Dissolution Kinetics of Dolomite in Water at Elevated Temperatures   总被引：1，自引：0，他引：1  

Ronghua Zhang  Shumin Hu  Xuetong Zhang  Wenbin Yu 《Aquatic Geochemistry》2007,13(4):309-338

Kinetic experiments of dolomite dissolution in water over a temperature range from 25 to 250°C were performed using a flow through packed bed reactor. Authors chose three different size fractions of dolomite samples: 18–35 mesh, 35–60 mesh, and 60–80 mesh. The dissolution rates of the three particle size samples of dolomite were measured. The dissolution rate values are changed with the variation of grain size of the sample. For the sample through 20–40 mesh, both the release rate of Ca and the release rate of Mg increase with increasing temperature until 200°C, then decrease with continued increasing temperature. Its maximum dissolution rate occurs at 200°C. The maximum dissolution rates for the sample through 40–60 mesh and 60–80 mesh happen at 100°C. Experimental results indicate that the dissolution of dolomite is incongruent in most cases. Dissolution of fresh dolomite was non-stoichiometric, the Ca/Mg ratio released to solution was greater than in the bulk solid, and the ratio increases with rising temperatures from 25 to 250°C. Observations on dolomite dissolution in water are presented as three parallel reactions, and each reaction occurs in consecutive steps as where the second part is a slow reaction, and also the reaction could occur as follows: The following rate equation was used to describe dolomite dissolution kinetics where refers to one of each reaction among the above reactions; k _ij is the rate constant for ith species in the jth reaction, a _i stands for activity of ith aqueous species, n is the stoichimetric coefficience of ith species in the jth reaction, and define . The experiments prove that dissolved Ca is a strong inhibitor for dolomite dissolution (release of Ca) in most cases. Dissolved Mg was found to be an inhibitor for dolomite dissolution at low temperatures. But dissolution rates of dolomite increase with increasing the concentration of dissolved Mg in the temperature range of 200–250°C for 20–40 mesh sample, and in the temperature range of 100–250°C for 40–80 mesh sample, whereas the Mg²⁺ ion adsorption on dolomite surface becomes progressively the step controlling reaction. The following rate equation is suitable to dolomite dissolutions at high temperatures from 200 to 250°C.where refers to dissolution rate (release of Ca), and are molar concentrations of dissolved Ca and Mg, k _ad stands for adsorption reaction rate constant, K _Mg refers to adsorption equilibrium constant. At 200°C for 40–60 mesh sample, the release rate of Ca can be described as:  相似文献   

Ca-Fe-Mg olivines: phase relations and a solution model     

Paula M. Davidson  Dilip K. Mukhopadhyay 《Contributions to Mineralogy and Petrology》1984,86(3):256-263

Reversed phase equilibrium experiments in the system (Ca, Mg, Fe)₂SiO₄ provide four tielines at P?1 bar and 1 kbar and 800° C–1,100° C. These tielines have been used to model the solution properties of the olivine quadrilateral following the methods described by Davidson et al. (1981) for quadrilateral clinopyroxenes. The discrepancy between the calculated phase relations and the experimentally determined tielines is within the uncertainty of the experiments. The solution properties of quadrilateral olivines can be described by a non-convergent site-disorder model that allows for complete partitioning of Ca on the M2 site, highly disordered Fe-Mg cation distributions and limited miscibility between high-Ca and low-Ca olivines. The ternary data presented in this paper together with binary solution models for the joins Fo-Mo and Fa-Kst have been used to evaluate two solution parameters: $$\begin{gathered} F^0 \equiv 2(\mu _{{\rm M}o}^0 - \mu _{{\rm K}st}^0 ) + \mu _{Fa}^0 - \mu _{Fo}^0 = 12.660 (1.6) kJ, \hfill \\ \Delta G_*^0 \equiv \mu _{{\rm M}gFe}^0 + \mu _{FeMg}^0 - \mu _{Fo}^0 - \mu _{Fa}^0 = 7.030 (3.9) kJ. \hfill \\ \end{gathered} $$ . Ternary phase quilibrium data for olivines tightly constrain the value of F⁰, but not that for ΔG _* ⁰ which describes nonideality in Fe-Mg mixing. From this analysis, we infer a function for the apparent standard state energy of Kst: $$\begin{gathered} \mu _{{\rm K}st}^0 = - 102.79 \pm 0.8 - (T - 298)(0.137026) \hfill \\ + (T - 298 - T1n(T/298))(0.155519) \hfill \\ + (T - 298)^2 (2.8242E - 05)/2 \hfill \\ + (T - 298)^2 (2.9665E + 03)/(2T(298)^2 ) kJ \hfill \\ \end{gathered} $$ where T is in Kelvins and the 298 K value is relative to oxides.  相似文献   

