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1.
This paper reports experimental data on columbite solubility in model water-saturated Li- and F-rich silicic melts with different
contents of alumina and alkalis. It was found that the columbite solubility is strongly affected by melt composition and is
maximal in peralkaline melt. The maximum contents of Ta and Nb in subaluminous and peraluminous melts at the contact with
columbite are lower by at least an order of magnitude. The peralkaline melt is relatively enriched in Nb, and the peraluminous
melt is enriched in Ta. The temperature dependence of solubility is positive but less pronounced than the effect of melt composition.
It is most distinct in the subaluminous melts. The Nb/Ta ratio of melt usually decreases with decreasing temperature. The
effect of pressure is relatively small. It was shown that columbite cannot crystallize on the liquidus of both peralkaline
and peraluminous magmas. Perhaps, columbite crystallization from a melt is possible only at final near-solidus stages at the
high degrees of crystallization of strongly evolved low-temperature melts. 相似文献
2.
Columbite solubility in granitic melts: consequences for the enrichment and fractionation of Nb and Ta in the Earth's crust 总被引：13，自引：0，他引：13
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 solubility of Ti- and P-rich accessory minerals has been examined as a function of pressure and K2O/Na2O ratio in two series of highly evolved silicate systems. These systems correspond to (a) alkaline, varying from alkaline to peralkaline with increasing K2O/Na2O ratio; and (b) strongly metaluminous (essentially trondhjemitic at the lowest K2O/Na2O ratio) and remaining metaluminous with increasing K2O/Na2O ratio (to 3). The experiments were conducted at a fixed temperature of 1000 °C, with water contents varying from 5 wt.% at low pressure (0.5 GPa), increasing through 5–10 wt.% at 1.5–2.5 GPa to 10 wt.% at 3.5 GPa. Pressure was extended outside the normal crustal range, so that the results may also be applied to derivation of hydrous silicic melts from subducted oceanic crust.
For the alkaline composition series, the TiO2 content of the melt at Ti-rich mineral saturation decreases with increasing pressure but is unchanged with increasing K content (at fixed pressure). The P2O5 content of the alkaline melts at apatite saturation increases with increased pressure at 3.5 GPa only, but decreases with increasing K content (and peralkalinity). For the metaluminous composition series (termed as “trondhjemite-based series” (T series)), the TiO2 content of the melt at Ti-rich mineral saturation decreases with increasing pressure and with increasing K content (at fixed pressure). The P2O5 content of the T series melts at apatite saturation is unchanged with increasing pressure, but decreases with increasing K content. The contrasting results for P and Ti saturation levels, as a function of pressure in both compositions, point to contrasting behaviour of Ti and P in the structure of evolved silicate melts. Ti content at Ti-rich mineral saturation is lower in the alkaline compared with the T series at 0.5 GPa, but is similar at higher pressures, whereas P content at apatite saturation is lower in the T series at all pressures studied. The results have application to A-type granite suites that are alkaline to peralkaline, and to I-type metaluminous suites that frequently exhibit differing K2O/Na2O ratios from one suite to another. 相似文献
4.
The exsolution of magmatic hydrosaline chloride liquids 总被引：14，自引：0，他引：14
Hydrosaline liquid represents the most Cl-enriched volatile phase that occurs in magmas, and the exsolution of this phase has important consequences for processes of hydrothermal mineralization and for volcanic emission of Cl to the atmosphere. To understand the exsolution of hydrosaline liquids in felsic to mafic magmas, the volatile abundances and (Cl/H2O) ratios of more than 1000 silicate melt inclusions (MI) have been compared with predicted and experimentally determined solubilities of Cl and H2O and associated (Cl/H2O) ratios of silicate melts that were saturated in hydrosaline chloride liquid with or without aqueous vapor in hydrothermal experiments. This approach identifies the minimum volatile contents and the values of (Cl/H2O) at which a hydrosaline chloride liquid exsolves from any CO2- or SO2-poor silicate melt. Chlorine solubility is a strong function of melt composition, so it follows that Cl solubility in magmas varies with melt evolution. Computations show that the (Cl/H2O) ratio of residual melt in evolving silicate magmas either remains constant or increases to a small extent with fractional crystallization. Consequently, the initial (Cl/H2O) in melt that is established early during partial melting has important consequences for the exsolution of vapor, vapor plus hydrosaline liquid, or hydrosaline liquid later during the final stages of melt ascent, emplacement, and crystallization or eruption. It is demonstrated that the melt (Cl/H2O) controls the type of volatile phase that exsolves, whereas the volatile abundances in melt control the relative timing of volatile phase exsolution (i.e., the time of earliest volatile exsolution relative to the rate of magma ascent and crystallization history).
