首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 46 毫秒
1.
Partition coefficients (D) for Nb and Ta between rutile and haplogranite melts in the K2O-Al2O3-SiO2 system have been measured as functions of the K2O/Al2O3 ratio, the concentrations of Nb2O5 and Ta2O5, the temperature, in air and at 1 atmosphere pressure. The Ds increase in value as the K* [K2O/(K2O + Al2O3)] molar ratio continuously decreases from highly peralkaline [K* ∼ 0.9] to highly peraluminous [K* ∼ 0.35] melts. The D values increase more dramatically with a unit decrease in K* in peraluminous melts than in peralkaline melts. This compositional dependence of Ds can be explained by the high activity of NbAlO4 species in peraluminous melts and the high activity of KONb species (or low activity of NbAlO4 species) in peralkaline melts. A coupled substitution, Al+3 + Nb+5 (or Ta+5) = 2Ti+4, accounts for the Ds of Nb (Ta) being much greater in peraluminous melts than in peralkaline melts because this substitution allows Nb (Ta) to enter into the rutile structure more easily. The Ds of Ta between rutile and melt are greater than those of Nb at comparable concentrations because the molecular electronic polarizability of Ta is weaker than that of Nb. The Nb+5 with a large polarizing power forms a stronger covalent bond with oxygen than Ta+5 with a small polarizing power. The formation of the strong bond, Nb-O, distorts the rutile structure more severely than the weak bond, Ta-O; therefore, it is easier for Ta to partition into rutile than for Nb. These results imply that the utilization of the Nb/Ta ratio in liquid as a petrogenetic indicator in granitic melts must be done with caution if rutile (or other TiO2-rich phases) is a liquidus phase. The crystallization of rutile will increase the Nb/Ta ratio of the residual liquid because the Ds of Ta between rutile and melts are greater than those of Nb. Received: 28 December 1998 / Accepted 27 September 1999  相似文献   

2.
The behaviour of niobium and tantalum in magmatic processes has been investigated by conducting MnNb2O6 and MnTa2O6 solubility experiments in nominally dry to water-saturated peralkaline (aluminium saturation index, A.S.I. 0.64) to peraluminous (A.S.I. 1.22) granitic melts at 800 to 1035 °C and 800 to 5000 bars. The attainment of equilibrium is demonstrated by the concurrence of the solubility products from dissolution, crystallization, Mn-doped and Nb- or Ta-doped experiments at the same pressure and temperature. The solubility products of MnNb2O6 (Ksp Nb) and MnTa2O6 (Ksp Ta) at 800 °C and 2 kbar both increase dramatically with alkali contents in water-saturated peralkaline melts. They range from 1.2 × 10−4 and 2.6 × 10−4 mol2/kg2, respectively, in subaluminous melt (A.S.I. 1.02) to 202 × 10−4 and 255 × 10−4 mol2/kg2, respectively, in peralkaline melt (A.S.I. 0.64). This increase from the subaluminous composition can be explained by five non-bridging oxygens being required for each excess atom of Nb5+ or Ta5+ that is dissolved into the melt. The Ksp Nb and Ksp Ta also increase weakly with Al content in peraluminous melts, ranging up to 1.7 × 10−4 and 4.6 × 10−4 mol2/kg2, respectively, in the A.S.I. 1.22 composition. Columbite-tantalite solubilities in subaluminous and peraluminous melts (A.S.I. 1.02 and 1.22) are strongly temperature dependent, increasing by a factor of 10 to 20 from 800 to 1035 °C. By contrast columbite-tantalite solubility in the peralkaline composition (A.S.I. 0.64) is only weakly temperature dependent, increasing by a factor of less than 3 over the same temperature range. Similarly, Ksp Nb and Ksp Ta increase by more than two orders of magnitude with the first 3 wt% H2O added to the A.S.I. 1.02 and 1.22 compositions, whereas there is no detectable change in solubility for the A.S.I. 0.64 composition over the same range of water contents. Solubilities are only slightly dependent on pressure over the range 800 to 5000 bars. The data for water-saturated sub- and peraluminous granites have been extrapolated to 600 °C, conditions at which pegmatites and highly evolved granites may crystallize. Using a melt concentration of 0.05 wt% MnO, 70 to 100 ppm Nb or 500 to 1400 ppm Ta are required for manganocolumbite and manganotantalite saturation, respectively. The solubility data are also used to model the fractionation of Nb and Ta between rutile and silicate melts. Predicted rutile/melt partition coefficients increase by about two orders of magnitude from peralkaline to peraluminous granitic compositions. It is demonstrated that the γNb2O5/γTa2O5 activity coefficient ratio in the melt phase depends on melt composition. This ratio is estimated to decrease by a factor of 4 to 5 from andesitic to peraluminous granitic melt compositions. Accordingly, all the relevant accessory phases in subaluminous to peraluminous granites are predicted to incorporate Nb preferentially over Ta. This explains the enrichment of Ta over Nb observed in highly fractionated granitic rocks, and in the continental crust in general. Received: 9 August 1996 / Accepted: 26 February 1997  相似文献   

