in particular contact aureoles, is most consistent with a negative slope (andalusite and/or sillimanite occurs upgrade of, and may show evidence for replacement of, cordierite). Mineral compositional trends as a function of grade are variable but taken as a whole are more consistent with a negative slope than a positive slope. Thermodynamic modelling of reaction 1 and associated equilibria results in a low pressure metapelitic petrogenetic grid in the system K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH) which satisfies most of the natural and experimental constraints. Contouring of the Fe–Mg divariant interval represented by reaction 1 allows for pressure estimation in garnet‐absent andalusite+cordierite‐bearing schists and hornfelses. The revised topology of reaction 1 allows for improved analysis of P–T paths from mineral assemblage sequences and microtextures in the same rocks.  相似文献   

19.
A refined thermodynamic model of H2O and CO2 bearing cordierite based on recent data on volatile incorporation into cordierite (Thompson et al. in Contrib Mineral Petrol 142:107–118, 2001; Harley and Carrington in J Petrol 42:1595–1620, 2001) reflects non-ideality of channel H2O and CO2 mixing. The dependence of cordierite H2O and CO2 contents on P, T and equilibrium fluid composition has been calculated for the range 600–800°C and 200–800 MPa. It has been used for establishing thermodynamic conditions of cordierite formation and the following retrograde P–T paths of cordierite rocks from many localities. Estimates of the H2O and CO2 activities have shown that cordierites in granites, pegmatites and high-pressure granulites were formed in fluid-saturated conditions and wide range of H2O/CO2 relations. Very low cordierite H2O contents in many migmatites may be caused not only by fluid-undersaturated conditions at rock formation and H2O leakage on retrograde P–T paths but also by the presence of additional volatile components like CH4 and N2. The pressure dependence of cordierite-bearing mineral equilibria on fluid H2O/CO2 relations has been evaluated.  相似文献   

20.
The molar volumes of 19 hydrous albitic liquids (1.9 to 6.1 wt% H2Ototal) were determined at one bar and 505–765 K. These volume data were derived from density measurements on hydrous glasses at 298 K, followed by measurements of the thermal expansion of each glass from 298 K to its respective glass transition temperature. The technique exploits the fact that the volume of a glass is equal to that of the corresponding liquid at the limiting fictive temperature (T f′), and that T f′ can be approximated as the temperature near the onset of the rapid increase in thermal expansion that occurs in the glass transition interval. The volume data of this study were combined with available volume data for anhydrous, Na2O-Al2O3-SiO2 liquids to derive the partial molar volume (±1) of the H2O component in an albitic melt at ∼565 K and one bar. To extend the determination of to higher temperatures and pressures, the molar volumes of the hydrous albitic liquids determined in this study were combined with those measured by previous authors at 1023–1223 K and 480–840 MPa, leading to the following fitted values (±1) at 1673 K and one bar: (±0.46)×10−3 cm−3/mol-K, and dVˉ H 2 O total /dP=−3.82 (±0.36)×10−4 cm3/mol-bar. The measured molar volumes of this study and those of previous authors can be recovered with a standard deviation of 0.5%, which is within the respective experimental errors. There is a significant difference between the values for derived in this study as a function of temperature and pressure and those obtained from an existing polynomial, primarily caused by the previous absence of accurate density measurements on anhydrous silicate liquids. The coefficients of thermal expansion (=4.72×10−4/K) and isothermal compressibility ( T =1.66×10−5/bar) for the H2O component at 1273 K and 100 MPa, indicate that H2Ototal is the single most expansive and compressible component in silicate liquids. For example, at 1473 K and 70 MPa (conditions of a mid-ocean ridge crustal magma chamber), the presence of just 0.4 wt% H2O will decrease the density of a basaltic liquid by more than one percent. An equivalent decrease in melt density could be achieved by increasing the temperature by 175 degrees or the decreasing pressure by 230 MPa. Therefore, even minor quantities of dissolved water will have a marked effect on the dynamic properties of silicate liquids in the crustal environment. Received: 20 August 1996 / Accepted: 15 March 1997  相似文献   

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