Comparing melt inclusion compositions with experimentally determined (Cl/H2O) ratios and corresponding volatile solubilities of hydrosaline liquid-saturated silicate melts suggests that some fractions of the eruptive, calc-alkaline dacitic magmas of the Bonnin and Izu arcs should have saturated in and exsolved hydrosaline liquid at pressures of 2000 bars. Application of these same melt inclusion data to the predicted volatile solubilities of Cu-, Au-, and Mo-mineralized, calc-alkaline porphyritic magmas suggests that the chemical evolution of dioritic magmas to more-evolved quartz monzonite compositions involves a dramatic reduction in Cl solubility that increases the probability of hydrosaline liquid exsolution. The prediction that quartz monzonite magmas should exsolve a hydrosaline chloride liquid, that is potentially mineralizing, is consistent with the general observation of metal-enriched, hypersaline fluid inclusions in the more felsic plutons of numerous porphyry copper systems. Moreover, comparing the volatile contents of melt inclusions from the potassic, alkaline magmas of Mt. Somma-Vesuvius with the predicted (Cl/H2O) ratios of hydrosaline liquid-saturated melts having compositions similar to those of the volatile-rich, alkaline magmas associated with the orthomagmatic gold–tellurium deposits of Cripple Creek, Colorado, suggests that hydrosaline chloride liquid should have exsolved at Cripple Creek as the magmas evolved to phonolite compositions. This prediction is consistent with the well-documented role of Cl-enriched, mineralizing hydrothermal fluids at this major gold-mining district. 相似文献
5.
Idiomorphic quartz crystals in topaz-bearing granite from the Salmi batholith contain primary inclusions of silicate melt and abundant mostly secondary aqueous fluid inclusions. Microthermometric measurements on melt inclusions give estimates for the granite solidus and liquidus of 640–680°C and 770–830°C, respectively. Using published solubility models for H2O in granitic melts and the obtained solidus/liquidus temperatures from melt inclusions, the initial water concentration of the magma is deduced to have been approximately 3 wt.% and the minimum pressure about 2 kbar. At this initial stage, volatile-undersaturation conditions of magma were assumed. These results indicate that the idiomorphic quartz crystals are magmatic in origin and thus real phenocrysts. During subsolidus cooling and fracturing of the granite, several generations of aqueous fluid inclusions were trapped into the quartz phenocrysts. The H2O inclusions have salinities and densities of 1–41 wt.% NaCl eq. and 0.53–1.18 g/cm3, respectively. 相似文献
6.
The aim of this experimental study was to determine the solubility of cassiterite in natural topaz- and cassiterite-bearing granite melts at temperatures close to the solidus. Profiles of Sn concentrations at glass–crystal (SnO2) interface were determined following the method of (Harrison, T.M., Watson, E.B., 1983. Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content. Contributions to Mineralogy and Petrology 84, 66–72). The cassiterite concentration calculated at the SnO2–glass interface is the SnO2 solubility. Experiments were performed at 700–850 °C and 2 kbar using a natural F-bearing peraluminous granitic melt with 2.8 wt.% normative corundum. Slightly H2O-undersaturated to H2O-saturated melt compositions were chosen in order to minimize the loss of Sn to the noble element capsule walls. At the nickel–nickel oxide assemblage (Ni–NiO) oxygen fugacity buffer, the solubility of cassiterite in melts containing 1.12 wt.% F increases from 0.32 to 1.20 wt.% SnO2 with an increasing temperature from 700 to 850 °C. At the Ni–NiO buffer and a given corundum content, SnO2 solubility increases by 10% to 20% relative to an increase of F from 0 to 1.12 wt.%. SnO2 solubility increases by 20% relative to increasing Cl content from 0 to 0.37 wt.% in synthetic granitic melts at 850 °C. We show that Cl is at least as important as F in controlling SnO2 solubility in evolved peraluminous melts at oxygen fugacities close to the Ni–NiO buffer. In addition to the strong effects of temperature and fO2 on SnO2 solubility, an additional controlling parameter is the amount of excess Al (corundum content). At Ni–NiO and 850 °C, SnO2 solubility increases from 0.47 to 1.10 wt.% SnO2 as the normative corundum content increases from 0.1 to 2.8 wt.%. At oxidizing conditions (Ni–NiO +2 to +3), Sn is mainly incorporated as Sn4+ and the effect of excess Al seems to be significantly weaker than at reducing conditions. 相似文献
7.
