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1.
The chemical interaction between fluorine and highly polymerized sodium aluminosilicate melts [Al/(Al+Si)= 0.125–0.250 on the join NaAlO2-SiO2] has been studied with Raman spectroscopy. Fluorine is dissolved to form F ions that are electrically neutralized with Na+ or Al3+. There is no evidence for association of fluorine with either Si4+ or Al3+ in four-fold coordination and no evidence of fluorine in six-fold coordination with Si4+ in these melt compositions. Upon solution of fluorine nonbridging oxygens are formed and are a part of structural units with nonbridging oxygen per tetrahedral cations (NBO/T) about 2 and 1. The proportions of these two depolymerized units in the melts increase systematically with increasing F/(F+O) at constant Al/(Al+Si) and with decreasing Al/(Al+Si) at constant F/(F+O). Depolymerization (increasing NBO/T) of silicate melts results from a fraction of aluminum and alkalies (in the present study; Na+) reacting to form fluoride complexes. In this process an equivalent amount of Na+ (orginally required for Al-3+charge-balance) or Al3+ (originally required Na+ to exist in tetrahedral coordination) become network-modifiers.The structural data have been used to develop a method for calculating the viscosity of fluorine-bearing sodium aluminosilicate melts at 1 atm. Where experimental viscosity data are available, the calculated and measured values are within 5% of each other.A method is also suggested by which the liquidus phase equilibria of fluorine-bearing aluminosilicate melts may be predicted. In accord with published experimental data it is suggested, for example, that — on the basis of the determined solubility mechanism of fluorine in aluminosilicate melts — with increasing fluorine content of feldspar-quartz systems, the liquidus boundaries between aluminosilicate minerals (e.g., feldspars) and quartz shift away from silica.  相似文献   

2.
Phase relations were investigated in the model water-saturated system Si-Al-Na-Li-F-O at high fluorine contents, a temperature of 800°C, and a pressure of 1 kbar. The obtained aluminosilicate melts are widely variable from quartz- to nepheline-normative compositions with agpaitic indexes both higher and lower than one. Various fluoride, aluminofluoride, and oxide phases were observed in the equilibrium assemblage depending on the melt composition: quartz and cryolite associate with the silica richest aluminosilicate melts, topaz and corundum coexist with peraluminous melts, and villiaumite was observed in highly peralkaline melts. Extensive immiscibility between aluminosilicate and aluminofluoride melts was observed in the system. Aluminofluoride melt coexists with quartz- and nepheline-normative aluminosilicate melts with agpaitic indexes (K a) of 0.7–1.4. The composition of aluminosilicate melt in equilibrium with aluminofluoride melt ranges from 33 to 70 wt % SiO2, from 12 to 24 wt % Al2O3, and from 5 to 16 wt % alkalis. The aluminofluoride melt is variable in composition, its Al/Na ratio ranges from 20/80 to 40/60 depending on the composition of the equilibrium aluminosilicate melt. The experimental aluminosilicate melts equilibrated with cryolite, topaz, and aluminofluoride melt coincide in major component proportions with the bulk compositions of cryolite- and topaz-bearing granites and melt inclusions in minerals.  相似文献   

3.
The water solubility in haplogranitic melts (normative composition Ab39Or32Qz29) coexisting with H2O-H2 fluids at 800 and 950 °C and 1, 2 and 3 kbar vapour pressure has been determined using IR spectroscopy. The experiments were performed in internally heated pressure vessels and the hydrogen fugacity (f H2) was controlled using the double capsule technique and oxygen buffer assemblages (WM and IW). Due to the limited lifetimes of these oxygen buffers the water solubility was determined from diffusion profiles (concentration-distance profiles) measured with IR spectroscopy in the quenched glasses. The reliability of the experimental strategy was demonstrated by comparing the results of short- and long-duration experiments performed with pure H2O fluids. The water solubility in Ab39Or32Qz29 melts equilibrated with H2O-H2 fluids decreases progressively with decreasing f H2O, as f H2 (or X H2) increases in the fluid phase. The effect of H2 on the evolution of the water solubility is similar to that of CO2 or another volatile with a low solubility in the melt and can be calculated in a first approximation with the Burnham water solubility model. Recalculation of high temperature water speciation for AOQ melts coexisting with H2O-H2 fluids at 800 °C, 2 kbar suggests that the concentrations of molecular H2O are proportional to f H2O (calculated using available mixing models), indicating Henrian behaviour for the solubility of molecular H2O in haplogranitic melts. Received: 29 June 1998 / Accepted: 10 March 1999  相似文献   

