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1.
The exsolution of magmatic hydrosaline chloride liquids   总被引:14,自引:0,他引:14  
Jim D. Webster   《Chemical Geology》2004,210(1-4):33-48
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   


2.
Status report on stability of K-rich phases at mantle conditions   总被引:1,自引:0,他引:1  
George E. Harlow  Rondi Davies 《Lithos》2004,77(1-4):647-653
Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM3+Si2O6) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning (K)D(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF3 limit F content between 6 and 8 GPa. The perovskite KMgF3 is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. (M4)K-substituted potassic richterite (ideally K(KCa)Mg5Si8O22(OH,F)2) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H2O K-cymrite (hydrous hexasanidine–KAlSi3O8·nH2O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H2O2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K1−xn)2(Mg1−nMn3+)2Si2O7H2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H2O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □2Mg2Si2O7H2–(K□)Mg2Si2O7H–K2Mg2Si2O7 (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi3O8, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered.  相似文献   

3.
Based on data on the composition of ore-bearing hydrothermal solutions and parameters of ore-forming processes at various antimony and antimony-bearing deposits, which were obtained in studies of fluid inclusions in ore minerals, we investigated the behavior of Sb(III) in the system Sb–Cl–H2S–H2O describing the formation of these deposits.

We also performed thermodynamic modeling of native-antimony and stibnite dissolution in sulfide (mHS = 0.0001−0.1) and chloride (mCl = 0.1−5) solutions and the joint dissolution of Sb(s)0 and Sb2S3(s) in sulfide-chloride solution (mHS = 0.01; mCl = 1) depending on Eh, pH, and temperature. All thermodynamic calculations were carried out using the Chiller computer program. Under the above conditions, stibnite precipitates in acid, weakly acid to neutral, and medium redox solutions, whereas native antimony precipitates before stibnite under more reducing conditions in neutral to alkaline solutions.

The metal-bearing capacity of hydrothermal solutions (200–250 °C) of different compositions and origins has been predicted. We have established that the highest capacity is specific for acid (pH = 2–3) high-chloride solutions poor in sulfide sulfur and alkaline (pH = 7–8) low-chloride low-sulfide solutions.  相似文献   


4.
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   

5.
Marcasite precipitation from hydrothermal solutions   总被引:3,自引:0,他引:3  
Pyrite and marcasite were precipitated by both slow addition of aqueous Fe2+ and SiO32− to an H2S solution and by mixing aqueous Fe2+ and Na2S4 solutions at 75°C. H2S2 or HS2 and H2S4 or HS4 were formed in the S2O32− and Na2S4 experiments, respectively. Marcasite formed at pH < pK1 of the polysulfide species present (for H2S2, pK1 = 5.0; for H2S4, pK1 = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H2S2 and HS2 are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H2S2 and HS2 are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS2 and S22− are strongly attracted to the positive pyrite growth sites. Masking of 1πg* electrons in the S2 group by the protons makes HS2 and H2S2 isoelectronic with AsS2− and As22−, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H2S2 was formed near the site of deposition by either partial oxidation of aqueous H2S by O2 or by the reaction of higher oxidation state sulfur species that are reactive with H2S at the conditions of formation e.g., S2O32− but not SO42−. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).  相似文献   


6.
花岗岩浆液态不混溶作用和饱和H2O花岗岩浆的热液出溶作用是花岗岩类矿床成矿流体形成的重要机制。利用最新式热液金刚石压腔,开展了成矿流体形成机制的原位观测实验。在岩浆热液出溶过程的实验中,初始样品为各类硅酸盐和纯H2O或LiCl水溶液,在H2O饱和状态中,硅酸盐熔体珠不断分异出富H2O的流体。花岗岩浆液态不混溶实验的初始样品为NaAlSi3O8-LiAlSiO4-SiO2-LiCl-H2O。在硅酸盐完全重熔后的降温过程中,硅酸盐熔体珠分离出富H2O熔体相和贫H2O熔体相,压力的突然降低促进了相分离的发生。研究表明:岩浆热液的出溶作用发生在H2O饱和的条件下,是岩浆的“第二次”沸腾作用,对花岗岩型稀有金属矿床的形成具有重要意义;花岗岩浆液态不混溶产生的富H2O熔体易于结晶出粗大晶体,暗示岩浆液态不混溶作用可能是一些花岗伟晶岩形成的主要机制。两类成矿流体形成机制实验条件的差异表明,Li是花岗岩浆发生不混溶作用的重要因素。在今后的研究中,应把热液金刚石压腔的原位观测与微束分析技术结合,在高温高压状态下分析成矿元素的迁移和富集规律。  相似文献   

