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1.
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   

2.
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   

3.
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   

4.
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   

5.
The solubility behavior of phosphorus in glasses and melts in the system Na2O-Al2O3-SiO2-P2O5 has been examined as a function of temperature and Al2O3 content with microRaman spectroscopy. The Al2O3 was added (2, 4, 5, 6, and 8 mol% Al2O3) to melts with 80 mol% SiO2 and ∼2 mol% P2O5. The compositions range from peralkaline, via meta-aluminous to peraluminous. Raman spectra were obtained of both the phosphorus-free and phosphorous-bearing glasses and melts between 25 and 1218 °C. The Raman spectrum of Al-free, P-bearing glass exhibits a characteristic strong band near 940 cm−1 assigned to P=O stretching in orthophosphate complexes together with a weaker band near 1000 cm−1 assigned P2O7 complexes. With increasing Al content, the proportion of P2O7 initially increases relative to PO4 and is joined by AlPO4 complexes which exhibit a characteristic P-O stretch mode slightly above 1100 cm−1. The latter complex appears to dominate in meta-aluminosilicate glass and is the only phosphate complex in peraluminous glasses. When P-bearing peralkaline silicate and aluminosilicate glasses are transformed to supercooled melts, there is a rapid decrease in PO4/P2O7 so that in the molten state, PO4 units are barely discernible. The P2O7/AlPO4 abundance ratio in peralkaline compositions increases with increasing temperature. This decrease in PO4/P2O7 with increasing temperature results in depolymerization of the silicate melts. Dissolved P2O5 in peraluminous glass and melts forms AlPO4 complexes only. This solution mechanism has no discernible influence on the aluminosilicate melt structure. There is no effect of temperature on this solution mechanism. Received: 7 October 1997 / Accepted: 11 May 1998  相似文献   

6.
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   

7.
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   

8.
Hydrothermal experiments were carried out at 2 kbar water pressure, 700 °–800 ° C, with the objective of determining the level of dissolved Zr required for precipitation of zircon from melts in the system SiO2-Al2O3-Na2O-K2O. The saturation level depends strongly upon molar (Na2O + K2O)/Al2O3 of the melts, with remarkably little sensitivity to temperature, SiO2 concentration, or melt Na2O/ K2O. For peraluminous melts and melts lying in the quartz-orthoclase-albite composition plane, less than 100 ppm Zr is required for zircon saturation. In peralkaline melts, however, zircon solubility shows pronounced, apparently linear, dependence upon (Na2O + K2O)/Al2O3, with the amount of dissolvable Zr ranging up to 3.9 wt.% at (Na2O + K2O)/Al2O3 = 2.0. Small amounts (1 wt.% each) of dissolved CaO and Fe2O3 cause a 25% relative reduction of zircon solubility in peralkaline melts.The main conclusion regarding zirconium/zircon behavior in nature is that any felsic, non-peralkaline magma is likely to contain zircon crystals, because the saturation level is so low for these compositions. Zircon fractionation, and its consequences to REE, Th, and Ta abundances must, therefore, be considered in modelling the evolution of these magmas. Partial melting in any region of the Earth's crust that contains more than 100 ppm Zr will produce granitic magmas whose Zr contents are buffered at constant low (< 100 ppm) values; unmelted zircon in the residual rock of such a melting event will impart to the residue a characteristic U- or V-shaped REE abundance pattern. In peralkaline, felsic magmas such as those that form pantellerites and comendites, extreme Zr (and REE, Ta) enrichment is possible because the feldspar fractionation that produces these magmas from non-peralkaline predecessors does not drive the melt toward saturation in zircon.Zircon solubility in felsic melts appears to be controlled by the formation of alkali-zirconosilicate complexes of simple (2:1) alkali oxide: ZrO2 stoichiometry.  相似文献   