Appraisal of groundwater quality in a crystalline aquifer: a chemometric approach     

P. D. Sreedevi  P. D. Sreekanth  S. Ahmed  D. V. Reddy 《Arabian Journal of Geosciences》2018,11(9):211

The purpose of this study is to assess the groundwater quality and identify the processes that control the groundwater chemistry in a crystalline aquifer. A total of 72 groundwater samples were collected during pre- and post-monsoon seasons in the year 2014 in a semi-arid region of Gooty Mandal, Anantapur district, Andhra Pradesh, India. The study utilized chemometric analysis like basic statistics, Pearson’s correlation coefficient (r), principal component analysis (PCA), Gibbs ratio, and index of base exchange to understand the mechanism of controlling the groundwater chemistry in the study area. The results reveal that groundwater in the study area is neutral to slightly alkaline in nature. The order of dominance of cations is Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ while for anions, it is \( {\mathrm{HCO}}_3^{-}>{\mathrm{Cl}}^{-} \)>\( {\mathrm{NO}}_3^{-} \)>\( {\mathrm{SO}}_4^{2-} \)>\( {\mathrm{CO}}_3^{2-}>{\mathrm{F}}^{-} \) in both seasons. Based on the Piper classification, most of the groundwater samples are identified as of sodium bicarbonate (\( {\mathrm{Na}}^{+}-{\mathrm{HCO}}_3^{-}\Big) \) type. According to the results of the principal component analysis (PCA), three factors and two factors were identified pre and post monsoon, respectively. The present study indicates that the groundwater chemistry is mostly controlled by geogenic processes (weathering, dissolution, and ion exchange) and some extent of anthropogenic activities.  相似文献   

Paragenesis of unusual Fe-cordierite (sekaninaite)-bearing paralava and clinker from the Kuznetsk coal basin,Siberia, Russia     

Rodney Grapes  Sophia Korzhova  Ella Sokol  Yurii Seryotkin 《Contributions to Mineralogy and Petrology》2011,162(2):253-273