Zircon (ZrSiO4) and hafnon (HfSiO4) solubilities in water-saturated granitic melts have been determined as a function of melt composition at 800° and 1035°C at 200 MPa. The solubilities of zircon and hafnon in metaluminous or peraluminous melts are orders of magnitude lower than in strongly peralkaline melt. Moreover, the molar ratio of zircon and hafnon solubility is a function of melt composition. Although the solubilities are nearly identical in peralkaline melts, zircon on a molar basis is up to five times more soluble than hafnon in peraluminous melts. Accordingly, calculated partition coefficients of Zr and Hf between zircon and melt are nearly equal for the peralkaline melts, whereas for metaluminous and peraluminous melts DHf/DZr for zircon is 0.5 to 0.2. Consequently, zircon fractionation will strongly decrease Zr/Hf in some granites, whereas it has little effect on the Zr/Hf ratio in alkaline melts or similar depolymerized melt compositions.The ratio of the molar solubilities of zircon and hafnon for a given melt composition, temperature, and pressure is proportional to the Hf/Zr activity coefficient ratio in the melt. The data imply that this ratio is nearly constant and probably close to unity for a wide range of peralkaline and similar depolymerized melts. However, it changes by a factor of two to five over a relatively small interval of melt compositions when a nearly fully polymerized melt structure is approached. For most ferromagnesian minerals in equilibrium with a depolymerized melt, DHf > DZr. Typical values of DHf/DZr range from 1.5 to 2.5 for clinopyroxene, amphibole, and titanite. Because of the change in the Hf/Zr activity ratio in the melt, the relative fractionation of Zr and Hf by these minerals will disappear or even be reversed when the melt composition approaches that of a metaluminous or peraluminous granite. It is thus not surprising that fractional crystallization of such granitic magmas leads to a decrease in Zr/Hf, whereas fractional crystallization of depolymerized melts tends to increase Zr/Hf. There is no need to invoke fluid metasomatism to explain these effects. Results demonstrate that for ions with identical charge and nearly identical radius, crystal chemistry does not alone determine relative compatibilities. Rather, the effect of changing activity coefficients in the melt may be comparable to or even larger than elastic strain effects in the crystal lattice. 相似文献
8.
Influence of fluorine on the enrichment of high field strength trace elements in granitic rocks 总被引：26，自引：2，他引：26
Hans Keppler 《Contributions to Mineralogy and Petrology》1993,114(4):479-488
The solubilities of zircon, rutile, manganocolumbite (MnNb2O6), manganotantalite (MnTa2O6), and the rare earth phosphates LaPO4, GdPO4, and YbPO4 in water-saturated haplogranitic melts containing 0–6 wt.% F were measured at 800° C and 2 kbar. The melt compositions investigated differ only in their F content, the proportions of Na, K, Al, and Si are identical in all experiments. While the solubilities of the rare earth phosphates are independent of F, the solubilities of all other minerals studied strongly increase with F. The TiO2 content of haplogranitic melt in equilibrium with rutile increases linearly from 0.26 wt.% without F to 0.47 wt.% for melts containing 6 wt.% F. Over the same range of F concentrations, the ZrO2 content of the melt in equilibrium with zircon increases with the square of the F content from less than 0.01 wt.% to 0.25 wt.%. The linear increase for rutile and the quadratic relationship for zircon suggest a complexing mechanism. Probably nonbridging oxygen atoms (NBO) expelled from coordination with Al by reaction with F form complexes with Ti and Zr, the ratio of NBO: metal cation being 1:1 for Ti, and 2:1 for Zr. Direct complexing by F is also a possibility. As titanium oxide phases and zircon are major sinks for HFS elements such as Ti, Nb, Ta, Zr, Hf, Th and REE in granites, their increased solubility in the presence of F favors the enrichment of these elements in residual mels. The Nb and Ta content of rutile in granitic pegmatites is due to extended solid solution of rutile with columbite group minerals, such as manganocolumbite and manganotantalite. The solubility of these components also increases with F, MnTa2O6 being more soluble than MnNb2O6. Rutile fractionation could therefore account for the increase in Ta/Nb frequently observed in highly differentiated granites. The solubility of the rare earth phosphates increases strongly from LaPO4 to GdPO4 to YbPO4, which explains the enrichment of heavy rare earth elements in highly evolved granites. In the presence of F, many HFS elements will be highly incompatible in granitic systems. Therefore, in a suite of granitic rocks generated by differentiation from the same source magma, a strong correlation should exist between HFS elements and F. However, because of the influence of F on the solubility of refractory phases such as zircon, a similar correlation could also result from different batches of magma containing different amounts of F equilibrating with the same refractory phase. 相似文献
9.