9.
The Oroscocha Quaternary volcano, in the Inner Arc Domain of the Andean Cordillera (southern Peru), emitted peraluminous rhyolites and trachydacites that entrained decimetric to millimetric lamprophyric blobs. These latter show kersantite modal compositions (equal proportion of groundmass plagioclase and K-feldspar) and potassic bulk-rock compositions (1<K2O/Na2O<2; 6.7–7.2 wt.% CaO). Kersantite blobs have shapes and microstructures consistent with an origin from a mixing process between mafic potassic melts and rhyolitic melts. Both melts did exchange their phenocrysts during the mixing process. In addition to index minerals of lamprophyres (Ba–Ti–phlogopite, F-rich apatite, andesine and Ca-rich sanidine), the groundmass of kersantite blobs displays essenite-rich diopside (up to 22 mol%), Ti-poor magnetite microlites, Ti-poor hematite microlites and a series of Ca–Ti–Zr- and REE-rich accessory minerals that have never been reported from lamprophyres. Titanite [up to 5.3 wt.% ZrO2 and 5.2 wt.% (Y2O3 + REE2O3)] and Zr- and Ca-rich perrierite (up to 7.2 wt.% ZrO2 and 10.8 wt.% CaO) predate LREE- and iron-rich zirconolite and Fe-, Ti-, Hf-, Nb- and Ce-rich baddeleyite (up to 5.3 wt.% Fe2O3, 3.2 wt.% TiO2, 1.5 wt.% HfO2, 1.2 wt.% Nb2O5, 0.25 wt.% CeO2) in the crystallization order of the groundmass. Isomorphic substitutions suggest iron to occur as Fe3+ in all the accessory phases. This feature, the essenitic substitution in the clinopyroxene and the occurrence of hematite microlites, all indicate a drastic increase of the oxygen fugacity (from FMQ − 1 to FMQ + 5 log units) well above the HM synthetic buffer within a narrow temperature range (1100–1000 °C). Such a late-magmatic oxidation is ascribed to assimilation of water from the felsic melts during magma mixing, followed by rapid degassing and water dissociation during eruption of host felsic lavas. Thus, magma mixing involving felsic melt end-members provides a mechanism for mafic potassic melts to be oxidized beyond the HM synthetic buffer curve.  相似文献   

10.
The effect of CaO, Na2O, and K2O on ferric/ferrous ratio in model multicomponent silicate melts was investigated in the temperature range 1450–1550?°C at 1-atm total pressure in air. It is demonstrated that the addition of these network modifier cations results in an increase of Fe3+/Fe2+ ratio. The influence of network modifier cations on the ferric/ferrous ratio increases in the order Ca?<?Na?<?K. Some old controversial conceptions concerning the effect of potassium on Fe3+/Fe2+ ratio in simple model liquids are critically evaluated. An empirical equation is proposed to predict the ferric/ferrous ratio in SiO2–TiO2–Al2O3–FeO–Fe2O3–MgO–CaO–Na2O–K2O–P2O5 melts at air conditions.  相似文献   

11.
Summary The results of microprobe analyses of clinopyroxenes from alkaline melasyenites and layered melagabbros, produced by intra-plate magmatism of Paleocene age at Punta delle Pietre Nere, are here given and discussed.The analysed pyroxenes range from diopsidic to acmite-rich compositions.The first crystallized pyroxenes (diopside) show AlVI contents suggesting shallow depths of crystallization. In addition pyroxenes from melasyenite and those from melagabbro display different Cr contents, Al/Ti and Mg/(Mg+Fe2++Fe3+) ratios confirming their crystallization from melts produced by different parental liquids.Diopsides and salites show an overall trend towards high Al, Ti and Fe3+, suggesting that the crystallization occurred under decreasing SiO2/Al2O3 ratios and under relatively highpH2O–pO2 conditions.Pyroxenes from the Pietre Nere melasyenite show a progressive variation towards acmite rich compositions at Mg/(Mg+Fe2++Fe3+) lower than 0.5; those from the layered melagabbro, instead, show a continuous enrichment in Ca Fe3+ AlSiO6. This different behaviour is due to the co-crystallization, with the latest pyroxenes, of phases with different K/Na and Si/Al ratios.
Kristallisations-Tendenzen der Pyroxene aus Alkali-Subvulkaniten auf Punta delle Pietre Nere (Gargano, Süditalien)
Zusammenfassung Es werden die Ergebnisse der Mikrosonden-Untersuchungen von Klinopyroxenen aus Alkali-Melasyeniten und schichtigen Alkali-Melagabbros, die durch Intra-plate-Magmatismus paläozenen Alters auf Punta delle Pietre Nere entstanden sind, beschrieben und erörtert.Die untersuchten Pyroxene reichen von diopsidischen bis zu Akmit-reichen Zusammensetzungen.Die zuerst kristallisierten Pyroxene (Diopsid) zeigen AlVI-Gehalte, die auf geringe Tiefe des Kristallisationsvorganges hinweisen. Dazu zeigen die Pyroxene aus dem Melasyenit und aus dem Melagabbro unterschiedliche Cr-Gehalte; die Al/Ti- und Mg/(Mg+Fe2++Fe3+)-Verhältnisse bestätigen deren Kristallisation aus Schmelzen, die aus unterschiedlichen Ursprungsmagmen stammen.Die Diopside und Salite zeigen eine einheitliche Tendenz zu hohem Al-, Ti- und Fe3+-Gehalt; dies deutet darauf hin, daß die Kristallisation unter abnehmenden SiO2/Al2O3-Verhältnissen und unter relativ hohenpH2O–pO2-Bedingungen stattfand.Die Pyroxene aus dem Punta delle Pietre Nere-Melasyenit zeigen eine zunehmende Änderung zu Akmit-reichen Zusammensetzungen bei weniger als 0,5 Mg/(Mg+Fe2++Fe3+); die Pyroxene aus dem schichtig differenzierten Melagabbro zeigen dagegen eine allmähliche Zunahme von CaFe3+AlSiO6. Dieses unterschiedliche Verhalten rührt daher, daß Mineralphasen mit unterschiedlichen K/Na- und Si/Al-Verhältnissen zugleich mit den zuletzt gebildeten Pyroxenen kristallisierten.