4.
Many experimental studies have been performed to evaluate the composition of coexisting silicate melts and magmatic volatile phases (MVP). However, few studies have attempted to define the relationship between melt chemistry and the acidity of a chloride-bearing fluid. Here we report data on melt composition as a function of the HCl concentration of coexisting brines. We performed 35 experimental runs with a NaCl-KCl-HCl-H2O brine (70 wt% NaCl [equivalent])-silicate melt (starting composition of Qtz0.38Ab0.33Or0.29, anhydrous) assemblage at 800°C and 100 MPa. We determined an apparent equilibrium constant
  相似文献   

5.
Liquidus phase relations have been experimentally determined in the systems Qz-Ab-Or-(H2O), Qz-Ab-(H2O) and Qz-Or-(H2O) at H2O-undersaturated conditions (a H2O = 0.07) and P = 5 kbar. Starting materials were homogeneous synthetic glasses containing 1 wt% H2O. The liquidus temperatures were bracketed by crystallization and dissolution experiments. The results of kinetic studies showed that crushed glasses are the best starting materials to overcome undercooling and to minimize the temperature difference between the lowest temperature of complete dissolution (melting) and the highest temperature at which crystallization can be observed. At P = 5 kbar and a H2O = 0.07, the Qz-Ab eutectic composition is Qz32Ab68 at 1095 °C (±10 °C) and the Qz-Or eutectic is Qz38Or62 at 1030 °C (±10 °C). The minimum temperature of the ternary system Qz-Ab-Or is 990 °C (±10 °C) and the minimum composition is Qz32Ab35‐ Or33. The Qz content of the minimum composition in the system Qz-Ab-Or-H2O remains constant with changing a H2O. The normative Or content, however, increases by approximately 10 wt% with decreasing a H2O from 1 to 0.07. Such an increase has already been observed in the system Qz-Ab-Or-H2O-CO2 at high a H2O and it is concluded that the use of CO2 to reduce water activities does not influence the composition of the minima in quartz-feldspar systems. The determined liquidus temperature in melts with 1 wt% H2O is very similar to that obtained in previous nominally “dry” experiments. This discrepancy is interpreted to be due to problems in obtaining absolutely dry conditions. Thus, the hitherto published solidus and liquidus temperatures for “dry” conditions are probably underestimated. Received: 27 March 1997 / Accepted: 1 October 1997  相似文献   

6.
Liquidus phase relations in the system diopside–kalsilite–forsterite–quartz with 3 wt% F were examined at 1 bar and the locations of important invariant points were determined at 18 kbar. At all pressures within this range a large liquidus field for fluorphlogopite (Phl) exists, and has a large influence on both melting and fractionation processes. One eutectic point was found to the silica-rich side of the plane Lc–Fo–Di at Di1Ks30Fo2Qz67, where a melt coexists with San, Qz, Phl and Di at 840 °C and 1 bar. Another eutectic point must exist in the silica-poor part of the system because the phase topology determines that thermal barriers must exist. At this point a feldspathoid, either Lc or Ks, must coexist with Fo, Phl and a Ca-bearing phase such as Di. The exact location and phase assemblage were not determined, but the equilibrium melt must have a composition rich in Di (>29 wt%) and extremely poor in Qz (<8 wt%). The composition of the first eutectic moves towards lower SiO2 contents with increasing pressure (Di3Ks40Fo1Qz56 at 18 kbar), whereas the second does not exist at 18 kbar due to the disappearance of Lc as a stable liquidus phase. Liquids which coexist with mafic minerals such as En, Fo, Phl and Di are important for the genesis of potassium-rich mafic rocks by partial melting in the mantle and for the early stages of fractional crystallisation. The equilibrium melt at the invariant point Fo + En + Phl + Di + L at 1125 °C is very poor in Fo and Di components at atmospheric pressure (Di5Ks37Fo5Qz53), whereas at 18 kbar the melt contains large amounts of Fo and Di (Di19Ks31- Fo28Qz21), and has a composition close to that of natural lamproites. Kamafugites do not correspond to melts in this system under any of the studied conditions, and appear to require CO2 in the source. Fractionation processes from primitive potassic basanite melts are controlled principally by the size (and not the mere presence) of the liquidus phase field for phlogopite: at high pressures where the Phl field is large, olivine is eliminated early from the fractionating assemblage and Cpx + Phl fractionation may lead to relatively silica-rich rock differentiates such as trachytes. At low pressures, extensive olivine and restricted Phl crystallisation prevents silica enrichment in the melt, resulting in phonolitic differentiates. Later crystallisation of alkali feldspar accentuates the trends laid down in the early stages of fractionation. Received: 2 February 1999 / Accepted: 14 October 1999  相似文献   