7.
We report compositions of homogenized quartz-hosted melt inclusions from a layered sequence of Li-, F-rich granites in the Khangilay complex that document the range of melt evolution from barren biotite granites to Ta-rich, lepidolite–amazonite–albite granites. The melt inclusions are crystalline at room temperature and were homogenized in a rapid-quench hydrothermal apparatus at 200 MPa before analysis. Homogenization runs determined solidus temperatures near 550 °C and full homogenization between 650 and 750 °C. The compositions of inclusions, determined by electron microprobe and Raman spectroscopy (for H2O), show regular overall trends of increasing differentiation from the least-evolved Khangilay units to apical units in the Orlovka intrusion. Total volatile contents in the most-evolved melts reach over 11 wt.% (H2O: 8.6 wt.%, F: 1.6 wt.%, B2O3: 1.5 wt.%). Concentrations of Rb range from about 1000 to 3600 ppm but other trace elements could not be measured reliably by electron microprobe. The resulting trends of melt evolution are similar to those described by the whole-rock samples, despite petrographic evidence for albite- and mica-rich segregations previously taken as evidence for post-magmatic metasomatism.

Melt variation trends in most samples are consistent with fractional crystallization as the main process of magma evolution and residual melt compositions plot at the granite minimum in the normative Qz–Ab–Or system. However, melts trapped in the highly evolved pegmatitic samples from Orlovka deviate from the minimum melt composition and show compositional variations in Al, Na and K that requires a different explanation. We suggest that unmixing of the late-stage residual melt into an aluminosilicate melt and a salt-rich dense aqueous fluid (hydrosaline melt) occurred. Experimental data show the effectiveness of this process to separate K (aluminosilicate melt) from Na (hydrosaline melt) and high mobility of the latter due to its low viscosity and relatively low density may explain local zones of albitization in the upper parts of the granite.  相似文献   


8.
Silicate-melt inclusions in magmatic rocks: applications to petrology   总被引:20,自引:0,他引:20  
Maria-Luce Frezzotti   《Lithos》2001,55(1-4):273-299
Silicate-melt inclusions in igneous rocks provide important information on the composition and evolution of magmatic systems. Such inclusions represent accidentally trapped silicate melt (±immiscible H2O and/or CO2 fluids) that allow one to follow the evolution of magmas through snapshots, corresponding to specific evolution steps. This information is available on condition that they remained isolated from the enclosing magma after their entrapment. The following steps of investigation are discussed: (a) detailed petrographic studies to characterise silicate-melt inclusion primary characters and posttrapping evolution, including melt crystallisation; (b) high temperature studies to rehomogenise the inclusion content and select chemically representative inclusions: chemical compositions should be compared to relevant phase diagrams.

Silicate-melt inclusion studies allow us to concentrate on specific topics; inclusion studies in early crystallising phases allow the characterisation of primary magmas, while in more differentiated rocks, they unravel the subsequent chemical evolution. The distribution of volatile species (i.e., H2O, CO2, S, Cl) in inclusion glass can provide information on the degassing processes and on recycling of subducted material. In intrusive rocks, silicate melt inclusions may preserve direct evidence of magmatic stage evolution (e.g., immiscibility phenomena). Melt inclusions in mantle xenoliths indicate that high-silica melts can coexist with mantle peridotites and give information on the presence of carbonate melt within the upper mantle. Thus, combining silicate-melt inclusion data with conventional petrological and geochemical information and experimental petrology can increase our ability to model magmatic processes.  相似文献   


9.
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   

10.
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 PT-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   


