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1.
The mobility of H2O and D2O by diffusion through quartz is illustrated with H2O-rich fluid inclusions synthesized at 600 °C and 337 MPa, within the α-quartz stability field. Inclusions are re-equilibrated at the same experimental conditions within a pure D2O fluid environment. Consequently, a gradient in volatile fugacities is the only driving force for diffusion, in the absence of pressure gradients and deformation processes. Up to 100 individual inclusions are analyzed in each experiment before and after re-equilibration by microscopic investigation, microthermometry, and Raman spectroscopy. Changes in fluid inclusion composition are obtained from the ice-melting temperatures, and density changes are obtained from total homogenization temperatures. After 1-day re-equilibration, inclusions already contain up to 11 mol % D2O. A maximum concentration of 63 mol % D2O is obtained after 40-day re-equilibration. D2O concentration profiles in quartz are determined from the concentration in inclusions as a function of their distance to the quartz surface. These profiles illustrate that deep inclusions contain less D2O than shallow inclusions. At equal depths, a variety of D2O concentration is observed as a function of fluid inclusion size: Small inclusions are stronger effected compared with large inclusions. A series of 19-day re-equilibration experiments are performed at 300, 400, 500, and 600 °C (at 337 MPa), at the same conditions as the original synthesis. The threshold temperature of diffusion is estimated around 450 °C at 337 MPa, because D2O is not detected in inclusions from re-equilibration experiments at 300 and 400 °C, whereas maximally 26 mol % D2O is detected at 500 °C. Our study indicates that the isotopic composition of natural fluid inclusions may be easily modified by re-equilibration processes, according to the experimental conditions at 600 °C and 337 MPa.  相似文献   

2.
The dehydration of a natural goethite to hematite is accompanied by a systematic hydrogen isotope fractionation. Closed system dehydration at, and below, 250°C results in a significantly greater degree of isotopic fractionation than does open system dehydration. This relationship is apparently reversed at 300°C. Both processes produce a progressive decrease in the DH ratio of the mineral hydrogen with increasing degree of dehydration. At temperatures of 160°C to 250°C the closed system mineralvapor fractionation factor is independent of temperature, while above 250°C, it varies strongly with temperature. The mineral-vapor fractionation factor associated with open system dehydration appears to be independent of temperature over the interval 160°C to 300°C. The closed system DH fractionation suggests that natural goethite undergoing dehydration in the presence of water can isotopically exchange with that water.CO2 loss from goethite during dehydration is correlated with the loss of H2O. The CO3 is thought to be present in carbonates which exist as impurities in the goethite. Loss of both H2O and CO2 appears to be diffusion-controlled.  相似文献   

3.
《Chemical Geology》2006,225(3-4):373-387
Rock-forming zeolites often exhibit complex solid solutions reflecting isomorphous substitutions between Si and Al in tetrahedral framework sites, between charge-balancing extraframework cations, and between water molecules and vacancies. Although the number of moles of charge on extraframework cations in a zeolite must equal the moles of Al in order to maintain charge balance, the relationships between Si–Al and extraframework substitutions vary considerably across this mineral group. Review of available compositional data suggests that there are three main modes of Si–Al substitution in zeolites: 1) coupled CaAl–NaSi substitution; 2) coupled substitution of a single extraframework cation plus Al for Si; and 3) completely uncoupled substitution among extraframework cations and Si and Al on tetrahedral sites. Among zeolites that exhibit the latter two modes of solid solution, Si–Al substitution can be described by an SiO2 (± H2O) compositional exchange vector from a hypothetical, pure-silica endmember composition. Recent calorimetric, structural, and theoretical investigations suggest that Si–Al substitution follows a non-ideal, athermal solution model characterized by no excess enthalpies of mixing and negative excess entropies of mixing. Because Si–Al exchange in these minerals can be explicitly or implicitly described by exchange of an SiO2 component, the Si/Al ratio in their framework can be predicted solely as a function of temperature, pressure, and the chemical potential of SiO2. Application of this model leads to calculated Si/Al ratios in stilbite (coexisting with albite), analcime, and chabazite consistent with observed mineral compositions and parageneses in very low-grade metamorphic environments. Coexistence of silica polymorphs with zeolites containing SiO2·nH2O exchange vectors potentially provides a means of performing thermobarometric calculations in very low-grade metamorphic and diagenetic environments.  相似文献   