7.
Phase relationships in the system kalsilite-forsterite-quartz with fluorine added by direct substitution for oxygen were examined at 28 kb. A large liquidus field for fluorphlogopite exists with approx. 4 wt% F added to the system and the thermal stability of phlogopite is increased by 300° C relative to the water saturated system. Fluorine expands the phase volume of enstatite relative to forsterite so that the peritectic point PHL+EN+FO+L, a model for melting of a phlogopite harzburgite, lies in the silica-undersaturated field. Experimental phlogopites have excess Si which correlates with F content and are Al-deficient. The high Si contents indicate solid solution with an end member intermediate between tri- and di-octahedral micas. Glasses with compositions analogous to partial melts from phlogopite harzburgite were examined by infrared spectroscopy in the mid- and far-IR regions. Results show that fluorine polymerises the melt by bonding with all the network modifying cations K, Mg and Al. At higher F contents, but still less than 1 wt%, tetrahedral KAlO2-groups are complexed by fluorine and removed from the aluminosilicate network simultaneously polymerising and increasing the Si/(Si+Al) ratio of the network. However, when HF rather than F is present, the overall effect will be to depolymerise melts due to the effect of OH released by dissolution of HF. The presence of abundant Si-F bonds is considered unlikely even in silica-rich magmas: the viscosity decrease characteristic of fluorine-bearing melts can be attributed to the formation of fluoride complexes.  相似文献   

8.
Experimental data indicate that high F concentrations in leucocratic aluminosilicate melts (of granite and nepheline syenite composition) bring about the crystallization of F-rich minerals (topaz, villiaumite, and cryolite) on the liquidus. The crystallization of the minerals is controlled by the silicity, agpaitic coefficient, and proportions of alkalis in the system SiO2-Al2O3-Na2O-K2O-F-H2O. Our earlier experimental data on this system are compared with petrographic and petrochemical data on granites and nepheline syenites containing accessory topaz, cryolite, and villiaumite. The composition of topaz- and cryolite-bearing rocks is proved to correspond to the experimentally established equilibrium fields of F-rich aluminosilicate melt with these minerals. It is proved that the high-F minerals can crystallize from melt. The partial substitution of K and Na for Li modifies phase relations in the system, first of all, significantly expands the equilibrium field of aluminosilicate melt and alkaline aluminofluoride melts. The two melts are proved to be immiscible within broad compositional ranges in the SiO2-Al2O3-Na2O-Li2O-F-H2O system at 800–650°C and 1 kbar. Experimental data indicate that fluoride brine can coexist with aluminosilicate melts in nature. This finds support data on melt inclusions in granites and alkaline rocks whose contents of major components, water and fluorine are close to those in the experimental glasses. Our data lend support to the hypothesis that large cryolite bodies at the Ivigtut, Pitinga, Ulog-Tanzek, and other deposits were formed by fluoride salt melts that separated from F-rich aluminosilicate magmas late in the course of their differentiation. It is experimentally established that fluoride salt melts are able to concentrate valuable trace elements, such as Li, W, Nb, Hf, Sc, U, Th, and REE, which suggests that such melts can play an important role in the origin of rare-metal deposits genetically related to rocks that crystallize from magmas rich in F.  相似文献   

9.
We have measured the water solubility between 1 atmosphere and 5 kilobars for a calcium aluminosilicate melt of molar composition CaO 0.28, Al2O3 0.06, SiO2 0.66 (An9Wo38Qz53). The water contents were measured via thermogravimetric analysis of isobarically quenched glasses, and range from 0.121 wt% H2O near 1 aim to 9.25 wt% H2O at 5 kilobars. The molar water solubility lies between those of SiO2 and albite melts below around three kilobars, and crosses the albite solubility curve above this pressure. The present results are compared with data in the literature on related calcium aluminosilicate melts. There seems to be little variation of water solubility with composition for calcium aluminosilicate melts, unlike analogous alkali aluminosilicate compositions. Examination of the data suggests that there may be a maximum in molar water solubility along the albite-anorthite join.  相似文献   