With 6 Figures  相似文献   

12.
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   

13.
Thermodynamic analysis of the system Na2O-K2O-CaO-Al2O3-SiO2-H2O-F2O–1 provides phase equilibria and solidus compatibilities of rock-forming silicates and fluorides in evolved granitic systems and associated hydrothermal processes. The interaction of fluorine with aluminosilicate melts and solids corresponds to progressive fluorination of their constituent oxides by the thermodynamic component F2O–1. The chemical potential (F2O–1) buffered by reaction of the type: MOn/2 (s)+n/2 [F2O–1]=MFn (s, g) where M=K, Na, Ca, Al, Si, explains the sequential formation of fluorides: carobbiite, villiaumite, fluorite, AlF3, SiF4 as well as the common coexistence of alkali- and alkali-earth fluorides with rock-forming aluminosilicates. Formation of fluorine-bearing minerals first starts in peralkaline silica-undersaturated, proceeds in peraluminous silica-oversaturated compositions and causes progressive destabilization of nepheline, albite and quartz, in favour of villiaumite, cryolite, topaz, chiolite. Additionally, it implies the increase of buffered fluorine solubilities in silicate melts or aqueous fluids from peralkaline silica-undersaturated to peraluminous silica-oversaturated environments. Subsolidus equilibria reveal several incompatibilities: (i) topaz is unstable with nepheline or villiaumite; (ii) chiolite is not compatible with albite because it only occurs only at very high F2O–1 levels. The stability of topaz, fluorite, cryolite and villiaumite in natural felsic systems is related to their peralkalinity (peraluminosity), calcia and silica activity, and linked by corresponding chemical potentials to rock-forming mineral buffers. Villiaumite is stable in strongly peralkaline and Ca-poor compositions (An<0.001). Similarly, cryolite stability requires coexistence with nearly-pure albite (An<2). Granitic rocks with Ca-bearing plagioclase (An>5) saturate with topaz or fluorite. Crystallization of topaz is restricted to peraluminous conditions, consistent with the presence of Li-micas or anhydrous aluminosilicates (cordierite, garnet, andalusite). Fluorite is predicted to be stable in peraluminous biotite granites, amphibole-, clinopyroxene- or titanite-bearing calc-alkaline suites as well as in peralkaline granitic and syenitic rocks. Fluorine concentrations in felsic melts buffered by the coexistence of F-bearing minerals and feldspars increase from peralkaline through metaluminous to mildly peraluminous compositions. At low-temperature conditions, the hydrothermal evolution of peraluminous granitic and greisen systems is controlled by white mica-feldspar-fluoride equilibria. With decreasing temperature, topaz gradually breaks down via: (i) (OH)F–1 substitution and fluorine transfer to fluorite by decalcification of plagioclase below 600 °C, (ii) formation of muscovite and additional fluorite at 475–315 °C, and (iii) formation of paragonite and cryolite, consuming F-rich topaz and albite below 315 °C. These equilibria explain the absence of magmatic fluorite in Ca-bearing topaz granitic rocks; its abundance in hydrothermal rocks is due to: (i) closed-system defluorination of topaz, (ii) open-system decalcification of plagioclase or (iii) hydrolytic alteration. These results provide a complete framework for the investigation of fluorine-bearing mineral stabilities in felsic igneous suites.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.Editorial responsibility: T.L. Grove  相似文献   