Sekaninaite (X_Fe > 0.5)-bearing paralava and clinker are the products of ancient combustion metamorphism in the western part of the Kuznetsk coal basin, Siberia. The combustion metamorphic rocks typically occur as clinker beds and breccias consisting of vitrified sandstone–siltstone clinker fragments cemented by paralava, resulting from hanging-wall collapse above burning coal seams and quenching. Sekaninaite–Fe-cordierite (X_Fe = 95–45) is associated with tridymite, fayalite, magnetite, ± clinoferrosilite and ±mullite in paralava and with tridymite and mullite in clinker. Unmelted grains of detrital quartz occur in both rocks (<3 vol% in paralavas and up to 30 vol% in some clinkers). Compositionally variable siliceous, K-rich peraluminous glass is <30% in paralavas and up to 85% in clinkers. The paralavas resulted from extensive fusion of sandstone–siltstone (clinker), and sideritic/Fe-hydroxide material contained within them, with the proportion of clastic sediments ≫ ferruginous component. Calculated dry liquidus temperatures of the paralavas are 1,120–1,050°C and 920–1,050°C for clinkers, with calculated viscosities at liquidus temperatures of 10^1.6–7.0 and 10^7.0–9.8 Pa s, respectively. Dry liquidus temperatures of glass compositions range between 920 and 1,120°C (paralava) and 920–960°C (clinker), and viscosities at these temperatures are 10^9.7–5.5 and 10^8.8–9.7 Pa s, respectively. Compared with worldwide occurrences of cordierite–sekaninaite in pyrometamorphic rocks, sekaninaite occurs in rocks with X_Fe (mol% FeO/(FeO + MgO)) > 0.8; sekaninaite and Fe-cordierite occur in rocks with X_Fe 0.6–0.8, and cordierite (X_Fe < 0.5) is restricted to rocks with X_Fe < 0.6. The crystal-chemical formula of an anhydrous sekaninaite based on the refined structure is | \textK_0.02 |(\textFe_1.54^{2 +} \textMg_0.40 \textMn_0.06 )_{\Upsigma 2.00}^M [(\textAl_1.98 \textFe_0.02^{2 +} \textSi_1.00 )_{\Upsigma 3.00}^T1 (\textSi_3.94 \textAl_2.04 \textFe_0.02^{2 +} )_{\Upsigma 6.00}^T2 \textO₁₈ ]. \left| {{\text{K}}_{0.02} } \right|({\text{Fe}}_{1.54}^{2 + } {\text{Mg}}_{0.40} {\text{Mn}}_{0.06} )_{\Upsigma 2.00}^{M} [({\text{Al}}_{1.98} {\text{Fe}}_{0.02}^{2 + } {\text{Si}}_{1.00} )_{\Upsigma 3.00}^{T1} ({\text{Si}}_{3.94} {\text{Al}}_{2.04} {\text{Fe}}_{0.02}^{2 + } )_{\Upsigma 6.00}^{T2} {\text{O}}_{18} ].  相似文献   

The solubility of calcite in water at 6–16 kbar and 500–800 °C     

Natalie?C.?CaciagliEmail author  Craig?E.?Manning 《Contributions to Mineralogy and Petrology》2003,146(3):275-285

The solubility of calcite in H₂O was measured at 6–16 kbar, 500–800 °C, using a piston-cylinder apparatus. The solubility was determined by the weight loss of a single crystal and by direct analysis of the quench fluid. Calcite dissolves congruently in the pressure (P) and temperature (T) range of this study. At 10 kbar, calcite solubility increases with increasing temperature from 0.016±0.005 molal at 500 °C to 0.057±0.022 molal at 750 °C. The experiments reveal evidence for hydrous melting of calcite between 750 and 800 °C. Solubilities show only a slight increase with increasing P over the range investigated. Comparison with work at low P demonstrates that the P dependence of calcite solubility is large between 1 and 6 kbar, increasing at 500 °C from 1.8×10^–5 molal at 1 kbar to 6.4×10^–3 molal at 6 kbar. The experimental results are described by:where T is in Kelvin and _H2O is the density of pure water in g/cm³. The equation is applicable at 1–20 kbar and 400–800 °C, where calcite and H₂O stably coexist. Extrapolated thermodynamic data for indicates that the dominant dissolved carbon species is CO_2,aq at all experimental conditions. The results require that equilibrium constant for the reaction:increases by several orders of magnitude between 1 and 6 kbar, and also rises with isobaric T increase. Published thermodynamic data for aqueous species fail to predict this behavior. The increase in calcite solubility with P and T demonstrates that there is a strong potential for calcite precipitation during cooling and decompression of water-rich metamorphic fluids sourced in the middle to lower crust.Editorial responsibility: T.L. Grove  相似文献   

Majoritic garnet grains within shock-induced melt veins in amphibolites from the Ries impact crater suggest ultrahigh crystallization pressures between 18 and 9 GPa     

Volker?St?hle  Rainer?AltherrEmail author  Lutz?Nasdala  Mario?Trieloff  Alexander?Varychev 《Contributions to Mineralogy and Petrology》2017,172(10):86