10.
Diffusion of water was experimentally investigated for melts of albitic (Ab) and quartz-orthoclasic (Qz29Or71, in wt %) compositions with water contents in the range of 0 to 8.5 wt % at temperatures of 1100 to 1200 °C and at pressures of 1.0 and 5.0 kbar. Apparent chemical diffusion coefficients of water (D water) were determined from concentration-distance profiles measured by FTIR microspectroscopy. Under the same P-T condition and water content the diffusivity of water in albitic, quartz-orthoclasic and haplogranitic (Qz28Ab38 Or34, Nowak and Behrens, this issue) melts is identical within experimental error. Comparison to data published in literature indicates that anhydrous composition only has little influence on the mobility of water in polymerized melts but that the degree of polymerization has a large effect. For instance, Dwater is almost identical for haplogranitic and rhyolitic melts with 0.5–3.5 wt % water at 850 °C but it is two orders of magnitude higher in basaltic than in haplogranitic melts with 0.2–0.5 wt % water at 1300 °C. Based on the new water diffusivity data, recently published in situ near-infrared spectroscopic data (Nowak 1995; Nowak and Behrens 1995), and viscosity data (Schulze et al. 1996) for hydrous haplogranitic melts current models for water diffusion in silicate melts are critically reviewed. The NIR spectroscopy has indicated isolated OH groups, pairs of OH groups and H2O molecules as hydrous species in polymerized silicate melts. A significant contribution of isolated OH groups to the transport of water is excluded for water contents above 10 ppm by comparison of viscosity and water diffusion data and by inspection of concentration profiles from trace water diffusion. Spectroscopic measurements have indicated that the interconversion of H2O molecules and OH pairs is relatively fast in silicate glasses and melts even at low temperature and it is inferred that this reaction is an active step for migration of water. However, direct jumps of H2O molecules from one cavity within the silicate network to another one can not be excluded. Thus, we favour a model in which water migrates by the interconversion reaction and, possibly, small sequences of direct jumps of H2O molecules. In this model, immobilization of water results from dissociation of the OH pairs. Assuming that the frequency of the interconversion reaction is faster than that of diffusive jumps, OH pairs and water molecules can be treated as a single diffusing species having an effective diffusion coefficient . The shape of curves of Dwater versus water content implies that increases with water content. The change from linear to exponential dependence of Dwater between 2 and 3 wt % water is attributed to the influence of the dissociation reaction at low water content and to the modification of the melt structure by incorporation of OH groups. Received: 26 March 1996 / Accepted: 23 August 1996  相似文献   

11.
高度演化花岗岩类多为富F的熔体溶液体系 ,具有鲜明的、不同于其他体系的地球化学行为。富F岩浆固相线和液相线的降低和岩浆寿命的延长 ,使残余熔体与热水热液的性状差异减小 ,模糊了岩浆与热液之间的界线。最近对于富F、B和P伟晶岩中熔融包裹体的研究获得了新的进展。在约 70 0~ 5 0 0℃的温度和 1 0 0 0× 1 0 5Pa的压力下 ,在伟晶岩石英中发现两种不同类型的熔体包裹体 ,一种是富硅酸盐、贫水的熔体包裹体 ,另一种是贫硅酸盐、富水的熔体包裹体。两种熔体在硅酸盐 (+F +B +P) 水体系的溶离线边界上同时被圈闭。这表明 ,在地壳浅部侵位的侵入体 ,当温度≥ 70 0℃时 ,水在富F、B和P的熔体中可以无限混溶 ;而一旦温度降低 ,就会分离为两种共存的熔体并伴随强烈的元素分异作用。在溶离线的富水一侧形成与正常硅酸盐熔体有很大不同的高度富挥发份的熔体 ,这种致密、高粘度、高扩散性以及高活动性的超富水 (hyper aqueousmelt)熔体 ,可以与水溶液流体相类比。这为岩浆热液过渡性流体的假说提供了新的有利的证据。此外 ,在这种具有超富水和熔体特征的过渡性流体中 ,微迹元素可能具有特殊的地球化学行为 ,如在许多晚期花岗岩包括淡色花岗岩和伟晶岩中稀土元素配分模式所显示的四分组效应等。富F熔体溶液体?  相似文献   