14.
The structure of H2O-saturated silicate melts and of silicate-saturated aqueous solutions, as well as that of supercritical silicate-rich aqueous liquids, has been characterized in-situ while the sample was at high temperature (to 800 °C) and pressure (up to 796 MPa). Structural information was obtained with confocal microRaman and with FTIR spectroscopy. Two Al-bearing glasses compositionally along the join Na2O•4SiO2-Na2O•4(NaAl)O2-H2O (5 and 10 mol% Al2O3, denoted NA5 and NA10) were used as starting materials. Fluids and melts were examined along pressure-temperature trajectories of isochores of H2O at nominal densities (from PVT properties of pure H2O) of 0.85 g/cm3 (NA10 experiments) and 0.86 g/cm3 (NA5 experiments) with the aluminosilicate + H2O sample contained in an externally-heated, Ir-gasketed hydrothermal diamond anvil cell.Molecular H2O (H2O°) and OH groups that form bonds with cations exist in all three phases. The OH/H2O° ratio is positively correlated with temperature and pressure (and, therefore, fugacity of H2O, fH2O) with (OH/H2O°)melt > (OH/H2O°)fluid at all pressures and temperatures. Structural units of Q3, Q2, Q1, and Q0 type occur together in fluids, in melts, and, when outside the two-phase melt + fluid boundary, in single-phase liquids. The abundance of Q0 and Q1 increases and Q2 and Q3 decrease with fH2O. Therefore, the NBO/T (nonbridging oxygen per tetrahedrally coordination cations), of melt is a positive function of fH2O. The NBO/T of silicate in coexisting aqueous fluid, although greater than in melt, is less sensitive to fH2O.The melt structural data are used to describe relationships between activity of H2O and melting phase relations of silicate systems at high pressure and temperature. The data were also combined with available partial molar configurational heat capacity of Qn-species in melts to illustrate how these quantities can be employed to estimate relationships between heat capacity of melts and their H2O content.  相似文献   

15.
Water Content of Basalt Erupted on the ocean floor   总被引：1，自引：0，他引：1  
Deep sea pillow basalts dredged from the ocean floor show that vesicularity changes with composition as well as with depth. Alkalic basalts are more vesicular than tholeiitic basalts erupted at the same depth. The vesicularity data, when related to experimentally determined solubility of water in basalt, indicate that K-poor oceanic tholeiites originally contained about 0.25 percent water, Hawaiian tholeiites of intermediate K-content, about 0.5 percent water, and alkali-rich basalts, about 0.9 percent water. Analyses of fresh basalt pillows show a systematic increase of H2O+ as the rocks become more alkalic. K-poor oceanic tholeiites contain 0.06–0.42 percent H2O+, Hawaiian tholeiites, 0.31–0.60 percent H2O+, and alkali rich basalts 0.49–0.98 percent H2O+. The contents of K2O, P2O5, F, and Cl increase directly with an increase in H2O+ content such that at 1.0 weight percent H2O+, K2O is 1.58 percent, P2O5 is 0.55 percent, F is 0.07 percent, and Cl is 0.1 percent. The measured weight percent of deuterium on the rim of one Hawaiian pillow is –6.0 (relative to SMOW); this value, which is similar to other indications of magmatic water, suggests that no appreciable sea water was absorbed by the pillow during or subsequent to eruption on the ocean floor.Concentrations of volatile constituents in the alkali basalt melts relative to tholeiitic melts can be explained by varying degrees of partial melting of mantle material or by fractional crystallization of a magma batch.Publication authorized by the Director, U.S. Geological Survey.  相似文献   