3.
The redox ratio of iron is used as an indicator of solution properties of silicate liquids in the system (SiO–Al2O3–K2O–FeO–Fe2O3–P2O5). Glasses containing 80–85 mol% SiO2 with 1 mol% Fe2O3 and compositions covering a range of K2O/Al2O3 were synthesized at 1400°C in air (fixed fO2). Variations in the ratio FeO/FeO1.5 resulting from the addition of P2O5 are used to determine the solution behavior of phosphorus and its interactions with other cations in the silicate melt. In 80 mol% SiO2 peralkaline melts the redox ratio, expressed as FeO/FeO1.5, is unchanged relative to the reference curve with the addition of 3 mol% P2O5. Yet, the iron redox ratio in the 85 mol% SiO2 potassium aluminosilicate melts is decreased relative to phosphorus-free liquids even for small amounts of P2O5 (0.5 mol%). The redox ratio in peraluminous melts is decreased relative to phosphorus- free liquids at P2O5 concentrations of 3 mol%. In peraluminous liquids, complexing of both Fe+3–O–P+5 and Al+3–O–P+5 occur. The activity coefficient of Fe+3 is decreased because more ferric iron can be accommodated than in phosphorus-free liquids. In peralkaline melts, there is no evidence that P+5 is removing K+ from either Al+3 or Fe+3 species. In chargebalanced melts with 3 mol% Fe2O3 and very high P2O5 concentrations, phosphorus removes K+ from K–O–Fe+3 complexes resulting in a redox increase. P2O5 should be accommodated easily in peraluminous rhyolitic liquids and phosphate saturation may be suppressed relative to metaluminous rhyolites. In peralkaline melts, phosphate solubility may increase as a result of phosphorus complexing with alkalis. The complexing stoichiometry may be variable, however, and the relative influence of peralkalinity versus temperature on phosphate solubility in rhyolitic melts deserves greater attention.  相似文献   

4.
The compositional dependence of the redox ratio (FeO/FeO1.5) has been experimentally determined in K2O-Al2O3-SiO2-Fe2O3-FeO (KASFF) and K2O-CaO-Al2O3-SiO2-Fe2O3-FeO (KCASFF) silicate melts. Compositions were equilibrated at 1,450° C in air, with 78 mol % SiO2. KASFF melts have from 1 to 5 mol % Fe2O3 and include both peraluminous (K2O2O3) and peralkaline (K2O>Al2O3) compositions. KCASFF melts have 1 mol % Fe2O3 encompassing peraluminous, metaluminous (CaO+K2O>Al2O3) and peralkaline compositions. Peralkaline KASFF melts with 1 mol % Fe2O3 have low and constant values for the redox ratio, whereas in peraluminous melts the redox ratio increases with increasing (K2O/Al2O3). Increasing total iron concentration increases the redox ratio in peraluminous melts and slightly decreases the redox ratio in peralkaline melts. Substituting CaO for K2O at fixed total iron (1 mol %) increases the redox ratio in both peraluminous and metaluminous KCASFF melts; however, the redox ratio in peralkaline KCASFF melts is not affected by this exchange. These data indicate that Fe3+ is in four-fold coordination, with K+ or Ca2+ providing local charge balance. The tetrahedral ferric species is most stable in peralkaline melts and least stable in peraluminous melts, due to the competition between Al3+ and Fe3+ for charge balancing cations in the latter melt. Tetrahedral Fe3+ is also less stable when Ca2+ provides local charge balance. The data are consistent with a network modifying role for Fe2+ in the melt.The data are interpreted to reflect the effects of melt composition on the partitioning of K+ and Ca2+ and Fe3+ and Al3+ between various species in the melt. These relationships are discussed in terms of homogeneous equilibria between various iron-bearing and iron-free melt species. The results also reflect the effect of liquid composition on the exchange potentials Fe3+ Al–1 and Ca0.5K–1. The exchange potentials are relatively constant in peralkaline melts, but decrease in metaluminous and peraluminous melts as both (CaO+K2O)/(CaO+K2O+Al2O3) and K2O/CaO decrease. These qualitative observations imply that minerals exhibiting these exchanges will also be similarly affected as liquid composition changes. Present address: Department of Geological Sciences, Virginia Tech, Blacksburg, VA 24061, USA  相似文献   