The speciation of water in silicate melts 总被引：1，自引：0，他引：1
Edward Stolper 《Geochimica et cosmochimica acta》1982,46(12):2609-2620
Previous models of water solubility in silicate melts generally assume essentially complete reaction of water molecules to hydroxyl groups. In this paper a new model is proposed that is based on the hypothesis that the observed concentrations of molecular water and hydroxyl groups in hydrous silicate glasses reflect those of the melts from which they were quenched. The new model relates the proportions of molecular water and hydroxyl groups in melts via the following reaction describing the homogeneous equilibrium between melt species: H2Omolecular (melt) + oxygen (melt) = 2OH (melt). An equilibrium constant has been formulated for this reaction and species are assumed to mix ideally. Given an equilibrium constant for this reaction of 0.1–0.3, the proposed model can account for variations in the concentrations of molecular water and hydroxyl groups in melts as functions of the total dissolved water content that are similar to those observed in glasses. The solubility of molecular water in melt is described by the following reaction: H2O (vapor) = H2Omolecular (melt).These reactions describing the homogeneous and heterogeneous equilibria of hydrous silicate melts can account for the following observations: the linearity between fH2O and the square of the mole fraction of dissolved water at low total water contents and deviations from linearity at high total water contents; the difference between the partial molar volume of water in melts at low total water contents and at high total water contents; the similarity between water contents of vapor-saturated melts of significantly different compositions at high pressures versus the dependence on melt composition of water solubility in silicate melts at low pressures; and the variations of viscosity, electrical conductivity, the diffusivity of “water,” the diffusivity of cesium, and phase relationships with the total dissolved water contents of melts.This model is thus consistent with available observations on hydrous melt systems and available data on the species concentrations of hydrous glasses and is easily tested, since measurements of the concentrations of molecular water and hydroxyl groups in silicate glasses quenched from melts equilibrated over a range of conditions and total dissolved water contents are readily obtainable. 相似文献
10.
I. A. Andreeva 《Petrology》2016,24(5):462-476
Melt inclusions were studied by various methods, including electron and ion microprobe analysis, to determine the compositions of melts and mechanisms of formation of rare-metal peralkaline granites of the Khaldzan Buregtey massif in Mongolia. Primary crystalline and coexisting melt inclusions were found in quartz from the rare-metal granites of intrusive phase V. Among the crystalline inclusions, we identified potassium feldspar, albite, tuhualite, titanite, fluorite, and diverse rare-metal phases, including minerals of zirconium (zircon and gittinsite), niobium (pyrochlore), and rare earth elements (parisite). The observed crystalline inclusions reproduce almost the whole suite of major and accessory minerals of the rare-metal granites, which supports the possibility of their crystallization from a magmatic melt. Melt inclusions in quartz from these rocks are completely crystallized. Their daughter mineral assemblage includes quartz, microcline, aegirine, arfvedsonite, polylithionite, a zirconosilicate, pyrochlore, and