4.
The diffusion coefficient of dissolved silica at 25.5 ± .5°C was determined as a function of concentration using a non-steady-state method whereby agar-gelled solutions containing dissolved silica from 0.09 to 1.50 mM (pH = 5.5) were placed in contact with distilled water in glass cells. Diffusion coefficients were obtained by measuring the dissolved silica content of the distilled water after a given length of time. The measured diffusion coefficients decreased as a function of increasing dissolved silica concentration, which is thought to reflect an increase in dimeric silica according to the equilibrium: 2Si(OH)4 = Si2O(OH)6 + H2O. The tracer diffusion coefficients for Si(OH)4 and Si2O(OH)6 and an association constant for the above reaction were determined by fitting the following equation to the experimental data: Dobs = αDmonomer + (1 − α)Ddimer where α is the fraction of total dissolved silica which is Si(OH)4. The best fit yielded tracer D's for Si(OH)4 and Si2O(OH)6 of 2.2 and 1.0 (in units of 10−5 cm2 sec−1), respectively, and an association constant of 330.  相似文献   

5.
Oxygen isotope analyses of quartz-Al2SiO5 pairs have been made for samples from the Mica Creek area, British Columbia. We have analysed quartz–kyanite nodules and quartz–kyanite and quartz–sillimanite in multiphase pelitic rocks from the staurolite–kyanite, kyanite, and sillimanite zones. Apparent temperatures calculated from oxygen isotopic fractionation range from 555 °C (staurolite–kyanite zone) to 695 °C (sillimanite zone). Temperatures from the quartz–kyanite nodules range from 630 to 675 °C. Some of the nodules show isotopic disequilibrium. Most of the results confirm predictions that bimineralic rocks will yield an estimate of peak metamorphic temperatures, when the less abundant mineral (an aluminium silicate) is the slower oxygen diffuser. Using cooling rates of 10–100 °C Ma?1 for the multiphase rocks, measured crystal sizes and modes, the Fast Grain Boundary diffusion model with ‘wet’ diffusion data (PH2O?1.0 kbar) yields predicted apparent temperatures which are generally lower than the measured apparent temperatures. The agreement is improved if slower diffusion coefficients are used. This suggests that f (H2O) during cooling was lower than that of the hydrothermal experiments and thus that there was little interaction with aqueous fluids of internal or external origin to modify the isotopic compositions. The measured apparent isotopic temperatures and apparent garnet–biotite Fe–Mg exchange temperatures show very poor agreement for the sillimanite zone samples, with the garnet–biotite Fe–Mg exchange temperatures generally higher than the oxygen isotope temperatures. Compared with the other calibrations that we tested the measured apparent temperatures using the Sharp calibration show the best agreeement with recently published P–T grids, although some variability in agreement is expected due to variable f (H2O) during cooling.  相似文献   