5.
The configurational heat capacity, shear modulus and shear viscosity of a series of Na2O–Fe2O3–Al2O3–SiO2 melts have been determined as a function of composition. A change in composition dependence of each of the physical properties is observed as Na2O/(Na2O + Al2O3) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts. Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous, the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time. As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to the lack of charge-balancing cations for the Al-tetrahedra.  相似文献   

6.
Structural interaction between dissolved fluorine and silicate glass (25°C) and melt (to 1400°C) has been examined with 19F and 29Si MAS NMR and with Raman spectroscopy in the system Na2O-Al2O3-SiO2 as a function of Al2O3 content. Approximately 3 mol.% F calculated as NaF dissolved in these glasses and melts. From 19F NMR spectroscopy, four different fluoride complexes were identified. These are (1) Na-F complexes (NF), (2) Na-Al-F complexes with Al in 4-fold coordination (NAF), (3) Na-Al-F complexes with Al in 6-fold coordination with F (CF), and (4) Al-F complexes with Al in 6-fold, and possibly also 4-fold coordination (TF). The latter three types of complexes may be linked to the aluminosilicate network via Al-O-Si bridges.The abundance of sodium fluoride complexes (NF) decreases with increasing Al/(Al + Si) of the glasses and melts. The NF complexes were not detected in meta-aluminosilicate glasses and melts. The NAF, CF, and TF complexes coexist in peralkaline and meta-aluminosilicate glasses and melts.From 29Si-NMR spectra of glasses and Raman spectra of glasses and melts, the silicate structure of Al-free and Al-poor compositions becomes polymerized by dissolution of F because NF complexes scavenge network-modifying Na from the silicate. Solution of F in Al-rich peralkaline and meta-aluminous glasses and melts results in Al-F bonding and aluminosilicate depolymerization.Temperature (above that of the glass transition) affects the Qn-speciation reaction in the melts, 2Q3 ⇔ Q4 + Q2, in a manner similar to other alkali silicate and alkali aluminosilicate melts. Dissolved F at the concentration level used in this study does not affect the temperature-dependence of this speciation reaction.  相似文献   

7.
The relationship between the redox ratio Fe+2/(Fe+2+Fe+3) and the K2O/(K2O + Al2O3) ratio (K2O*) were experimentally investigated in silicate melts with 78 mol% SiO2 in the system SiO2-Al2O3-K2O-FeO-Fe2O3, in air at 1,400° C. Quenched glass compositions were analyzed by electron microprobe and wet chemical microtitration techniques. Minimum values of the redox ratio were obtained at K2O*0.5. The redox ratio in peralkaline melts (K2O*>0.5) increases slightly with K2O* whereas this ratio increases dramatically in peraluminous melts (K2O*<0.5) as K2O is replaced by Al2O3. These data indicate that all Fe+3 (and Al+3) occur as tetrahedral species charge balanced with K+ in peralkaline melts. In peraluminous melts, Fe+3 (and Al+3) probably occur as both tetrahedral species using Fe+2 as a charge-balancing cation and as network-modifying cations associated with non-bridging oxygen.  相似文献   