a rare-earth fluorocarbonate. The melt inclusions were homogenized in an internally heated gas vessel at a temperature of 850°C and a pressure of 3 kbar. After the experiments, many inclusions were homogeneous and consisted of silicate glass. In addition to silicate glass, some inclusions contained tiny quench zircon crystals confined to the boundary of inclusions, which indicates that the melts were saturated in zircon. In a few inclusions, glass coexisted with a CO2 phase. This allowed us to estimate the content of CO2 in the inclusion as 1.5 wt %. The composition of glasses from the homogeneous melt inclusions is similar to the composition of the rare-metal granites, in particular, with respect to SiO2 (68–74 wt %), TiO2 (0.5–0.9 wt %), FeO (2.2–4.6 wt %), MgO (0.02 wt %), and Na2O + K2O (up to 8.5 wt %). On the other hand, the glasses of melt inclusions appeared to be strongly depleted compared with the rocks in CaO (0.22 and 4 wt %, respectively) and Al2O3 (5.5–7.0 and 9.6 wt %, respectively). The agpaitic index is 1.1–1.7. The melts contain up to 3 wt % H2O and 2–4 wt % F. The trace element analysis of glasses from homogenized melt inclusions in quartz showed that the rare-metal granites were formed from extensively evolved rare-metal alkaline melts with high contents of Zr, Nb, Th, U, Ta, Hf, Rb, Pb, Y, and REE, which reflects the metallogenic signature of the Khaldzan Buregtey deposit. The development of unique rare metal Zr–Nb–REE mineralization in these rocks is related to the prolonged crystallization differentiation of melts and assimilation of enclosing carbonate rocks. 相似文献
11.
Fred A. Blaine Robert L. Linnen Gerhard E. Brügmann 《Geochimica et cosmochimica acta》2005,69(5):1265-1273
Haplobasaltic melts with a 101 kPa dry eutectic composition (An42Di58) and varying water contents were equilibrated with their platinum capsule at 1523 K and 200 MPa in an internally heated pressure vessel (IHPV) equipped with a rapid quench device. Experimental products were inclusion-free glasses representative of the Pt-saturated silicate melts at the experimental conditions. Platinum concentrations were determined using an isotope dilution multicollector inductively coupled plasma mass spectrometer and water contents and distribution by Karl Fischer titration and Fourier transform infrared spectroscopy, respectively.The water content of the melt has no intrinsic effect on platinum solubility, for concentrations between 0.9 wt.% and 4.4 wt.% H2O (saturation). Platinum solubility increases with increasing water content, but this effect is an indirect effect because increasing water content at fixed fH2 (imposed by the IHPV) increases the oxygen fugacity of the experiment.The positive oxygen fugacity dependence of Pt solubility in a hydrous silicate melt at 200 MPa is identical to that in anhydrous melts of the same composition determined in previous studies at 101 kPa. This study extends the range of platinum solubilities to oxygen fugacities lower than was previously possible. Combining the data of this and previous studies, Pt solubility is related to oxygen fugacity (in bar) at 1523 K by the equation:
[Pt]total(ppb)=1389×fO2+7531×(fO2)1/2 相似文献
12.
以合成花岗岩、水、不同浓度的盐酸溶液、氢氟酸溶液作为反应初始物,在850℃,100 MPa,接近于NNO的条件下开展了金在不同花岗质熔体中溶解度的实验研究,实验固液相产物中的金含量使用石墨炉原子吸收法测定。实验结果显示,金在花岗质熔体中的溶解度变化范围为1.87～156.62μg/g,流体相中金的溶解度为0.31～6.92μg/g;金在熔体相中的溶解度较其在共存液相中的高。花岗质熔体相中金的溶解度明显受熔体化学组成的影响,过碱性富钠花岗质熔体中金的溶解度明显高些;金在花岗质熔体中的溶解度随着熔体中Na2O/K2O摩尔比增大而增大;在氟氯共存岩浆体系中,氟含量变化对金在熔体相中的溶解度影响不明显,而液相中氯含量增大有利于提高金在流体相中的含量。 相似文献
13.