6.
Diffusion-controlled growth rates of polycrystalline enstatite reaction rims between forsterite and quartz were determined at 1,000 °C and 1 GPa in presence of traces of water. Iron-free, pure synthetic forsterite with normal oxygen and silicon isotopic compositions and quartz extremely enriched in 18O and 29Si were used as reactants. The relative mobility of 18O and 29Si in reactants and rims were determined by SIMS step scanning. The morphology of the rim shows that enstatite grows by a direct replacement of forsterite. Rim growth is modelled within a mass-conserving reference frame that implies advancement of reaction fronts from the initial forsterite-quartz interface in both directions. The isotopic compositions at the two reaction interfaces are controlled by the partial reactions Mg2SiO4=0.5 Mg2Si2O6+MgO at the forsterite-enstatite, and MgO+SiO2=0.5 Mg2Si2O6 at the enstatite-quartz interface, implying that grain boundary diffusion of MgO is rate-controlling. Isotopic profiles show no silicon exchange across the propagating reaction interfaces. This propagation, controlled by MgO diffusion, is faster than the homogenisation of Si by self-diffusion behind the advancing fronts. From this, and using % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamiramaaDa % aaleaacaWGtbGaamyAaiaacYcacaWGfbGaamOBaaqaaiaadAfacaWG % VbGaamiBaaaaaaa!3DD2! DSi,EnVolD_{Si,En}^{Vol} at dry conditions from the literature, results a % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGabmirayaafa % Waa0baaSqaaiaadofacaWGPbGaaiilaiaadweacaWGUbaabaaaaOGa % eqiTdqgaaa!3CCD! D￠Si,En dD'_{Si,En}^{} \delta value of 3᎒-24 m3 s-1 at 1,000 °C. The isotopic profiles for oxygen are more complex. They are interpreted as an interplay between the propagation of the interfaces, the homogenisation of the isotope concentrations by grain boundary self-diffusion of O within the rim, and the isotope exchange across the enstatite-quartz interface, which was open to 18O influx from quartz. Because of overlapping diffusion processes, boundary conditions are unstable and D´Ox,En' cannot be quantified. Using measured rim growth rates, the grain boundary diffusivity D´MgO' of MgO in iron-free enstatite is 8᎒-22 m3 s-1 at 1,000 °C and 1 GPa. Experiments with San Carlos olivine (fo92) as reactant reveal lower rates by a factor of about 4. Our results show that isotope tracers in rim growth experiments allow identification of the actual interface reactions, recognition of the rate-controlling component and further calculation of D´' values for specific components.  相似文献   

7.
Carbon and hydrogen isotopic compositions of New Zealand geothermal gases   总被引：1，自引：0，他引：1  
Carbon and hydrogen isotopic compositions are reported for methane, hydrogen and carbon dioxide from four New Zealand geothermal areas: Ngawha, Wairakei, Broadlands and Tikitere. Carbon-13 contents are between ?24.4 and ?29.5%. (PDB) for methane, and between ?3.2 and ?9.1%. for carbon dioxide. Deuterium contents are between ?142 and ?197%. (SMOW) for methane and between ?310 and ?600%. for hydrogen. The different areas have different isotopic compositions with some general relationships to reservoir temperature.The isotopic exchange of hydrogen with water indicates acceptable reservoir temperatures of 180–260°C from most spring samples but often higher than measured temperatures in well samples. Indicated temperatures assuming 13C equilibria between CH4 and CO2 are 100–200°C higher than measured maxima. This difference may be due to partial isotopic equilibration or may reflect the origin of the methane. Present evidence cannot identify whether the methane is primordial, or from decomposing sediments or from reduction of magmatic CO2. The isotopic equilibria between CH4, CO2, H2 and H2O are reviewed and a new semi-empirical temperature scale proposed for deuterium exchange between methane and water.  相似文献   

8.
The thermal behaviour of silica rocks upon heat treatment is dependent on the constituent minerals and petrographic texture types. These constituents can be shown to be mainly quartz in the form of two types of chalcedony (Length-fast (LF) chalcedony and Length-slow (LS) chalcedony, the latter also being termed quartzine) and moganite. Even though the thermal behaviour of LF-chalcedony is well understood, major uncertainties persist concerning the high-temperature behaviour of LS-chalcedony and moganite. We present here a comparative study of these three constituents of common silica rocks. Our results show that the chemical reaction is the same in all three, Si–OH + HO–Si → Si–O–Si + H2O, but that the reaction kinetics and activation temperatures are very different. LS-chalcedony begins to react from 200 °C upwards, that is at temperatures 50 °C below the ones observed in LF-chalcedony, and shows the fastest reaction kinetics of this ‘water’ loss. Chemically bound water (SiOH) in moganite is more stable at high temperatures and no specific activation temperature is necessary for triggering the temperature-induced ‘water’ loss. Moganite is also found to act as a stabilizer in silica rocks preventing them from temperature-induced fracturing. These findings have implications for the study of potential heat treatment temperatures of silica rocks (in industry and heritage studies), but they also shed light on the different structures of SiO2 minerals and the role of OH impurities therein.  相似文献   