Shock-induced melt veins in amphibolites from the Nördlinger Ries often have chemical compositions that are similar to bulk rock (i.e., basaltic), but there are other veins that are confined to chlorite-rich cracks that formed before the impact and these are poor in Ca and Na. Majoritic garnets within the shock veins show a broad chemical variation between three endmembers: (1) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}{\text{Al}}_{2} ({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (normal garnet, Grt), (2) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}[{\text{M}}^{2 + } ({\text{Si,Ti}})]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\)  (majorite, Maj), and (3) \({}^{\text{VIII}}({{\text {Na} {\text M}^{2+}}_2}) {}^{\text{VI}}[ ({\text{Si,Ti}}){\text {Al}}]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (Na-majorite₅₀Grt₅₀), whereby M²⁺ = Mg²⁺, Fe²⁺, Mn²⁺, Ca²⁺. In particular, we observed a broad variation in ^VI(Si,Ti) which ranges from 0.12 to 0.58 cations per formula unit (cpfu). All these majoritic garnets crystallized during shock pressure release at different ultrahigh pressures. Those with high ^VI(Si,Ti) (0.36–0.58 cpfu) formed at high pressures and temperatures from amphibole-rich melts, while majoritic garnets with lower ^VI(Si,Ti) of 0.12–0.27 cpfu formed at lower pressures and temperatures from chlorite-rich melts. Furthermore, majoritic garnets with intermediate values of ^VI(Si,Ti) (0.24–0.39) crystallized from melts with intermediate contents of Ca and Na. To the best of our knowledge the ‘MORB-type’ Ca–Na-rich majoritic garnets with maximum contents of 2.99 wt% Na₂O and calculated crystallisation pressures of 16–18 GPa are the most extreme representatives ever found in terrestrial shocked materials. At the Ries, the duration of the initial contact and compression stage at the central location of impact is estimated to only ~ 0.1 s. We used a ~ 200-µm-thick shock-induced vein in a moderately shocked amphibolite to model its pressure–temperature–time (P–T–t) path. The graphic model manifests a peak temperature of ~ 2600 °C for the vein, continuum pressure lasting for ~ 0.02 s, a quench duration of ~ 0.02 s and a shock pulse of ~ 0.038 s. The small difference between the continuum pressure and the pressure of majoritic garnet crystallization underlines the usefulness of applying crystallisation pressures of majoritic garnets from metabasites for calculation of dynamic shock pressures of host rocks. Majoritic garnets of chlorite provenance, however, are not suitable for the determination of continuum pressure since they crystallized relatively late during shock release. An extraordinary glass- and majorite-bearing amphibole fragment in a shock-vein of one amphibolite documents the whole unloading path.  相似文献   

Opening and resetting temperatures in heating geochronological systems   总被引：2，自引：0，他引：2  

Emmanuel Gardés  Jean-Marc Montel 《Contributions to Mineralogy and Petrology》2009,158(2):185-195

We present a theoretical model for diffusive daughter isotope loss in radiochronological systems with increasing temperature. It complements previous thermochronological models, which focused on cooling, and allows for testing opening and resetting of radiochronometers during heating. The opening and resetting temperatures are, respectively,where R is the gas constant, E and D ₀ are the activation energy and the pre-exponential factor of the Arrhenius law for diffusion of the daughter isotope, a the half-size of the system (radius for sphere and cylinder and half-thickness for plane sheet) and τ the heating time constant, related to the heating rate by For opening and resetting thresholds corresponding to 1 and 99% loss of daughter isotope, respectively, the retention parameters for sphere, cylinder and plane sheet geometries are A _op = 1.14 × 10⁵, 5.07 × 10⁴ and 1.27 × 10⁴ and A _rs = 2.40, 1.37 and 0.561. According to this model, the opening and resetting temperatures are significantly different for most radiochronometers and are, respectively, lower and higher than the closure temperature. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