12.
The magmatic-hydrothermal evolution of two barren granites associated with the Tertiary Questa Caldera in northern New Mexico was reconstructed on the basis of microthermometric and laser-ablation inductively coupled plasma mass spectrometry analysis of fluid and melt inclusions in quartz of magmatic and hydrothermal origin. During progressive crystallization and fluid exsolution, the Cs content of the residual melt increased from 1 ppm to values as high as 5500 ppm, which requires an increase in crystallinity by at least 99.98%. In conjunction with a Rayleigh fractionation model simulating the melt evolution at fluid-saturated vs. fluid-undersaturated conditions, the melt inclusion data can be used to determine the crystallinity at which fluid saturation was reached. Our results suggest that both plutons attained fluid saturation before 30% crystallization and that evolved residual melts accumulated in their roof zones. At ∼90% crystallization, the exsolving fluids were of low salinity (∼5 wt.% NaClequiv) and in the one-phase field, in accordance with phase relations at the reconstructed P and T conditions (∼1.1 to 1.3 kbar, 700 to 720°C). Fluid-melt partition coefficients for a range of metals determined on assemblages of coeval melt and fluid inclusions were generally too low to allow efficient metal extraction from the melt (DX, fluid-melt < 22). As a result, the metal concentrations in both the residual melt and the coexisting fluid increased with progressive crystallization. Absolute metal contents in the fluids exsolving from barren systems appear low, however, when compared with mineralized systems. It is concluded that the absence of mineralization in the Rito del Medio and Cañada Pinabete plutons primarily stems from a low salinity of the exsolving fluids, resulting in a less efficient metal extraction from the melt.  相似文献   

13.
We have experimentally investigated the kinetics of melting of an aplitic leucogranite (quartz+sodic plagioclase of ≈Ab90+K-feldspar+traces of biotite) at 690, 740, and 800°C, all at 200 MPa H2O. Leucogranite cylinders, 3.5 mm in diameter and 7 mm in length, were run in the presence of excess H2O using cold-seal pressure vessels for 11–2,925 h. At 690 and 740°C and any experimental time, and 800°C and short run times, silicate glass (melt at run conditions) occurs as interconnected films along most of the mineral boundaries and in fractures, with the predominant volume occurring along quartz/feldspars boundaries and quartz/plagioclase/K-feldspar triple junctions. Glass film thickness is roughly constant throughout a given experimental charge and increases with experimental temperature and run duration. The results indicate that H2O-saturated partial melting of a quartzo-feldspathic protolith will produce an interconnected melt phase even at very low degrees (<5 vol%) of partial melting. Crystal grain boundaries are therefore completely occluded with melt films even at the lowest degrees of partial melting, resulting in a change in the mechanism of mass transport through the rock from advection of aqueous vapor to diffusion through silicate melt. At 690 and 740°C the compositions of glasses are homogeneous and (at both temperatures) close to, but not on, the H2O-saturated 200 MPa haplogranite eutectic; glass compositions do not change with run duration. At 800°C glasses are heterogeneous and plot away from the minimum, although their molar ratios ASI (=mol Al2O3/CaO+Na2O+K2O) and Al/Na are constant throughout the entire charge at any experimental time. Glass compositions within individual 800°C experiments form linear trends in (wt%) normative quartz–albite–orthoclase space. The linear trends are oriented perpendicular to the 200 MPa H2O haplogranite cotectic line, reflecting nearly constant albite/orthoclase ratio versus variable quartz/feldspar ratio, and have endpoints between the 800°C isotherms on the quartz and feldspar liquidus surfaces. With increasing experimental duration the trends migrate from the potassic side of the minimum toward the bulk rock composition located on the sodic side, due to more rapid (and complete) dissolution of K-feldspar relative to plagioclase. The results indicate that partial melting at or slightly above the solidus (690–740°C) is interface reaction-controlled, and produces disequilibrium melts of near-minimum composition that persist metastably for up to at least 3 months. Relict feldspars show no change in composition or texture, and equilibration between melt and feldspars might take from a few to tens of millions of years. Partial melting at temperatures well above the solidus (800°C) produces heterogeneous, disequilibrium liquids whose compositions are determined by the diffusive transport properties of the melt and local equilibrium with neighboring mineral phases. Feldspars recrystallize and change composition rapidly. Partial melting and equilibration between liquids and feldspars might take from a few to tens of years (H2O-saturated conditions) at these temperatures well above the solidus.  相似文献   