9.
We present H2O analyses of MgSiO3 pyroxene crystals quenched from hydrous conditions in the presence of olivine or wadsleyite at 8–13.4 GPa and 1,100–1,400°C. Raman spectroscopy shows that all pyroxenes have low clinoenstatite structure, which we infer to indicate that the crystals were high clinoenstatite (C2/c) during conditions of synthesis. H2O analyses were performed by secondary ion mass spectrometry and confirmed by unpolarized Fourier transform infrared spectroscopy on randomly oriented crystals. Measured H2O concentrations increase with pressure and range from 0.08 wt.% H2O at 8 GPa and 1,300°C up to 0.67 wt.% at 13.4 GPa and 1,300°C. At fixed pressure, H2O storage capacity diminishes with increasing temperature and the magnitude of this effect increases with pressure. This trend, which we attribute to diminishing activity of H2O in coexisting fluids as the proportion of dissolved silicate increases, is opposite to that observed previously at low pressure. We observe clinoenstatite 1.4 GPa below the pressure stability of clinoenstatite under nominally dry conditions. This stabilization of clinoenstatite relative to orthoenstatite under hydrous conditions is likely owing to preferential substitution of H2O into the high clinoenstatite polymorph. At 8–11 GPa and 1,200–1,400°C, observed H2O partitioning between olivine and clinoenstatite gives values of D ol/CEn between 0.65 and 0.87. At 13 GPa and 1,300°C, partitioning between wadsleyite and clinoenstatite, D wd/CEn, gives a value of 2.8 ± 0.4.  相似文献   

10.
Thermodynamic modeling of the SiO2–TiO2–Al2O3–Fe2O3–MnO–MgO–CaO–Na2O–K2O–P2O5–H2O (STAFMMCNKPOH) system at 600°C, 5 kbar has been applied to investigate dissolution and re-precipitation of quartz. Comparing silica molality in the STAFMMCNKPOH and SiO2–H2O systems, there is seen to be no effect of mineral assemblage on quartz solubility. From quantitatively estimated water/rock ratio required to dissolve quartz completely, one can deduce that the segregation of quartz appears to be due to diffusive transport of silica in inner pore fluid rather than to advective transport (in fluid flow).  相似文献   

11.
《Environmental Geology》2009,58(8):1629-1638
The most important intakes of thermal waters within the Sudetic Geothermal Region occur in three separate hydrogeothermal systems: (1) Lądek, (2) Duszniki and (3) Cieplice. All these waters are of meteoric origin and circulate in crystalline rocks to different depths. Their outflow temperatures are between less than 20°C and to about 87°C. To evaluate the geothermal fields in the light of their prospectiveness, to further exploration of thermal energy resources, we took an effort to apply selected isotopic and chemical geothermometers to assess the maximum possible temperatures, which may be found in the reservoirs. The only chemical geothermometers which give a reliable range of reservoir temperatures are SiO2 (chalcedony), Na–Ka–Ca and partly Na–K ones. The oxygen isotopic geothermometer in the SO4–H2O system gives a real range of estimated reservoir temperatures only for deeply circulating waters in the Cieplice area. On the other hand, in the case of CO2 rich waters in the Duszniki area, where outflow temperatures do not exceed 30°C, application of chemical or isotopic temperature indicators always leads to erroneous results due to the lack of equilibrium in the thermodynamic system of water–rock interaction.  相似文献   

12.
A continuous flow method, by a combination of thermal conversion elemental analyzer (TC/EA) with isotope ratio mass spectrometry (MS), is presented for determination of both H isotope composition and H2O concentration of garnet from eclogite. Together with biotite NBS-30, the garnet was tested by preheating mineral grains at different temperatures. Preheating at 90°C for 12 h was found to be capable of eliminating adsorption water on sample surface. This results in constant δD values and total H2O contents for the garnet, with weighted means of −93 ± 2‰ and 522 ± 11 ppm (wt), respectively. The garnet that was preheated at 350°C for 4 h also gave constant δD values of −86 ± 6‰ and H2O contents of 281 ± 13 ppm (wt). The latter result for the H2O contents agrees with the H2O contents 271 ± 58 ppm (wt) measured by Fourier transform infrared spectroscopy for quantitative analysis of structural hydroxyl in the same garnet. Stepwise-heating TC/EA-MS analyses for the garnet show that the molecular H2O are depleted in D relative to the structural OH and has higher mobility than the structural OH. Therefore, the TC/EA-MS method can be used not only for quantitative determination of both H isotope composition and H2O concentration of hydrous and anhydrous minerals, but also for the concentration of structural hydroxyl after high-T dehydration.  相似文献   