8.
The saturation surface of pseudobrookite (Fe2TiO5) was determined for melts in the system SiO2-Al2O3-K2O-FeO-Fe2O3-TiO2 at 1400° C and 1 atm. The variation in concentrations of Fe2O3, TiO2 and Fe2TiO5 in liquids can be used to infer relative changes in activity coefficients of these components with changing K2O/(K2O+Al2O3) of the melts. Saturation concentrations of these components are low and relatively constant in the peraluminous melts and increase with increasing K2O/(K2O+Al2O3) in peralkaline liquids. The activity coefficients of Fe2O3 and TiO2 and Fe2TiO5, therefore, are higher in peraluminous liquids than in peralkaline liquids in this system. In addition, the iron redox ratio was measured as a function of K2O/(K2O+Al2O3) for liquids just below the saturation surface; was fixed so all variations in redox ratio are entirely due to changes in melt composition. The redox ratio from unsaturated liquids was applied to saturated liquids where redox analysis of the glass is impossible. The homogeneous equilibrium experiments indicate that the activity coefficient of Fe2O3 relative to that of FeO is significantly greater in peraluminous melts than peralkaline melts. Both the heterogeneous and homogeneous equilibria suggest that in peralkaline liquids K+in excess of that required to charge balance tetrahedral Al+3 is used to stabilize both Fe+3 and Ti+4. Calculations show that ferric iron and titanium compete equally effectively for charge-balancing potassium but neither can outcompete aluminum. The observed changes in solution properties of Fe2O3 and TiO2 in the synthetic melts are used to explain variations in Fe-Ti oxide stabilities in natural peraluminous and peralkaline rhyolites and granites. Since the activity coefficients of both ferric iron and titanium are significantly higher in peraluminous liquids than in peralkaline liquids, Fe-Ti oxides should occur earlier in the crystallization sequence in peraluminous rhyolites than in peralkaline rhyolites. In addition, iron will be reduced in peraluminous granites and rhyolites relative to peralkaline ones under comparable P, T, and . Finally, observed crystallization patterns for minerals containing highly charged cations other than ferric iron and titanium are evaluated in the context of this and other experimental studies.  相似文献   

9.
The behavior of tantalum and zirconium in pegmatitic systems has been investigated through the determination of Ta and Zr solubilities at manganotantalite and zircon saturation from dissolution and crystallization experiments in hydrous, Li-, F-, P- and B-bearing pegmatitic melts. The pegmatitic melts are synthetic and enriched in flux elements: 0.7–1.3 wt% Li2O, 2–5.5 wt% F, 2.8–4 wt% P2O5 and 0–2.8 wt% B2O3, and their aluminum saturation index ranges from peralkaline to peraluminous (ASILi = Al/[Na + K + Li] = 0.8 to 1.3) with various K/Na ratios. Dissolution and crystallization experiments were conducted at temperatures varying between 700 and 1,150°C, at 200 MPa and nearly water-saturated conditions. For dissolution experiments, pure synthetic, end member manganotantalite and zircon were used in order to avoid problems with slow solid-state kinetics, but additional experiments using natural manganotantalite and zircon of relatively pure composition (i.e., close to end member composition) displayed similar solubility results. Zircon and manganotantalite solubilities considerably increase from peraluminous to peralkaline compositions, and are more sensitive to changes in temperature or ASI of the melt than to flux content. A model relating the enthalpy of dissolution of manganotantalite to the ASILi of the melt is proposed: ∆H diss (kJ/mol) = 304 × ASILi − 176 in the peralkaline field, and ∆H diss (kJ/mol) = −111 × ASILi + 245 in the peraluminous field. The solubility data reveal a small but detectable competitivity between Zr and Ta in the melt, i.e., lower amounts of Zr are incorporated in a Ta-bearing melt compared to a Ta-free melt under the same conditions. A similar behavior is observed for Hf and Ta. The competitivity between Zr (or Hf) and Ta increases from peraluminous to peralkaline compositions, and suggests that Ta is preferentially bonded to non-bridging oxygens (NBOs) with Al as first-neighbors, whereas Zr is preferentially bonded to NBOs formed by excess alkalies. As a consequence Zr/Ta ratios, when buffered by zircon and manganotantalite simultaneously, are higher in peralkaline melts than in peraluminous melts.  相似文献   