14.
We studied the mineralogy, mineral chemistry, and compositions of 48 interior silicate inclusions and a large K-rich surface inclusion from the Colomera IIE iron meteorite. Common minerals in the interior silicate inclusions are Cr diopside and Na plagioclase (albite). They are often enclosed by or coexist with albitic glasses with excess silica and minor Fe-Mg components. This mineral assemblage is similar to the “andesitic” material found in the Caddo County IAB iron meteorite for which a partial melt origin has been proposed. The fairly uniform compositions of Cr diopside (Ca44Mg46Fe10) and Na plagioclase (Or2.5Ab90.0An7.5 to Or3.5Ab96.1An0.4) in Colomera interior inclusions and the angular boundaries between minerals and metal suggest that diopside and plagioclase partially crystallized under near-equilibrium conditions from a common melt before emplacement into molten metal. The melt-crystal assemblage has been called “crystal mush.” The bulk compositions of the individual composite inclusions form an array between the most diopside-rich inclusion and plagioclase. This is consistent only with a simple mechanical mixing relationship, not a magmatic evolution series. We propose a model in which partly molten metal and crystal mush were mixed together by impact on the IIE parent body. Other models involving impact melting of the chondritic source material followed by growth of diopside and plagioclase do not easily explain near equilibrium growth of diopside and Na plagioclase, followed by rapid cooling. In the K-rich surface inclusion, K feldspar, orthopyroxene, and olivine were found together with diopside for the first time. K feldspar (sanidine, Or92.7Ab7.2An0.1 to Or87.3Ab11.0An1.7) occurs in an irregular veinlike region in contact with large orthopyroxene crystals of nearly uniform composition (Ca1.3Mg80.5Fe17.8 to Ca3.1Mg78.1Fe18.9) and intruding into a relict olivine with deformed-oval shape. Silica and subrounded Cr diopside are present within such K-feldspar regions. Some enrichments of the albite component have been detected at the end of curved elongated nodules of K feldspar intruded into the mafic silicates. The textural relationships suggest that a K-rich melt was present. A K-rich melt is neither the first melt of a chondritic system nor a differentiation product of a Na-rich partial melt of chondritic material. The K-rich material may have originated as a fluid phase that leached K from surrounding materials and segregated by a mechanism similar to that proposed for the Na-rich inclusions.  相似文献   

15.
To investigate the influence of temperature and composition on the diffusivities of dissolved carbon dioxide and argon in silicate melts, diffusion experiments were performed at magmatic pressure and temperature conditions in (a) albite melts with excess Na2O (0-8.6 wt%) and a constant Si/Al ratio of 3, and (b) albite70quartz30 to jadeite melts with decreasing SiO2 content and a constant Na/Al ratio of 1. We obtained diffusion coefficients at 500 MPa and 1323-1673 K. In the fully polymerized system Ab70Qz30 - Jd, the change in composition only has a weak effect on bulk CO2 diffusivity, but Ar diffusivity increases clearly with decreasing SiO2 content. In the system Ab + Na2O, bulk CO2 and Ar diffusivity increase significantly with gradual depolymerisation. The relatively small change in composition on molar basis in the depolymerized system leads to a significantly larger change in diffusivities compared to the fully polymerized Ab70Qz30-Jd join. Within error, activation energies for bulk CO2 and Ar diffusion in both systems are identical with decreasing silica content (Ab + Na2O: 159 ± 25 kJ mol−1 for bulk CO2 and 130 ± 8 kJ mol−1 for Ar; Ab70Qz30-Jd: 163 ± 16 kJ mol−1 for bulk CO2 and 148 ± 15 kJ mol−1 for Ar) even though this results in depolymerisation in one system and not the other.Although there is a variation in CO2 speciation with changing composition as observed in quenched glasses, it has previously established that this is not a true representation of the species present in the melt, with the ratio of molecular CO2 to carbonate decreasing during quenching. Thus, diffusion coefficients for the individual CO2 species cannot be directly derived by measuring molecular CO2 and CO32- concentration-distance profiles in the glasses. To obtain diffusivities of individual CO2 species, we have made two assumptions that (1) inert Ar can be used as a proxy for molecular CO2 diffusion characteristics as shown by our previous work and (2) the diffusivity of CO32− can be calculated assuming it is identical to network forming components (Si4+ and Al3+). This is derived from viscosity data (Eyring eqn.) and suggests that CO32− diffusion would be several orders of magnitude slower than molecular CO2 diffusion.The systematics of measured bulk CO2 diffusivity rates and comparison with the Ar proxy all suggest that the faster molecular CO2 species is much more dominant in melts than measurements on resulting quenched glasses would suggest. This study has confirmed an observation of surprisingly consistent bulk CO2 diffusivity across a range of natural compositions were Ar diffusivity significantly increases. This is consistent with an actual increase in molecular CO2 mobility (similar to Ar) that is combined with an increase in the proportion of the slower carbonate in the melt.These results demonstrate that the CO2 diffusion and speciation model provides an insight into the transport processes in the melt and is promising and an alternative tool to in situ speciation measurements at magmatic conditions, which at the moment are technically extremely difficult. We present the first high pressure high temperature in situ MIR spectra of a CO2 bearing albitic glass/melt suggesting that molecular CO2 is a stable species at high temperature, which is qualitatively consistent with the modelled CO2 speciation data.  相似文献   