13.
The Proterozoic Vazante Group carbonate rocks were submitted to multiple stages of fluid circulation from diagenesis to orogenesis as documented by detailed mineralogical, fluid inclusion and isotopic studies of the Upper Morro do Pinheiro and Lower Pamplona members from the Serra do Poço Verde Formation in the southern part of the paleo-basin. These units are the main hosts for the hypogene, structurally-controlled zinc silicate deposits in the Vazante Zinc District, including the Vazante mine, which is considered to be the largest willemitic (Zn2SiO4) deposit in the world, with estimated total resources of 40–60 Mt at 20% Zn. Five hydrothermal alteration types were identified in the Southern Extension of the Vazante Group. (I) Early stage alteration comprises dolomite substitution bands and nodules, associated with moderate salinity H2O-NaCl-CaCl2 fluids, with temperatures around 90 °C, interpreted as late-diagenetic. The calculated C and O isotopic compositions of the fluids suggest meteoric and/or connate origin and interaction with organic carbon. (II) Pre-ore stage alteration is evidenced by dog-tooth dolomite and quartz with minor Fe-oxi/hydroxides which fills dissolution voids formed by H2O-NaCl-CaCl2 ± MgCl2 fluids at temperatures around 100° to 150 °C. The C isotopic data also indicate interaction with organic carbon. The two first stages are poor in ore-related elements. (III) Ore stage encompasses four phases of mineral precipitation. The first is distal and characterized by red stained dolostones due to disseminated hematite and red dolomite. The second is the main phase of the ore stage, composed of massive red dolomite, massive hematite and willemite with enrichment mainly in Fe2O3, SiO2, Ag, As, Cd, Cu, Ni, Pb, Se and Zn. The third phase comprises white dolomite, hematite and traces of willemite with enrichment in MnO, Cd, Ni and Pb. The calculated C and O isotopic compositions of the fluids (at 180 °C) associated with pervasive alteration yielded values heavier than the diagenetic stage and lower than the host rock. The fourth phase corresponds to Zn-chlorite and quartz which are associated with H2O-NaCl fluids of variable salinities and distinct temperatures (90–140 °C and 170–190 °C). (IV) Pyrite-bearing vein characterized by pyrite, sphalerite, white dolomite, fine hematite and late quartz, with C and O isotopic and fluid inclusion compositions that are similar to the three phases of dolomite of the ore stage. These data suggest a co-genetic relationship of these two alteration styles. (V) The late sulfide stage characterized by rare galena-bearing stringers with sphalerite, chalcocite, greenockite, covellite and white dolomite that cross-cut the main ore stage phases. The ore-related fluid compositions associated with the silicate zinc mineralization in the southern part of the Vazante Group are also similar to the fluids reported in previous work for the sulfide zinc-lead deposits in the northern part, indicating favorable conditions for metal transport during the Brasiliano Orogeny. Sulfide ore would have precipitated in zones where sulfur was available and silicate zinc in structures where mineralizing fluids interacted with evolved meteoric water. This finding implies that carbonate sequences in other districts with sulfide lead-zinc deposits may also host hypogene silicate zinc deposits.  相似文献   

14.
Partitioning of manganese between forsterite and silicate liquid   总被引：1，自引：0，他引：1  
Partition coefficients for Mn between forsterite and liquid in the system MgO-CaO-Na2O-Al2O3-SiO2 (+ about 0.2% Mn) were measured by electron microprobe for a variety of melt compositions over the temperature range 1250–1450°C at one atm pressure. The forsterite-liquid partition coefficient of Mn (mole ratio, MnO in Fo/MnO in liquid, designated Dmnfo?Liq) depends on liquid composition as well as temperature: at 1350°C, DMnFo?Liqranges from 0.60 (basic melt, SiO2 = 47wt%) to 1.24 (acidic melt, SiO2 = 65wt%). At lower temperatures, the partition coefficient is more strongly dependent on melt composition.The effects of melt composition and temperature on DMnfo?Liq can be separately evaluated by use of the Si:O atomic ratio of the melts. A plot of DmnFo?Liq measured at various temperatures vs melt Si:O for numerous liquid compositions reveals discrete, constant-temperature curves that are not well defined by plotting DMnFo?Liq against other melt composition parameters such as melt basicity or MgO content. For constant Si:O in the melt, In DMnFo?Liq vs reciprocal absolute temperature is linear; however, the slope of the plot becomes more positive for higher values of Si:O, indicating a higher energy state for Mn2+ ions in acidic melts than in basic melts.Comparison of Mn partitioning data for the iron-free system used in this study with data of other workers on iron-bearing compositions suggests that the effect of iron on Mn partitioning between olivine and melt is small over the range of basalt liquidus temperatures.  相似文献   