10.
Experiments have been conducted in a peralkaline Ti-KNCMASH system representative of MARID-type bulk compositions to delimit the stability field of K-richterite in a Ti-rich hydrous mantle assemblage, to assess the compositional variation of amphibole and coexisting phases as a function of P and T, and to characterise the composition of partial melts derived from the hydrous assemblage. K-richterite is stable in experiments from 0.5 to 8.0 GPa coexisting with phlogopite, clinopyroxene and a Ti-phase (titanite, rutile or rutile + perovskite). At 8.0 GPa, garnet appears as an additional phase. The upper T stability limit of K-richterite is 1200–1250 °C at 4.0 GPa and 1300–1400 °C at 8.0 GPa. In the presence of phlogopite, K-richterite shows a systematic increase in K with increasing P to 1.03 pfu (per formula unit) at 8.0 GPa/1100 °C. In the absence of phlogopite, K-richterite attains a maximum of 1.14 K pfu at 8.0 GPa/1200 °C. Titanium in both amphibole and mica decreases continuously towards high P with a nearly constant partitioning while Ti in clinopyroxene remains more or less constant. In all experiments below 6.0 GPa ΣSi + Al in K-richterite is less than 8.0 when normalised to 23 oxygens+stoichiometric OH. Rutiles in the Ti-KNCMASH system are characterised by minor Al and Mg contents that show a systematic variation in concentration with P(T) and the coexisting assemblage. Partial melts produced in the Ti-KNCMASH system are extremely peralkaline [(K2O+Na2O)/Al2O3 = 1.7–3.7], Si-poor (40–45 wt% SiO2), and Ti-rich (5.6–9.2 wt% TiO2) and are very similar to certain Ti-rich lamproite glasses. At 4.0 GPa, the solidus is thought to coincide with the K-richterite-out reaction, the first melt is saturated in a phlogopite-rutile-lherzolite assemblage. Both phlogopite and rutile disappear ca. 150 °C above the solidus. At 8.0 GPa, the solidus must be located at T≤1400 °C. At this temperature, a melt is in equilibrium with a garnet- rutile-lherzolite assemblage. As opposed to 4.0 GPa, phlogopite does not buffer the melt composition at 8.0 GPa. The experimental results suggest that partial melting of MARID-type assemblages at pressures ≥4.0 GPa can generate Si-poor and partly ultrapotassic melts similar in composition to that of olivine lamproites. Received: 23 December 1996 / Accepted: 20 March 1997  相似文献   

11.
The effect of fluorine and fluorine + chlorine on melt viscosities in the system Na2O-Fe2O3-Al2O3-SiO2 has been investigated. Shear viscosities of melts ranging in composition from peraluminous [(Na2O + FeO) < (Al2O3 + Fe2O3)] to peralkaline [(Na2O + FeO) > (Al2O3 + Fe2O3)] were determined over a temperature range 560-890 °C at room pressure in a nitrogen atmosphere. Viscosities were determined using the micropenetration technique in the range of 108.8 to 1012.0 Pa s. The compositions are based on addition of FeF3 and FeCl3 to aluminosilicate melts with a fixed amount of SiO2 (67 mol%). Although there was a significant loss of F and Cl during glass syntheses, none occurred during the viscometry experiments. The presence of fluorine causes a decrease in the viscosity of all melts investigated. This is in agreement with the structural model that two fluorines replace one oxygen; resulting in a depolymerisation of the melt and thus a decrease in viscosity. The presence of both chlorine and fluorine results in a slight increase in the viscosity of peraluminous melts and a decrease in viscosity of peralkaline melts. The variation in viscosity produced by the addition of both fluorine and chlorine is the opposite to that observed in the same composition melts, with the addition of chlorine alone (Zimova M. and Webb S.L. (2006) The effect of chlorine on the viscosity of Na2O-Fe2O3-Al2O3-SiO2 melts. Am. Mineral.91, 344-352). This suggests that the structural interaction of chlorine and fluorine is not linear and the rheology of magmas containing both volatiles is more complex than previously assumed.  相似文献   