11.
Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H2O and CO2 (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg−1 and MnMg−1 on the octahedral site, some minor KNa−1 on the Ch0 channel site, and Fe3+Al−1 on the T11 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□−1Mg−1), and of Be and other divalent cations on the tetrahedral T11 site (NaBe□−1Al−1 and Na(Mg,Fe2+)□−1Al−1). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: Ch(Na,K)0–1 VI(Mg,Fe2+,Mn,Li)2 IVSi5 IVAl3 IV(Al, Be, Mg, Fe2+, Fe3+)O18 *xCh(H2O, CO2…). Our results show that the population of (Mg, Fe2+) on the T11-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under PT conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M2+–Na.  相似文献   

12.
Infrared spectroscopy and ion micro-probe measurements showed that the major constituent minerals of eclogites from the Kokchetav massif, which have been subducted to 180 km depths, contain significant amounts of water up to 870 ppm H2O (by weight) in omphacite, 130 ppm H2O in garnet and 740 ppm H2O in rutile. Omphacite shows three hydroxyl absorption bands at 3440–3460, 3500–3530 and 3600–3625 cm− 1, garnet has a single band at 3580–3630 cm− 1 and rutile has a single sharp band at 3280 cm− 1. The hydroxyl absorbance at these wavenumbers changes with the crystal orientation in polarized infrared radiation, indicating that the water is structurally incorporated in these minerals. The water contents in omphacite and garnet increase systematically with the metamorphic pressure of the host eclogites. The partitioning coefficient of the water content between coexisting garnet and omphacite is similar in different eclogites, DGrt/Omp0.1–0.2, but decreases slightly at high pressure. Based on the mineral proportions of the eclogites, we estimate bulk-rock water content in the eclogites ranging from 3070 to 300 ppm H2O (by weight). Although hydrous minerals are absent in the diamond-grade eclogite (60 kbar and 1000 °C), trace amounts of water are incorporated in the nominally anhydrous minerals such as omphacite and garnet. The presence of significant water in these minerals implies that the subducting oceanic crust can transport considerable amounts of water into the deep upper mantle beyond the stability of hydrous minerals. Such water may be stored in the deep upper mantle and have an important influence on dynamics in the Earth's interior.  相似文献   

13.
Partitioning coefficients between olivine and silicate melts   总被引:3,自引:0,他引:3  
J.H. Bdard 《Lithos》2005,83(3-4):394-419
Variation of Nernst partition coefficients (D) between olivine and silicate melts cannot be neglected when modeling partial melting and fractional crystallization. Published natural and experimental olivine/liquidD data were examined for covariation with pressure, temperature, olivine forsterite content, and melt SiO2, H2O, MgO and MgO/MgO + FeOtotal. Values of olivine/liquidD generally increase with decreasing temperature and melt MgO content, and with increasing melt SiO2 content, but generally show poor correlations with other variables. Multi-element olivine/liquidD profiles calculated from regressions of D REE–Sc–Y vs. melt MgO content are compared to results of the Lattice Strain Model to link melt MgO and: D0 (the strain compensated partition coefficient), EM3+ (Young's Modulus), and r0 (the size of the M site). Ln D0 varies linearly with Ln MgO in the melt; EM3+ varies linearly with melt MgO, with a dog-leg at ca. 1.5% MgO; and r0 remains constant at 0.807 Å. These equations are then used to calculate olivine/liquidD for these elements using the Lattice Strain Model. These empirical parameterizations of olivine/liquidD variations yield results comparable to experimental or natural partitioning data, and can easily be integrated into existing trace element modeling algorithms. The olivine/liquidD data suggest that basaltic melts in equilibrium with pure olivine may acquire small negative Ta–Hf–Zr–Ti anomalies, but that negative Nb anomalies are unlikely to develop. Misfits between results of the Lattice Strain Model and most light rare earth and large ion lithophile partitioning data suggest that kinetic effects may limit the lower value of D for extremely incompatible elements in natural situations characterized by high cooling/crystallization rates.  相似文献   