16.
Cordierite–quartz and plagioclase–quartz intergrowths in a paragneiss from northern Labrador (the Tasiuyak Gneiss) were studied using SEM, STEM and TEM. The gneiss experienced granulite facies conditions and partial melting during both regional and, subsequently, during contact metamorphism. The microstructures examined all results from the contact metamorphism. Cordierite–quartz intergrowths occur on coarse and fine scales. The former sometimes exist as a ‘geometric’ intergrowth in which the interface between cordierite and quartz appears planar at the resolution of the optical microscope and SEM. The latter exists in several microstructural variants. Plagioclase is present as a minor component of the intergrowth in some examples of both the coarse and fine intergrowth. Grain boundaries in cordierite–quartz intergrowths are occupied by amorphous material or a mixture of amorphous material and chlorite. Cordierite and quartz are terminated by crystal faces in contact with amorphous material. Chlorite is sometimes found on cordierite surfaces and penetrating into cordierite grains along defects. Quartz contains (former) fluid inclusions 10–20 nm in maximum dimension. The presence of planar interfaces between cordierite and the amorphous phase is reminiscent of those between crystals and glass in volcanic rocks, but in the absence of compelling evidence that the amorphous material represents former melt, it is interpreted as a reaction product of cordierite. Plagioclase–quartz intergrowths occur in a number of microstructural variants and are commonly associated with cordierite–quartz intergrowths. The plagioclase–quartz intergrowths display simple, non‐planar interfaces between plagioclase and quartz. Quartz contains (former) fluid inclusions of dimensions similar to those observed in cordierite–quartz intergrowths. The boundary between quartz and enclosing K‐feldspar is cuspate, with quartz cusps penetrating a few tens of nanometres into K‐feldspar, commonly along defects in K‐feldspar and sometimes with very low dihedral angles at their tips. This cuspate microstructure is interpreted as melt pseudomorphs. The plagioclase–quartz intergrowths share some features with myrmekite, but differ in some respects: the composition of the plagioclase (An37Ab62Or1–An38Ab61Or1); the association with cordierite–quartz intergrowths; and microstructures that are atypical of myrmekite (e.g. quartz vermicules shared with cordierite–quartz intergrowths). It is inferred that the plagioclase–quartz intergrowths may have formed from, or in the presence of, melt. Inferred melt‐related microstructures preserved on the nanometre scale suggest that melt on grain boundaries was more pervasive than is evident from light optical and SEM observations.  相似文献   