12.
Water-saturated and water-undersaturated experiments (a H2 O = 1.0 and 0.5) were performed in the temperature range 780–1040°C at 2 and 5 kbar in order to determine the upper thermal stability of phlogopite in granitic melts. Starting compositions were: (A) subaluminous mixtures of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous haplogranitic glass; (B) peraluminous mixtures (normative corundum  = 4 %) of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous peraluminous haplogranitic glass. The molar quartz: albite: orthoclase ratio of the glasses of the 2␣kbar runs was 35:39:26 and that of the 5 kbar runs 30:42:28. In the subaluminous system, phlogopite is stable up to 820°C at a H2 O = 1.0 and up to 780°C at a H2 O = 0.5. At higher temperatures, it is replaced by enstatite. In the peraluminous system phlogopite has a remarkably higher thermal stability (up to 1000°C at 5 kbar and a H2 O = 1.0) and there is a temperature interval of 80°C at a H2 O = 1.0, and 90–100°C at a H2 O = 0.5 between the first appearance of enstatite and the disappearance of phlogopite. In the peraluminous system, phlogopite is a solid solution (ss) of phlogopite, muscovite, talc and eastonite components. The crystalline product of the phlogopitess breakdown reaction is an aluminous enstatite. The MgO-content of the melt depends on the normative corundum content of the starting material and the run temperature. It is independent of pressure. In the subaluminous system, the MgO-content ranges between 0.05 and 0.3 wt % in the temperature interval 780–880°C at both investigated water activities. The MgO-content of the peraluminous melts at a H2 O = 1.0 ranges between 0.4 and 1.7 wt % and at a H2 O = 0.5 between 0.2 and 1.4 wt % in the temperature range 780–980°C. Received: 28 August 1995 / Accepted: 6 August 1996  相似文献   

13.
 Calorimetric and P–V–T data for the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B2O3) at T=700 ∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets; they range from −221.1 to −259.4 kJ mol−1 (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol−1 (formation from the elements). The heat capacity of Mg5Al5Si6O21(OH)7 has been measured from T=50 ∘C to T=500 ∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents the heat capacity over the entire temperature range to within the experimental uncertainty: C P (Mg-sursassite) =(1571.104 −10560.89×T −0.5−26217890.0 ×T −2+1798861000.0×T −3) J K−1 mol−1 (T in K). The P V T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the bulk modulus was determined as 116.0±1.3 GPa, (K ′=4), V T,0 =446.49 3 exp[∫(0.33±0.05) × 10−4 + (0.65±0.85)×10−8 T dT], (K T/T) P  = −0.011± 0.004 GPa K−1. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg 1998); the best agreement was obtained with Δf H 0 298 (Mg-sursassite) = −13901.33 kJ mol−1, and S 0 298 (Mg-sursassite) = 614.61 J K−1 mol−1. Received: 21 September 2000 / Accepted: 26 February 2001  相似文献   

14.
The Khawr Fakkan block of the Semail ophiolite (United Arab Emirates) exhibits a suite of 10–100 m scale metaluminous to peraluminous granitic intrusions, ranging from cordierite-andalusite-biotite monzogranites to garnet-tourmaline leucogranites, which intrude mantle sequence harzburgites and lower crustal sequence cumulate gabbros. Structural constraints suggest that the subduction of continental sedimentary material beneath the hot proto-ophiolite in an intra-oceanic arc environment led to granulite facies metamorphism at the subduction front and the generation of granitic melts which were emplaced up to the level of the ophiolite Moho. Compositions indicate the analysed granitoids were largely minimum melts that crystallised at variable a H2O and pressures of 3 to 5 kbar. The LILE (Sr, Rb and Ba) covariation modelling suggests that the granitoids formed largely by the dehydration melting of muscovite rich metasediments. Initial 87Sr/86Sr ratios of analysed dykes vary between 0.710 and 0.706 at initial ɛNd values of between −6.3 and −0.5. Cogenetic units of a composite sill from Ra's Dadnah yield a Sm-Nd isochron age of 98.8 ± 9.5 Ma (MSWD = 1.18). Geochemical and isotopic characteristics of the analysed granitic intrusions indicate that the subducted continental material was derived from oceanic trench fill (Haybi complex) sediments, preserved as greenschist (Asimah area) to granulite facies (Bani Hamid area) ophiolitic metamorphic sole terranes. The Sr-Nd isotope systematics suggest that hybrid granitic melts were derived from pre-magmatic mixing of two contrasting subduction zone sources. Received: 17 December 1998 / Accepted: 19 July 1999  相似文献   