14.
The stability and phase relations of phengitic muscovite in a metapelitic bulk composition containing a mixed H2O+CO2 fluid were investigated at 6.5–11 GPa, 750–1050°C in synthesis experiments performed in a multianvil apparatus. Starting material consisted of a natural calcareous metapelite from the coesite zone of the Dabie Mountains, China, ultrahigh-pressure metamorphic complex that had experienced peak metamorphic pressures greater than 3 GPa. The sample contains a total of 2.1 wt.% H2O and 6.3 wt.% CO2 bound in hydrous and carbonate minerals. No additional fluid was added to the starting material. Phengite is stable in this bulk composition from 6.5 to 9 GPa at 900°C and coexists with an eclogitic phase assemblage consisting of garnet, omphacite, coesite, rutile, and fluid. Phengite dehydrates to produce K-hollandite between 8 and 11 GPa, 750–900°C. Phengite melting/dissolution occurs between 900°C and 975°C at 6.5–8 GPa and is associated with the appearance of kyanite in the phase assemblage. The formation of K-hollandite is accompanied by the appearance of magnesite and topaz-OH in the phase assemblage as well as by significant increases in the grossular content of garnet (average Xgrs=0.52, Xpy=0.19) and the jadeite content of omphacite (Xjd=0.92). Mass balance indicates that the volatile content of the fluid phase changes markedly at the phengite/K-hollandite phase boundary. At P≤8 GPa, fluid coexisting with phengite appears to be relatively CO2-rich (XCO2/XH2O=2.2), whereas fluid coexisting with K-hollandite and magnesite at 11 GPa is rich in H2O (XCO2/XH2O=0.2). Analysis of quench material and mass balance calculations indicate that fluids at all pressures and temperatures examined contain an abundance of dissolved solutes (approximately 40 mol% at 8 GPa, 60 mol% at 11 GPa) that act to dilute the volatile content of the fluid phase. The average phengite content of muscovite is positively correlated with pressure and ranges from 3.62 Si per formula unit (pfu) at 6.5 GPa to 3.80 Si pfu at 9 GPa. The extent of the phengite substitution in muscovite in this bulk composition appears to be limited to a maximum of 3.80–3.85 Si pfu at P=9 GPa. These experiments show that phengite should be stable in metasediments in mature subduction zones to depths of up to 300 km even under conditions in which aH2O1. Other high-pressure hydrous phases such as lawsonite, MgMgAl-pumpellyite, and topaz-OH that may form in subducted sediments do not occur within the phengite stability field in this system, and may require more H2O-rich fluid compositions in order to form. The wide range of conditions under which phengite occurs and its participation in mixed volatile reactions that may buffer the composition of the fluid phase suggest that phengite may significantly influence the nature of metasomatic fluids released from deeply subducted sediments at depths of up to 300 km at convergent plate boundaries.  相似文献   

15.
We have experimentally studied the formation of diamonds in alkaline carbonate–carbon and carbonate–fluid–carbon systems at 5.7–7.0 GPa and 1150–1700 °C, using a split-sphere multi-anvil apparatus (BARS). The starting carbonate and fluid-generating materials were placed into Pt and Au ampoules. The main specific feature of the studied systems is a long period of induction, which precedes the nucleation and growth of diamonds. The period of induction considerably increases with decreasing P and T, but decreases when adding a C–O–H fluid to the system. In the range of P and T corresponding to the formation of diamonds in nature, this period lasts for tens of hours. The reactivity of the studied systems with respect to the diamond nucleation and growth decreases in this sequence: Na2CO3–H2C2O4·2H2O–C>K2CO3–H2C2O4·2H2O–C>>Na2CO3–C>K2CO3–C. The diamond morphology is independent of P and T, and is mainly governed by the composition of the crystallization medium. The stable growth form is a cubo-octahedron in the Na2CO3 melt, and an octahedron in the K2CO3 melt. Regardless of the composition of the carbonate melt, only octahedral diamond crystals formed in the presence of the C–O–H fluid. The growth rates of diamond varied in the range from 1.7 μm/h at 1420 °C to 0.1–0.01 μm/h at 1150 °C, and were used to estimate, for the first time, the possible duration of the crystallization of natural diamonds. From the analysis of the experimental results and the petrological evidence for the formation of diamonds in nature, we suggest that fluid-bearing alkaline carbonate melts are, most likely, the medium for the nucleation and growth of diamonds in the Earth's upper mantle.  相似文献   