Ephesite,Na(LiAl2) [Al2Si2O10] (OH)2: I. thermal stability and standard state thermodynamic properties     

Udo Warhus  Niranjan D. Chatterjee 《Contributions to Mineralogy and Petrology》1984,85(1):74-79

Ephesite, Na(LiAl₂) [Al₂Si₂O₁₀] (OH)₂, has been synthesized for the first time by hydrothermal treatment of a gel of requisite composition at 300≦T(° C)≦700 and \(P_{H_2 O}\) upto 35 kbar. At \(P_{H_2 O}\) between 7 and 35 kbar and above 500° C, only the 2M₁ polytype is obtained. At lower temperatures and pressures, the 1M polytype crystallizes first, which then inverts to the 2M₁ polytype with increasing run duration. The X-ray diffraction patterns of the 1M and 2M₁ poly types can be indexed unambiguously on the basis of the space groups C2 and Cc, respectively. At its upper thermal stability limit, 2M₁ ephesite decomposes according to the reaction (1) $$\begin{gathered} {\text{Na(LiAl}}_{\text{2}} {\text{) [Al}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{{\text{10}}} {\text{] (OH)}}_{\text{2}} \hfill \\ {\text{ephesite}} \hfill \\ {\text{ = Na[AlSiO}}_{\text{4}} {\text{] + LiAl[SiO}}_{\text{4}} {\text{] + }}\alpha {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}} {\text{ + H}}_{\text{2}} {\text{O}} \hfill \\ {\text{nepheline }}\alpha {\text{ - eucryptite corundum}} \hfill \\ \end{gathered}$$ Five reversal brackets for (1) have been established experimentally in the temperature range 590–750° C, at \(P_{H_2 O}\) between 400 and 2500 bars. The equilibrium constant, K, for this reaction may be expressed as (2) $$log K{\text{ = }}log f_{{\text{H}}_{\text{2}} O}^* = 7.5217 - 4388/T + 0.0234 (P - 1)T$$ where \(f_{H_2 O}^* = f_{H_2 O} (P,T)/f_{H_2 O}^0\) (1,T), with T given in degrees K, and P in bars. Combining these experimental data with known thermodynamic properties of the decomposition products in (1), the following standard state (1 bar, 298.15 K) thermodynamic data for ephesite were calculated: H _f,298.15 ⁰ =-6237372 J/mol, S _298.15 ⁰ =300.455 J/K·mol, G _298.15 ⁰ =-5851994 J/mol, and V _298.15 ⁰ =13.1468 J/bar·mol.  相似文献   

The magnesiowüstite: iron equilibrium and its implications for the activity-composition relations of (Mg,Fe)<Subscript>2</Subscript>SiO<Subscript>4</Subscript> olivine solid solutions     

Hugh?St. C.?O'NeillEmail author  Mark?I.?Pownceby  Catherine?A.?McCammon 《Contributions to Mineralogy and Petrology》2003,146(3):308-325

The chemical potential of oxygen (µO₂) in equilibrium with magnesiowüstite solid solution (Mg, Fe)O and metallic Fe has been determined by gas-mixing experiments at 1,473 K supplemented by solid-cell EMF experiments at lower temperatures. The results give:where IW refers to the Fe-"FeO" equilibrium. The previous work of Srecec et al. (1987) and Wiser and Wood (1991) agree well with this equation, as does that of Hahn and Muan (1962) when their reported compositions are corrected to a new calibration curve for lattice parameter vs. composition. The amount of Fe³⁺ in the magnesiowüstite solid solution in equilibrium with Fe metal was determined by Mössbauer spectroscopy on selected samples. These data were combined with literature data from gravimetric studies and fitted to a semi-empirical equation:These results were then used to reassess the activity-composition relations in (Mg, Fe)₂SiO₄ olivine solid solutions at 1,400 K, from the partitioning of Mg and Fe²⁺ between olivine and magnesiowüstite in equilibrium with metallic Fe experimentally determined by Wiser and Wood (1991). The olivine solid solution is constrained to be nearly symmetric with , with a probable uncertainty of less than ±0.5 kJ/mol (one standard deviation). The results also provide a useful constraint on the free energy of formation of Mg₂SiO₄.Editorial responsibility: B. Collins  相似文献   