15.
It is shown the possibility to determine the coordination of paramagnetic ions in disordered solid structures, e.g., in barium borate glasses. For this purpose the electron paramagnetic resonance (EPR) method was used to study α-and β-BaB2O4 crystals and glasses of 45·BaO × 55·B2O3 and 40·BaO × 60·B2O3 (mol%) composition activated by Ag+ and Pb2+ ions. After the samples were exposed to X-rays at 77 K, different EPR centers were observed in them. In α-and β-BaB2O4 crystals and glasses the EPR centers Ag2+, Ag0, Pb+, Pb3+, and hole centers of O− type were studied. The EPR parameters of these centers and their arrangement in crystal structure were determined. It is shown that Pb3+ ions in β-BaB2O4 crystals occupy Ba2+ position in an irregular polyhedron from the eight oxygen, whereas in α-BaB2O4 crystals they occupy Bа2 position in a sixfold coordination. Pb+ ions in α-BaB2O4 crystals occupy Bа1 position in a ninefold coordination from oxygen. In barium borate glasses, Pb3+ ions were studied in coordination polyhedron from six oxygen atoms and in a polyhedron from nine to ten oxygen atoms. It is assumed that the established difference in the structural position of Pb3+ ions in glasses is due to their previous incorporation in associative cation–anion complexes (AC) and “free” structure-forming cations (FC). Computer simulations have been performed to analyze the stability of specific associative complexes and to compare their bond lengths with experimental data.  相似文献   

16.
Preiswerkite and Na-(Mg,Fe)-margarite are two unusual micas very rare in Nature. They have been observed together in two eclogite occurrences (La Compointrie, France; Liset, Norway) as retrogression products in coronae or symplectites around kyanite. The chemical compositions and some physical properties of these micas are presented. The possible solid solutions and the conditions of stability are discussed. The preiswerkites display slight solid solution towards phengitic muscovite and Na-phlogopite. On the other hand, there is negligible solid solution towards more aluminous compositions; AlIV ≤ 4 appears to be a composition limit for natural (K,Na)-micas. The margarites have an unusual Na-(Mg,Fe)-rich composition. They can be considered as a solid solution of about 2/3 mol% of margarite and 1/3 mol% of the theoretical end-member Na2(Mg,Fe)1AlVI 4[Si4AlIV 4]O20(OH)4 (“Mica L”), with a possible substitution towards paragonite. The Marg2/3 Mica L1/3 composition (i.e. NaCa2(Mg,Fe)0.5 AlVI 6 [Si6AlIV 6]O30(OH)6) might represent a particularly stable crystallographic configuration and could be considered as a true end-member. Many “sodian” margarites described in the literature are, in fact, complex solid solutions between margarite, paragonite and Marg2/3 Mica L1/3. The rarity of these micas is not related to extreme or unusual P-T conditions. They seem to be related to unusual chemical compositions, appearing in H2O-saturated Na-Al-rich Si-poor systems, principally, if not only, at greenschist- or amphibolite-facies P-T conditions. Moreover, they are subject to crystallographic constraints whereby the high proportion of Al-tetrahedra create considerable distortion which prevents the entry of K into the interlayer site, thus necessitating Na (preiswerkite or ephesite) or Ca (margarite or clintonite) instead. Received: 21 April 1998 / Accepted: 25 January 1999  相似文献   

17.
A review of published and newly measured densities for 40 hydrous silicate glasses indicates that the room-temperature partial molar volume of water is 12.0 ± 0.5 cm3/mol. This value holds for simple or mineral compositions as well as for complex natural glasses, from rhyolite to tephrite compositions, prepared up to 10–20 kbar pressures and containing up to 7 wt% H2O. This volume does not vary either with the molar volume of the water-free silicate phase, with its degree of polymerization or with water speciation. Over a wide range of compositions, this constant value implies that the volume change for the reaction between hydroxyl ions and molecular water is zero and that, at least in glasses, speciation does not depend on pressure. Consistent with data from Ochs and Lange (1997, 1999), systematics in volume expansion for SiO2–M2O systems (M=H, Li, Na, K) suggests that the partial molar thermal expansion coefficient of H2O is about 4 × 10−5 K−1 in silicate glasses. Received: 30 June 1999 / Accepted: 5 November 1999  相似文献   