Igor S. Peretyazhko Victor Ye. Zagorsky Sergey Z. Smirnov Mikhail Y. Mikhailov 《Chemical Geology》2004,210(1-4):91-111
Coexisting melt (MI), fluid-melt (FMI) and fluid (FI) inclusions in quartz from the Oktaybrskaya pegmatite, central Transbaikalia, have been studied and the thermodynamic modeling of PVTX-properties of aqueous orthoboric-acid fluids has been carried out to define the conditions of pocket formation. At room temperature, FMI in early pocket quartz and in quartz from the coarse-grained quartz–oligoclase host pegmatite contain crystalline aggregates and an orthoboric-acid fluid. The portion of FMI in inclusion assemblages decreases and the volume of fluid in inclusions increases from the early to the late growth zones in the pocket quartz. No FMI have been found in the late growth zones. Significant variations of solid/fluid ratios in the neighboring FMI result from heterogeneous entrapment of coexisting melts and fluids by a host mineral. Raman spectroscopy, SEM EDS and EMPA indicate that the crystalline aggregates in FMI are dominated by mica minerals of the boron-rich muscovite–nanpingite CsAl2[AlSi3O10](OH,F)2 series as well as lepidolite. Topaz, quartz, potassium feldspar and several unidentified minerals occur in much lower amounts. Fluid isolations in FMI and FI have similar total salinity (4–8 wt.% NaCl eq.) and H3BO3 contents (12–16 wt.%). The melt inclusions in host-pegmatite quartz homogenize at 570–600 °C. The silicate crystalline aggregates in large inclusions in pocket quartz completely melt at 615 °C. However, even after those inclusions were significantly overheated at 650±10 °C and 2.5 kbar during 24 h they remained non-homogeneous and displayed two types: (i) glass+unmelted crystals and (ii) fluid+glass. The FMI glasses contain 1.94–2.73 wt.% F, 2.51 wt.% B2O3, 3.64–5.20 wt.% Cs2O, 0.54 wt.% Li2O, 0.57 wt.% Ta2O5, 0.10 wt.% Nb2O5, 0.12 wt.% BeO. The H2O content of the glass could exceed 12 wt.%. Such compositions suggest that the residual melts of the latest magmatic stage were strongly enriched in H2O, B, F, Cs and contained elevated concentrations of Li, Be, Ta, and Nb. FMI microthermometry showed that those melts could have crystallized at 615–550 °C.
Crystallization of quartz–feldspar pegmatite matrix leads to the formation of H2O-, B- and F-enriched residual melts and associated fluids (prototypes of pockets). Fluids of different compositions and residual melts of different liquidus–solidus P–T-conditions would form pockets with various internal fluid pressures. During crystallization, those melts release more aqueous fluids resulting in a further increase of the fluid pressure in pockets. A significant overpressure and a possible pressure gradient between the neighboring pockets would induce fracturing of pockets and “fluid explosions”. The fracturing commonly results in the crushing of pocket walls, formation of new fractures connecting adjacent pockets, heterogenization and mixing of pocket fluids. Such newly formed fluids would interact with a primary pegmatite matrix along the fractures and cause autometasomatic alteration, recrystallization, leaching and formation of “primary–secondary” pockets. 相似文献
14.
Field relations, mineralogy, major- and trace-element contents (including REE analyses of whole-rock samples and minerals) of three Proterozoic granites and their associated molybdenite mineralized aplites have been studied at Allebuoda, Munka and Kåtaberget in northern Sweden. The granites crystallized from melts that were not saturated with water. The mineralized potassic aplites formed by quenching of residual melts caused by sudden pressure drop, H2O saturation and vapour escape during tectonic rupturing. Leucogranites with higher Na2O/K2O ratios from Allebuoda and Munka crystallized during H2O-saturated equilibrium conditions in which the exsolved vapour could continuously migrate away. The pressure was probably 3 kbar at Munka, and somewhat lower at Allebuoda.
The granites have REE patterns characterized by LREE enrichments and negative Eu anomalies. In comparison, the potassic aplites and the more sodic leucogranites are depleted in LREE, enriched in HREE and have larger negative Eu anomalies. Allanite and monazite are the most important REE carriers in the granites. These minerals are strongly enriched in LREE, whereas fluorite and xenotime, which are more abundant in the aplites, are most enriched in HREE. Due to the strong control of accessory minerals on the REE balance, REE are of limited use in petrogenetic modelling of highly evolved granitic systems. 相似文献
15.