16.
The results of the 7 years (1994–2000) of monthly monitoring of spring water before and during eruptions show response to volcanic activity. Low salinity and temperature characterize most of the springs, which are located on the flanks of Popocatepetl Volcano. The pH ranges from 5.8 to 7.8 and temperature from 3 to 36 °C. Oxygen and hydrogen isotopic data show that the water is of meteoric origin, but SO42−, Cl, F, HCO3, B, and SO42−/Cl variations precede main eruptive activity, which is considered linked to influx of magmatic gases and acid fluids that react with sublimates and host rock and mix with the large water system. Na+, Ca2+, SiO2 and Mg2+ concentrations in the water also increased before eruptive activity. The computed partial pressure of CO2 in equilibrium with spring waters shows values higher than air-saturated water (ASW), with the highest values up to 0.73 bar of pCO2. Boron is detected in the water only preceding the larger eruptions. When present, boron concentration is normally under health standard limits, but in two cases the concentration was slightly above. Other components are within health standard limits, except for F in one spring.  相似文献   

17.
R. V. Conceio  D. H. Green 《Lithos》2004,72(3-4):209-229
A model metasomatized lherzolite composition contains phlogopite and pargasite, together with olivine, orthopyroxene, clinopyroxene and spinel or garnet as subsolidus phases to 3 GPa. Previous works established that at ≥1.5 GPa, phlogopite is stable above the dehydration solidus, determined by the melting behaviour of pargasite and coexisting phases. At 2.8 GPa, melts with residual phlogopite+garnet lherzolite mineralogy at 1195 °C and with garnet lherzolite mineralogy at 1250 °C are both olivine nephelinite with K/Na (atomic)=0.51 and K/Na=0.65, respectively. Recent work shows that melting along the dehydration (fluid-absent) solidus of the phlogopite+pargasite lherzolite at pressures <1.5 GPa is very different with the presence of phlogopite, decreasing the solidus below that of pargasite lherzolite. At 1.0 GPa, both phlogopite and pargasite disappear at temperatures at or slightly above the solidus. The compositions of two melts at 1.0 GPa, 1075 °C (with different water contents), in equilibrium with residual spinel lherzolite mineralogy are silica-saturated trachyandesite (5% melt fraction, 3% H2O) to silica-oversaturated basaltic andesite (8% melt fraction, 4.5% H2O). Both compositions may be classified as ‘shoshonites’ on the basis of normative compositions, silica-saturation, and K/Na ratio. Decompression melting of metasomatized lithospheric lherzolite with minor phlogopite and pargasite may produce primary ‘shoshonitic’ magmas by dehydration melting at 1 GPa, 1050–1150 °C. Such magmas may be parental to Proterozoic batholithic syenites occurring in Brazil.  相似文献   

18.
A combined fluid inclusion and mineral thermobarometric study in groups of synchronous inclusions in quartz within weakly foliated granites from the Chottanagpur Gneissic Complex, India, reveals super dense carbonic (CO2 with minor CH4 and H2O) inclusions and hypersaline (H2O–NaCl ± NaHCO3) inclusions, with halite- and nahcolite daughter phases. This study documents the highest density (1.115 g cm− 3) CO2 fluids ever reported in granites. Fluid isochores, constructed from CO2 (± CH4) and halite-bearing inclusions, coupled with two-feldspar thermometry constrain the minimum P–T at 8 kbar/ 750 °C for fluid entrapment in granites. By contrast, the carbonic inclusions in quartz from granite-hosted metapelite enclaves contain substantial CH4 (up to 30 mol%), and the entrapment pressure ( 4.3 kbar/600 °C) is considerably lower compared to those in the granites. By implication, the sillimanite-free granites were not derived from the metapelitic enclaves, and instead were formed by partial melting of fluid-heterogeneous lower crustal protoliths, with fluid entrapment at magmatic conditions.  相似文献   