15.
The granulite complex around Jenapore, Orissa, Eastern Ghats granulite belt, bears the imprint of two episodes of strong deformation (D1 and D2) attended with foliation (fabric) development (S1 and S2). Two distinct metamorphic events at P-T conditions of ∼900°C at ∼9 kbar and ∼600°C at ∼6 kbar are correlated with D1 and D2 respectively. The reaction textures in S1-microdomains are interpreted to be the product of near isobaric cooling at ∼9 kbar from 950°C to 600°C, whereas those in the S2-microdomains are considered to be the result of an up-pressure trajectory from ∼6 kbar at 600°C. The D1-M1 high P-T granulite event is interpreted to be Archean in age (ca. 3 Ga) on the basis of the isotopic data obtained from the charnockite suite of the area. The later relatively low P-T granulite facies event, attendant to D2-S2 is considered to be related to the Grenvillian orogeny as represented by the dominant isotopic record in the belt.  相似文献   

16.
Hydrothermal syntheses were made mainly in the binary system SiO2-H2O in a temperature range between 300 ° C and 500 ° C and pressures from 0.2 kbar up to 4.0 kbar with various starting materials. In this way the transformation behavior of different amorphous silicas via cristobalite and keatite to quartz were observed. This behavior depends mainly on the parameters: pressure, temperature, run duration and state of the starting material. Four reaction paths have been observed: in most experiments the complete reaction sequence “amorphous silica→cristobalite→keatite→quartz” took place. Less often the reactions: “amorphous silica→cristobalite→quartz” and: “amorphous silica→keatite→quarts” were observed. Very few samples were found with a direct transition of amorphous silica into quartz at high pressures. A kinetic model is given in form of a pressure-temperature-time diagram of the system SiO2-H2O under hydrothermal conditions.  相似文献   

17.
Effective binary diffusion coefficients of Si during the interdiffusion of hydrous, 3 and 6% H2O, dacitic and rhyolitic melts have been determined at 1.0 GPa, 1100°–1400°C. Water is shown to enhance diffusivities by one to two orders of magnitude above dry Si diffusivities in the same compositional system for SiO2 compositions 65–75wt%. The effect of silica content on diffusion is small and typically within experimental error. With 3% H2O in the melts the Arrhenius equation for Si diffusion at 70% SiO2 is: $${\text{D = }}2.583\operatorname{x} 10^{ - {\text{ }}8} {\text{ }}\exp ( - 126.5/R{\text{T}})$$ where D is the diffusivity in m2/s, the activation energy (126.5) is in kJ/mol, R is in J/mol and T in Kelvin. Although less-well constrained, the Si diffusivity at 70% SiO2 with 6% H2O in the melts can be described by: $${\text{D = }}2.692\operatorname{x} 10^{ - {\text{ }}7} {\text{ }}\exp ( - 131.4/R{\text{T}})$$ The activation energies for diffusion are substantially below the activation energy of 236.4kJ/mol measured during anhydrous interdiffusion in the same system (Baker 1990). The decrease in activation energy with the initial addition of 3% water and the relative insensitivity of the activation energy to the additional water is related to the abundance of OH species in the melt, and the reduction of (Si,Al)-O bond strengths due to the interaction of hydroxyls with the (Si,Al)-O network. Changes in the pre-exponential factor of Arrhenius equations are attributed to the abundance of H2O species in the melts. No decoupling of non-alkalies from SiO2 during interdiffusion of the two melts was observed, although alkalies diffuse much more rapidly than non-alkalies (but were not measured quantitatively in this study) and can become decoupled. Interdiffusion of Si and all non-alkalies is demonstrated to be predictable, at least to within a factor of ten, by the Eyring equation. Using the diffusion data of this study for nonalkalies and of other studies for alkalies and Sr isotopes the contamination of a host rhyolitic magma by dacitic enclaves, 5 and 50 cm radius, has been modeled for temperatures of 1000°, 900°, and 800° C with water contents of 3 and 6%. Even when the effects of phenocrysts on diffusion in the dacitic enclaves are estimated the results of the modeling demonstrate that significant contamination is possible in the case of small enclaves, and even large enclaves have the potential to affect the composition of their host magma in geologically short times.  相似文献   