18.
Low-temperature heat capacity measurements for MgCr2O4 have only been performed down to 52 K, and the commonly quoted third-law entropy at 298 K (106 J K−1 mol−1) was obtained by empirical extrapolation of these measurements to 0 K without considering the magnetic or electronic ordering contributions to the entropy. Subsequent magnetic measurements at low temperature reveal that the Néel temperature, at which magnetic ordering of the Cr3+ ions in MgCr2O4 occurs, is at ∼15 K. Hence a substantial contribution to the entropy of MgCr2O4 has been missed. We have determined the position of the near-univariant reaction MgCr2O4+SiO2=MgSiO3+Cr2O3. The reaction, which has a small positive slope in P-T space, has been bracketed at 100 K intervals between 1273 and 1773 K by reversal experiments. The reaction is extremely sluggish, and lengthy run times with a flux (H2O, BaO-B2O3 or K2O-B2O3) are needed to produce tight reversal brackets. The results, combined with assessed thermodynamic data for Cr2O3, MgSiO3 and SiO2, give the entropy and enthalpy of formation of MgCr2O4 spinel. As expected, our experimental results are not in good agreement with the presently available thermodynamic data. We obtain Δ f H ∘ 298=−1759.2±1.5 kJ mol−1 and S ∘ 298=122.1±1.0 J K−1 mol−1 for MgCr2O4. This entropy is some 16 J K−1 mol−1 more than the calorimetrically determined value, and implies a value for the magnetic entropy of MgCr2O4 consistent with an effective spin quantum number (S') for Cr3+ of 1/2 rather than the theoretical 3/2, indicating, as in other spinels, spin quenching. Received: 9 May 1997 / Accepted: 28 July 1997  相似文献   

19.
Equilibrium volumes and expansivities of three liquids in the system anorthite (CaAl2Si2O8)–diopside (CaMgSi2O6) have been derived from dilatometric measurements of the equilibrium length of samples in the glass transition range. The typical temperature range of 40 K for the measurements is limited at low temperature by the very long times necessary to reach structural equilibrium and at high temperature by the penetration of the rod used to measure sample dilatation. Despite such narrow intervals, the expansivities are determined to better than 3% thanks to the high precision with which length changes are measured. The coefficient of volume thermal expansion (1/V dV/dT) of the fully relaxed liquid just above the glass transition is found to decrease linearly from diopside composition (139 ± 4 × 10−6 K−1) to anorthite composition (59 ± 2 × 10−6 K−1). These values are greater than those determined for the same liquids at superliquidus temperatures, demonstrating that expansivities of silicate melts may decrease markedly with increasing temperature. A predictive model based upon partial molar volumes which vary as a linear function of the logarithm of temperature is proposed. Received: 25 February 2000 / Accepted: 29 May 2000  相似文献   

20.
The effect of composition and temperature on the relaxed adiabatic bulk modulus of melts in the P2O5-Al2O 3-Na2SiO3 system have been investigated in the temperature range of 1140 to 1450 °C using ultrasonic interferometric methods at frequencies of 3, 5 and 7 MHz. The density of these melts was determined using Pt-double-bob Archimedean densitometry techiques. P2O5 is known to dramatically affect the structure and the chemical and physical properties of granitic and pegmatitic melts as a function of the peralkalinity of the melt. The physical results of the structural changes occurring in Na2O-Al2O3-SiO2 melt upon the addition of P2O5 are observed by variations in the properties such as density and compressibility. For the present peralkaline melts, the bulk modulus and density decrease with addition of 15 mol% P2O5, and increase with the addition of 15 mol% Al2O3. The addition of P2O5 to the present melts results in a larger increase in melt compressibility than that observed with increasing polymerization between Na2SiO3 and Na2Si2O5 melts. This would suggest that not only is the polymerization of the melt increasing with the addition of P2O5 (Mysen et al. 1981; Nelson and Tallant 1984; Gan and Hess 1992), but that the tetrahedrally co-ordinated phosphorus complexes are influencing the bond lengths and energies within the melt structure; resulting in the structure becoming more compressible than expected, although incompressible (Vaughan and Weidner 1987) tetrahedral P2O5 polyhedra (Mysen et al. 1981; Gan and Hess 1992; Toplis et al. 1994) are being added to the melt structure.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号