19.
Fluid inclusions in mantle xenoliths   总被引:23,自引:0,他引:23  
Fluid inclusions in olivine and pyroxene in mantle-derived ultramafic xenoliths in volcanic rocks contain abundant CO2-rich fluid inclusions, as well as inclusions of silicate glass, solidified metal sulphide melt and carbonates. Such inclusions represent accidentally trapped samples of fluid- and melt phases present in the upper mantle, and are as such of unique importance for the understanding of mineral–fluid–melt interaction processes in the mantle. Minor volatile species in CO2-rich fluid inclusions include N2, CO, SO2, H2O and noble gases. In some xenoliths sampled from hydrated mantle-wedges above active subduction zones, water may actually be a dominant fluid species. The distribution of minor volatile species in inclusion fluids can provide information on the oxidation state of the upper mantle, on mantle degassing processes and on recycling of subducted material to the mantle. Melt inclusions in ultramafic xenoliths give information on silicate–sulphide–carbonatite immiscibility relationships within the upper mantle. Recent melt-inclusion studies have indicated that highly silicic melts can coexist with mantle peridotite mineral assemblages. Although trapping-pressures up to 1.4 GPa can be derived from fluid inclusion data, few CO2-rich fluid inclusions preserve a density representing their initial trapping in the upper mantle, because of leakage or stretching during transport to the surface. However, the distribution of fluid density in populations of modified inclusions may preserve information on volcanic plumbing systems not easily available from their host minerals. As fluid and melt inclusions are integral parts of the phase assemblages of their host xenoliths, and thus of the upper mantle itself, the authors of this review strongly recommend that their study is included in any research project relating to mantle xenoliths.  相似文献   

20.
In order to identify and characterise fluids associated with metamorphic rocks from the Chaves region (North Portugal), fluid inclusions were studied in quartz veinlets, concordant with the main foliation, in graphitic-rich and nongraphitic-rich lithologies from areas with distinct metamorphic grade. The study indicates multiple fluid circulation events with a variety of compositions, broadly within the C–H–O–N–salt system. Primary fluid inclusions in quartz contain low salinity aqueous–carbonic, H2O–CH4–N2–NaCl fluids that were trapped near the peak of regional metamorphism, which occurred during or immediately after D2. The calculated PT conditions for the western area of Chaves (CW) is P=300–350 MPa and T500 °C, and for the eastern area (CE), P=200–250 MPa and T=400–450 °C. A first generation of secondary fluid inclusions is restricted to discrete cracks at the grain boundaries of quartz and consists of low salinity aqueous–carbonic, H2O–CO2–CH4–N2–NaCl fluids. PT conditions from the fluid inclusions indicate that they were trapped during a thermal event, probably related with the emplacement of the two-mica granites.

A second generation of secondary inclusions occurs in intergranular fractures and is characterised by two types of aqueous inclusions. One type is a low salinity, H2O–NaCl fluid and the second consists of a high salinity, H2O–NaCl–CaCl2 fluid. These fluid inclusions are not related to the metamorphic process and have been trapped after D3 at relatively low P (hydrostatic)–T conditions (P<100 MPa and T<300 °C).

Both the early H2O–CH4–N2–NaCl fluids in quartz from the graphitic-rich lithologies and the later H2O–CO2–CH4–N2–NaCl carbonic fluid in quartz from graphitic-rich and nongraphitic-rich lithologies seem to have a common origin and evolution. They have low salinity, probably resulting from connate waters that were diluted by the water released from mineral dehydration during metamorphism. Their main component is water, but the early H2O–CH4–N2–NaCl fluids are enriched in CH4 due to interaction with the C-rich host rocks.

From the early H2O–CH4–N2–NaCl to the later aqueous–carbonic H2O–CO2–CH4–N2–NaCl fluids, there is an enrichment in CO2 that is more significant for the fluids associated with nongraphitic-rich lithologies.

The aqueous–carbonic fluids, enriched in H2O and CH4, are primarily associated with graphitic-rich lithologies. However, the aqueous–carbonic CO2-rich fluids were found in both graphitic and nongraphitic-rich units from both the CW and CE studied areas, which are of medium and low metamorphic grade, respectively.  相似文献   


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