16.
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   

17.
Glassy orthopyroxene granodiorite-tonalite (named pincinite after type locality) was described from basaltic lapilli tuffs of the Pliocene maar near Pinciná village in the Slovakian part of the Pannonian Basin. Two pincinite types exhibit a qualitatively similar mineral composition (quartz, An20–55 plagioclase, intergranular silicic glass with orthopyroxene and ilmenite, ±K-feldspar), but strongly different redox potential and formation PT conditions. Peraluminous pincinite is reduced (6–7% of total iron as Fe3+ in corundum-normative intergranular dacitic glass) and contains ilmenite with 8–10 mol% Fe2O3 and orthopyroxene dominated by ferrosilite. High-density (up to 0.85 g/cm3) primary CO2 inclusions with minor H2, CH4, H2S, CO and N2 (<2 mol% total) are present in Qtz and Plg. Equilibrium PT conditions inferred from the intergranular Opx–Ilm–Glass assemblage and fluid density correspond to 1,170±50°C, 5.6±0.4 kbar, respectively. Metaluminous pincinite is more oxidised (25–27% of total iron as Fe3+ in diopside-normative intergranular glass of rhyolite–trachyte–dacite composition) and contains Fe2O3-rich ilmenite (17–29 mol%) associated with enstatite. Fluid inclusions are composed of CO2–H2O mixtures with up to 38 mol% H2O. Raman spectroscopy revealed H2S along with dominant CO2 in the carbonic phase. Equilibrium PT parameters for the intergranular Opx–Ilm–Glass assemblage correspond to 740±15°C, 2.8±0.1 kbar, respectively. Reducing gas species (<2 mol% total) in the CO2-inclusions of the peraluminous pincinite resulted from hydrogen diffusion due to fH2 gradient imposed during decrease of redox potential from the log fO2 values near QFM during Qtz + Plg growth, to QFM-2 incidental to the superimposed Opx + Ilm assemblage in the intergranular melt. The decrease in oxygen fugacity was recorded also in the metaluminous pincinite, where log fO2 values changed from ~QFM + 2.6 to QFM + 0.4, but hydrogen diffusion did not occur. Absence of OH-bearing minerals, major and trace element abundances (e.g. REE 300–320, Nb 55–57, Th 4–31, Zr 240–300 ppm, FeOtot/MgO up to 11), and Sr–O isotope ratios in the pincinites are diagnostic of high-temperature anorogenic magmas originated by dehydration melting of biotite in quartz-feldspathoid crust (87Sr/86Sr>0.705–0.706, 18O>9 V-SMOW) around alkali basalt reservoir in depths between 17 and 20 km, and around late stage derivatives of the basalt fractionation, intruding the crust up to depths of 10–11 km. Low water activity in the pincinite parental melt was caused by CO2-flux from the Tertiary basaltic reservoirs and intrusions. The anatexis leads to generation of a melt-depleted granulitic crust beneath the Pannonian Basin, and the pincinites are interpreted as equivalents of igneous charnockites and enderbites quenched at temperatures above solidus and unaffected by sub-solidus re-equilibration and metamorphic overprint.  相似文献   

18.
Mossbauer spectroscopy has been used to determine the redox equilibria of iron and structure of quenched melts on the composition join Na2Si2O5-Fe2O3 to 40 kbar pressure at 1400° C. The Fe3+/ΣFe decreases with increasing pressure. The ferric iron appears to undergo a gradual coordination transformation from a network-former at 1 bar to a network-modifier at higher (≧10 kbar) pressure. Ferrous iron is a network-modifier in all quenched melts. Reduction of Fe3+ to Fe2+ and coordination transformation of remaining Fe3+ result in depolymerization of the silicate melts (the ratio of nonbridging oxygens per tetrahedral cations, NBO/T, increases). It is suggested that this pressure-induced depolymerization of iron-bearing silicate liquids results in increasing NBO/T of the liquidus minerals. Furthermore, this depolymerization results in a more rapid pressure-induced decrease in viscosity and activation energy of viscous flow of iron-bearing silicate melts than would be expected for iron-free silicate melts with similar NBO/T.  相似文献   

19.
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   

20.
Oldoinyo Lengai, located in the Gregory Rift in Tanzania, is a world-famous volcano owing to its uniqueness in producing natrocarbonatite melts and because of its extremely high CO2 flux. The volcano is constructed of highly peralkaline [PI = molar (Na2O + K2O)/Al2O3 > 2–3] nephelinite and phonolites, both of which likely coexisted with carbonate melt and a CO2-rich fluid before eruption. Results of a detailed melt inclusion study of the Oldoinyo Lengai nephelinite provide insights into the important role of degassing of CO2-rich vapor in the formation of natrocarbonatite and highly peralkaline nephelinites. Nepheline phenocrysts trapped primary melt inclusions at 750–800 °C, representing an evolved state of the magmas beneath Oldoinyo Lengai. Raman spectroscopy, heating-quenching experiments, low current EDS and EPMA analyses of quenched melt inclusions suggest that at this temperature, a dominantly natritess-normative, F-rich (7–14 wt%) carbonate melt and an extremely peralkaline (PI = 3.2–7.9), iron-rich nephelinite melt coexisted following degassing of a CO2 + H2O-vapor. We furthermore hypothesize that the degassing led to re-equilibration between the melt and liquid phases that remained and involved 1/ mixing between the residual (after degassing) alkali carbonate liquid and an F-rich carbonate melt and 2/ enrichment of the coexisting nephelinite melt in alkalis. We suggest that in the geological past similar processes were responsible for generating highly peralkaline silicate melts in continental rift tectonic settings worldwide.  相似文献   

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