17.
Detailed melt and fluid inclusion studies in quartz hosts from the Variscan Ehrenfriedersdorf complex revealed that ongoing fractional crystallization of the highly evolved H2O-, B-, and F-rich granite magma produced a pegmatite melt, which started to separate into two immiscible phases at about 720°C, 100 MPa. With cooling and further chemical evolution, the immiscibilty field expanded. Two conjugate melts, a peraluminous one and a peralkaline one, coexisted down to temperatures of about 490°C. Additionally, high-salinity brine exsolved throughout the pegmatitic stage, along with low-density vapor. Towards lower temperatures, a hydrothermal system gradually developed. Boiling processes occurred between 450 and 400°C, increasing the salinities of hydrothermal fluids at this stage. Below, the late hydrothermal stage is dominated by low-salinity fluids. Using a combination of synchrotron radiation-induced X-ray fluorescence analysis and Raman spectroscopy, the concentration of trace elements (Mn, Fe, Zn, As, Sb, Rb, Cs, Sr, Zr, Nb, Ta, Ag, Sn, Ta, W, rare earth elements (REE), and Cu) was determined in 52 melt and 8 fluid inclusions that are representative of distinct stages from 720°C down to 380°C. Homogenization temperatures and water contents of both melt and fluid inclusions are used to estimate trapping temperatures, thus revealing the evolutionary stage during the process. Trace elements are partitioned in different proportions between the two pegmatite melts, high-salinity brines and exsolving vapors. Concentrations are strongly shifted by co ncomitant crystallization and precipitation of ore-forming minerals. For example, pegmatite melts at the initial stage (700°C) have about 1,600 ppm of Sn. Concentrations in both melts decrease towards lower temperatures due to the crystallization of cassiterite between 650 and 550°C. Tin is preferentially fractionated into the peralkaline melt by a factor of 2–3. While the last pegmatite melts are low in Sn (64 ppm at 500°C), early hydrothermal fluids become again enriched with about 800 ppm of Sn at the boiling stage. A sudden drop in late hydrothermal fluids (23 ppm of Sn at 370°C) results from precipitation of another cassiterite generation between 400 and 370°C. Zinc concentrations in peraluminous melts are low (some tens of parts per million) and are not correlated with temperature. In coexisting peralkaline melts and high-T brines, they are higher by a factor of 2–3. Zinc continuously increases in hydrothermal fluids (3,000 ppm at 400°C), where the precipitation of sphalerite starts. The main removal of Zn from the fluid system occurs at lower temperatures. Similarly, melt and fluid inclusion concentrations of many other trace elements directly reflect the crystallization and precipitation history of minerals at distinctive temperatures or temperature windows.  相似文献   

18.
An experimental study of the effect of boron in the water saturated Q-Or-Ab-B2O3-H2O system has been performed at P=1 Kbar to provide experimental data and explain the role of boron in some late magmatic and early hydrothermal events. Experiments were conducted between 500° C and 800° starting from a gel, or a previously crystallized gel, and variable amounts of boron (0 to 18% B2O3) added to water. The phases obtained were: quartz, sanidine, albite, silicate liquid quenched to glass, and aqueous vapour phase. Boric acids, borates and isotropic low index materials were found in the quenched vapour phase. An aluminium silicate-like mineral, not yet fully identified, is also present.The solidus temperature of the Q-Or-Ab composition is lowered by 60° C when 5 wt. % B2O3 is added and by more than 130° C when 17wt. % B2O3 is added. Compositions of equilibrated silicate melts and vapours were obtained between 780° C and 750° C for various B2O3 concentrations. The vapour phase is B and Si rich. It is also enriched in Na with respect to K, and in alkalis with respect to Al. Its silicate solute content is higher than in experiments with pure water. The solubility of water is increased by the addition of boron in Q-Or-Ab melts. Microprobe data show that the melts equilibrated with vapour phases become hyperaluminous and more potassic than sodic. The partition coefficient of boron is in favour of the vapour (k D=B2O3% in melt/B2O3% in vapour=0.33±0.02). The effect of the interaction between the silicate phases and the vapour is discussed. Comparison is made between the behaviour of boron and that of chlorine and fluorine. Geological applications are also provided, which concern the influence of boron on minimum melting, on muscovite stability and on the hypersolvus-subsolvus transition.  相似文献   

19.
Crystal-melt relations at a water vapour pressure of 1 kilobar have been determined for planes at 3, 5, 7.5, and 10 weight per cent anorthite in the system NaAlSi3O8KAlSi3O8-CaAl2Si2O8-SiO2. The ratio of the silicate components in the liquids which are in univariant equilibrium with plagioclase, alkali feldspar, quartz and gas are Ab31Or28Q38An3 (weight per cent) at 730°±5–10° C, Ab21Or34Q40An5 at 745°±5–10° C and Ab10Or39 Q43.5An7.5 at 780°±10° C. The univariant curve on which the above compositions lieoriginates on the H2O-saturated Or-An-Q plane at a composition containing less than 10 weight per cent An and terminates within 1.5 weight per cent An of the H2O-saturated Or-Ab-Q plane. Experimental data for the synthetic system have been used to illustrate a discussion on the partial melting of metasediments and the possible significance of such a process with respect to the genesis of granitic rocks. Data taken from the literature (Winkler and v. Platen, 1960, 1961a) have been used to illustrate that the normative salic composition of a sediment has a strong influence on the composition of any melt which form when such a rock is subjected to high temperatures and pressures.  相似文献   

20.
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   

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