18.
Fly ash is a product arising from coal combustion in thermal power plants. It represents a major source of environmental pollution. It is well known by its chemical composition rich of SiO2 and Al2O3. With the aim of preserving the environment against this contamination, fly ash was used along with the starting materials for producing glass cordierite (2MgO, 2Al2O3, 5SiO2). Four formulations were developed by mixing the silica gel, magnesium chloride (MgCl2.6H2O) and fly ash in the percentages enclosing the stoichiometry of cordierite (2MgO, 2Al2O3, 5SiO2). Different experimental techniques (DTA/TGA, X-ray diffraction, FTIR and SEM) were used to characterise the prepared formulations. The results shown that for all formulations, a cordierite phase was obtained at 1200 °C along with several secondary phases such as mullite, cristobalite, silicon oxide, enstatite and spinel. At 1300 °C, pure indialite (α-cordierite) was obtained along with a small amount of spinel. The four formulations sintered at 1200 °C exhibit a homogenous morphology and high porosity. The acicular-shaped indialite grains were observed in both formulations with excess of alumina and excess of magnesia.  相似文献   

19.
《Applied Geochemistry》2001,16(9-10):1055-1066
Laboratory hydrothermal experiments provide unique information regarding the fate of volatile and/or incompatibles (e.g. B, Li, and As) during oceanic crust subduction. Examination of chemical redistribution between the subducted slab, mantle wedge, arc volcanics and overlying ocean water during subduction is critical to gain further insight into arc volcanism and chemical oceanic budgets. For instance, efficient mobilization of B at shallow depths may be a key aspect of its oceanic budget, and can help to explain the systematics of B-δ11B and B-10Be in arc lavas. Fluid–rock interactions at elevated temperatures and pressures in accretionary prisms were studied using a rocking autoclave hydrothermal apparatus to monitor sediment–porewater interaction over the range of 25 to 350°C, at 800 bars. Clay-rich hemi-pelagic sediments from the décollement zone of Ocean Drilling Program Site 808, Nankai Trough, were reacted with NaCl–CaCl2 solutions at water/rock ratios of ∼3.5 to 1.5 (w/w) to mimic alteration processes in the shallow subduction zone. Fluids were extracted at 25–50°C intervals and were analyzed for major and trace chemical constituents. The fluid chemistry changed significantly during the course of these experiments, but there was generally only minor modification of the solid phase; only B, Li, As, Br, and Pb are significantly depleted. During the heating cycle, dissolved Na, Mg and SO4 decreased sharply and NH4, SiO2, K, B, and Li increased at T⩾300°C. Calcium drops gradually at low temperatures, but concentrations rise sharply at T⩾300°C. Decomposition of organic matter, SO42− depletion, and Mg-fixation dominate at low temperatures; however, albitization of calcic plagioclase leads to marked Na depletions and Ca enrichments at T⩾300°C. Dissolved SiO2 remained below saturation with respect to quartz and amorphous silica throughout the entire experiment. B and Li mobilization with large isotopic fractionations occurred at low temperature. Exchangeable B (δ11B=∼15‰) is completely leached before reaching 150°C. Substantial O2 exchange between fluids and the solid phase occurred at T⩾200°C in the spiked experiment, where δ18O varies more than 100‰ in the fluids. During retrograde cooling, dissolved Mg, SO4, Ca, Si, K and Sr are released as a result of carbonate or anhydrite dissolution, and marked B re-adsorption occurred at temperatures below 60°C.  相似文献   

20.
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   

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