Energetics of hydration of cordierite and water barometry in cordierite-granulites     

A. Bhattacharya  S. K. Sen 《Contributions to Mineralogy and Petrology》1985,89(4):370-378

The Gibbs free energy and volume changes attendant upon hydration of cordierites in the system magnesian cordierite-water have been extracted from the published high pressure experimental data at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P _total, assuming an ideal one site model for H₂O in cordierite. Incorporating the dependence of ΔG and ΔV on temperature, which was found to be linear within the experimental conditions of 500°–1,000°C and 1–10,000 bars, the relation between the water content of cordierite and P, T and \(f_{{\text{H}}_{\text{2}} {\text{O}}} \) has been formulated as $$\begin{gathered} X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} = \hfill \\ \frac{{f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }}{{\left[ {{\text{exp}}\frac{1}{{RT}}\left\{ {64,775 - 32.26T + G_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{1, }}T} - P\left( {9 \times 10^{ - 4} T - 0.5142} \right)} \right\}} \right] + f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }} \hfill \\ \end{gathered} $$ The equation can be used to compute H₂O in cordierites at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) <1. Our results at different P, T and partial pressure of water, assuming ideal mixing of H₂O and CO₂ in the vapour phase, are in very good agreement with the experimental data of Johannes and Schreyer (1977, 1981). Applying the formulation to determine \(X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} \) in the garnet-cordierite-sillimanite-plagioclase-quartz granulites of Finnish Lapland as a test case, good agreement with the gravimetrically determined water contents of cordierite was obtained. Pressure estimates, from a thermodynamic modelling of the Fe-cordierite — almandine — sillimanite — quartz equilibrium at \(P_{{\text{H}}_{\text{2}} {\text{O}}} = 0\) and \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P_total, for assemblages from South India, Scottish Caledonides, Daly Bay and Hara Lake areas are compatible with those derived from the garnetplagioclase-sillimanite-quartz geobarometer.  相似文献   

(Ca,Mg)2Si2O6 clinopyroxenes: A solution model based on nonconvergent site-disorder     

Paula M. Davidson  John Grover  Donald H. Lindsley 《Contributions to Mineralogy and Petrology》1982,80(1):88-102

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   

Oxygen isotope fractionation between rutile and water   总被引：1，自引：0，他引：1  

Sunit K. Addy  G. D. Garlick 《Contributions to Mineralogy and Petrology》1974,45(2):119-121

Synthetic rutile-water fractionations (1000 ln α) at 775, 675, and 575° C were found to be ?2.8, ?3.5, and ?4.8, respectively. Partial exchange experiments with natural rutile at 575° C and with synthetic rutile at 475° C failed to yield reliable fractionations. Isotopic fractionation within the range 575–775° C may be expressed as follows: 1 $$1000\ln \alpha ({\rm T}i{\rm O}_{2 } - H_2 O) = - 4.1 \frac{{10^6 }}{{T_{k^2 } }} + 0.96$$ . Combined with previously determined quartz-water fractionations, the above data permit calibration of the quartz-rutile geothermometer: 1 $$1000\ln \alpha ({\text{S}}i{\rm O}_{2 } - Ti{\rm O}_{2 } ) = 6.6 \frac{{10^6 }}{{T_{k^2 } }} - 2.9$$ . When applied to B-type eclogites from Europe, as an example, the latter equation yields a mean equilibration temperature of 565° C.  相似文献   

Heat capacity of hydrous trachybasalt from Mt Etna: comparison with CaAl<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript> (An)–CaMgSi<Subscript>2</Subscript>O<Subscript>6</Subscript> (Di) as basaltic proxy compositions     