Oliver J. Schatz David Dolej John Stix Anthony E. Williams-Jones Graham D. Layne 《Chemical Geology》2004,210(1-4):135-147
Fluid-saturated experiments were conducted to investigate the partitioning of boron among haplogranitic melt, aqueous vapor and brine at 800 °C and 100 MPa. Experiments were carried out in cold-seal pressure vessels for 1 to 21 days, and utilized powdered synthetic subaluminous haplogranite glass doped with 1000 ppm B (crystalline H3BO3) and variable amounts of NaCl and H2O at a fluid/haplogranite mass RATIO=1:1. Run-product glasses were analyzed for boron concentration by secondary ion mass spectrometry (SIMS) and for major elements and chlorine by electron microprobe. The composition of the coexisting fluid was calculated by mass balance. Boron partition coefficients between aqueous vapor and hydrous granitic melt range from 3.1 to 6.3, and demonstrate a clear preference of boron for the vapor over the hydrous melt. Partition coefficients between brine and hydrous granitic melt vary from 0.45 to 1.1, suggesting that boron has no preference for the brine or the melt. The bulk fluid–melt partition coefficients for low-salinity and high-salinity experiments are DB(vapor/melt)=4.6±1.3 and DB(brine/melt)=0.91±0.49, respectively. The corresponding vapor–brine partition coefficient is 5.0±3.1, demonstrating that boron partitions preferentially into the vapor over the brine at the conditions of this study. The preferential incorporation of boron in the aqueous vapor is controlled by borate speciation and solution mechanism. The dominant borate species in aqueous fluids, H3BO3o, is highly soluble in aqueous vapor (XB2O3=0.187); however, B2O3 is immiscible in NaCl liquid. Consequently, concentrations of boron in aqueous vapor are significantly higher than in the coexisting brine. Furthermore, Na–B complexing in the melt at high chlorine fluid contents stabilizes boron in the melt thereby contributing to the non-preferential partitioning of boron between brine and melt. The commonly observed association of tourmalinization (boron metasomatism), brecciation and ore deposition in nature is consistent with the preferential partitioning of boron into aqueous vapor of magmatic-hydrothermal systems predicted by this study. 相似文献
16.
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
17.
The data obtained on the sodic part of the SiO2-Al2O3-Na2O-K2O system with F at 800°C and 1 kbar provide the basis for constructing a phase diagram showing the region of an aluminosilicate melt. In this system, oxide and fluoride phases are identified that control the stability field of the melt and the solubility of F. Liquid immiscibility was detected in aluminous nepheline-and quartz-normative Li-bearing compositions (the latter compositions are characterized by a wider immiscibility field). Solubility of F was determined in an aluminosilicate melt saturated with respect to F, i.e., coexisting with phases rich in this element. The F concentrations in the glasses range from 2 to 20 wt %. The quartz-normative glasses are poorer in F (no more than 5 wt % F) than the nepheline-normative glasses (which contain mostly 5–10 wt % F). The maximum F concentrations (> 10 wt %) in the phase diagram lie on both sides of the albite composition point in the region of ultragpaitic nepheline-normative melts and in the region of normal syenite melts. Changes in the phase relations when Na is substituted for K were determined in the quartz-normative silicate melt. 相似文献
18.
Tectonically controlled fluid flow and water-assisted melting in the middle crust: An example from the Central Alps 总被引：2，自引：0，他引：2
Melting triggered by influx of a free aqueous fluid in the continental crust has commonly been inferred, but the source of water in such contexts remains a matter of debate. We focus on the Tertiary migmatites in the Southern Steep Belt of the Central Alps (Switzerland) to discuss the petrology, structures and geodynamic setting of water-assisted melting. These migmatites comprise various structural types (e.g. metatexites, diatexites, melt in shear zones), which reflect variable leucosome fractions. The melting event itself as well as the variable melt fractions are related to the amount of aqueous fluids. At a given P and T, melt-fractions in rocks of minimum melt composition correlate with the amount of infiltrated aqueous fluids. In more granodioritic systems the water distributes between melt and newly crystallizing hydrous phases such as amphibole, such that the melt fraction correlates with the contents of H2O, Al, and Ca in the system. Phase-equilibrium modelling indicates that the stabilization of amphibole leads to slightly lower melt fractions than in a granitic system at the same P, T and bulk water content. Phase-equilibrium models further indicate that in the Alpine migmatite belt: (1) several wt.% water (fluid:rock ratio of 1:30) are necessary to produce the inferred melt fraction; (2) the activity of H2O in the fluid is high; and (3) spatially associated metapelites are unlikely as a source for the required aqueous fluids.