D.?GiordanoEmail author  A.?R.?L.?Nichols  M.?Potuzak  D.?Di?Genova  C.?Romano  J.?K.?Russell 《Contributions to Mineralogy and Petrology》2015,170(5-6):48

The specific heat capacity (C _p) of six variably hydrated (~3.5 wt% H₂O) iron-bearing Etna trachybasaltic glasses and liquids has been measured using differential scanning calorimetry from room temperature across the glass transition region. These data are compared to heat capacity measurements on thirteen melt compositions in the iron-free anorthite (An)–diopside (Di) system over a similar range of H₂O contents. These data extend considerably the published C _p measurements for hydrous melts and glasses. The results for the Etna trachybasalts show nonlinear variations in, both, the heat capacity of the glass at the onset of the glass transition (i.e., C _p ^g ) and the fully relaxed liquid (i.e., C _p ^l ) with increasing H₂O content. Similarly, the “configurational heat capacity” (i.e., C _p ^c  = C _p ^l  ? C _p ^g ) varies nonlinearly with H₂O content. The An–Di hydrous compositions investigated show similar trends, with C _p values varying as a function of melt composition and H₂O content. The results show that values in hydrous C _p ^g , C _p ^l and C _p ^c in the depolymerized glasses and liquids are substantially different from those observed for more polymerized hydrous albitic, leucogranitic, trachytic and phonolitic multicomponent compositions previously investigated. Polymerized melts have lower C _p ^l and C _p ^c and higher C _p ^g with respect to more depolymerized compositions. The covariation between C _p values and the degree of polymerization in glasses and melts is well described in terms of SM_hydrous and NBO/T _hydrous. Values of C _p ^c increase sharply with increasing depolymerization up to SM_hydrous ~ 30–35 mol% (NBO/T _hydrous ~ 0.5) and then stabilize to an almost constant value. The partial molar heat capacity of H₂O for both glasses (\( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{g}} \)) and liquids (\( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \)) appears to be independent of composition and, assuming ideal mixing, we obtain a value for \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \) of 79 J mol^?1 K^?1. However, we note that a range of values for \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \) (i.e., ~78–87 J mol^?1 K^?1) proposed by previous workers will reproduce the extended data to within experimental uncertainty. Our analysis suggests that more data are required in order to ascribe a compositional dependence (i.e., nonideal mixing) to \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \).  相似文献   

Aluminum partitioning between olivine and ultrabasic silicate liquid to 6 GPa     

Carl B. Agee  David Walker 《Contributions to Mineralogy and Petrology》1990,105(3):243-254

Trace element analyses of 1-atm and high-pressure experiments show that in komatiite and peridotite, the olivine (OL)/liquid (L) distribution coefficient for Al₂O₃ ( ) increases with pressure and temperature. Olivine in equilibrium with liquid accepts as much as 0.2 wt% Al₂O₃ in solution at 6 GPa. Convergence to equilibrium compositions at this high level is shown by cation diffusion of Al into synthetic forsterite crystals of low-Al contents in the presence of melt. Convergence to low-Al equilibrium compositions at lower P and T is shown by diffusion of Al out of synthetic forsterite with high initial Al content. Isobaric and isothermal experimental data subsets reveal that temperature and pressure variations both have real effects on . Variation in silicate melt composition has no detectable effect on within the limited range of experimentally investigated mixtures. Least-squares regression for 24 experiments, using komatiite and peridotite, performed at 1 atm to 6 GPa and 1300 to 1960°C, gives the best fit equation: Increase in with increasingly higher-pressure melting is consistent with incorporation of a spinel-like component of low molar volume into olivine, although other substitutions possibly involving more complex coupling cannot be ruled out. High P-T ultrabasic melting residues, if pristine, may be recognized by the high calculated from microprobe analyses of Al₂O₃ concentrations in residual olivines and estimated Al₂O₃ concentration in the last liquid removed. In general the low levels of Al in natural olivine from mantle xenoliths suggest that pristine residues are rarely recovered.  相似文献