We present a tectonic scenario for the southern margin of the Central Alps, to which these migmatites are confined, and we propose that water was produced from dehydration reactions in metapelites in the Southern Alps. We model fluid production rates at the time of melting and demonstrate that the resulting fluid flow pattern is mainly controlled by the differences in permeability between the fluid source region and melting region. The proposed model requires strong gradients in temperature and permeability for the two tectonic blocks. This is consistent with the scenario involving indenter tectonics at the boundary between the Central and the Southern Alps in Oligocene times. 相似文献
19.
Ilya V. Veksler 《Chemical Geology》2004,210(1-4):7-31
Several types of fluid immiscibility may affect the evolution of volatile-rich magmatic systems at the magmatic–hydrothermal transition. The topology of silicate–salt–H2O systems implies that three-fluid immiscibility (silicate melt+hydrosaline melt+vapour) should be stable in a broad range of compositions and P–T conditions. The most important factor controlling the immiscibility appears to be the Coulombic properties (electric charges Z and ionic radii r) of the main network-modifying cations and the capacity for immiscibility appears to decrease in the following sequence: Mg>Ca>Sr>Ba>Li>Na>K. Liquid immiscibility is enhanced in peralkaline compositions and in the presence of nonsilicate anions such as F−, Cl−, CO32− and BO33−. In volatile-rich magmatic systems, the H2O is likely to react with the chloride, fluoride, borate and carbonate species and the chemical effects of high-temperature hydrolysis may be greatly enhanced by phase separation in systems with multiple immiscible fluid phases. Natural granitic magmas can thus exsolve a range of chemically and physically diverse hydrosaline liquids and the role of these fluid phases is likely to be especially significant in pegmatites and Li–F rare-metal granites. 相似文献
20.
The phase relationships of three peralkaline rhyolites fromthe Kenya Rift have been established at 150 and 50 MPa, at oxygenfugacities of NNO - 1·6 and NNO + 3·6 (log fO2relative to the Ni–NiO solid buffer), between 800 and660°C and for melt H2O contents ranging between saturationand nominally anhydrous. The stability fields of fayalite, sodicamphiboles, chevkinite and fluorite in natural hydrous silicicmagmas are established. Additional phases include quartz, alkalifeldspar, ferrohedenbergite, biotite, aegirine, titanite, montdoriteand oxides. Ferrohedenbergite crystallization is restrictedto the least peralkaline rock, together with fayalite; it isreplaced at low melt water contents by ferrorichterite. Riebeckite–arfvedsoniteappears only in the more peralkaline rocks, at temperaturesbelow 750°C (dry) and below 670°C at H2O saturation.Under oxidizing conditions, it breaks down to aegirine. In themore peralkaline rocks, biotite is restricted to temperaturesbelow 700°C and conditions close to H2O saturation. At 50MPa, the tectosilicate liquidus temperatures are raised by 50–60°C,and that of amphibole by 30°C. Riebeckite–arfvedsonitestability extends down nearly to atmospheric pressure, as aresult of its F-rich character. The solidi of all three rocksare depressed by 40–100°C compared with the solidusof the metaluminous granite system, as a result of the abundanceof F and Cl. Low fO2 lowers solidus temperatures by at least30°C. Comparison with studies of metaluminous and peraluminousfelsic magmas shows that plagioclase crystallization is suppressedas soon as the melt becomes peralkaline, whatever its CaO orvolatile contents. In contrast, at 100 MPa and H2O saturation,the liquidus temperatures of quartz and alkali feldspar arenot significantly affected by changes in rock peralkalinity,showing that the incorporation of water in peralkaline meltsdiminishes the depression of liquidus temperatures in dry peralkalinesilicic melts compared with dry metaluminous or peraluminousvarieties. At 150 MPa, pre-eruptive melt H2O contents rangefrom 4 wt % in the least peralkaline rock to nearly 6 wt % inthe two more peralkaline compositions, in broad agreement withprevious melt inclusion data. The experimental results implymagmatic fO2 at or below the fayalite–quartz–magnetitesolid buffer, temperatures between 740 and 660°C, and meltevolution under near H2O saturation conditions. KEY WORDS: peralkaline; rhyolite; phase equilibria 相似文献