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1.
The solubility and stability of synthetic grossular were determined at 800 °C and 10 kbar in NaCl-H2O solutions over a large range of salinity. The measurements were made by evaluating the weight losses of grossular, corundum, and wollastonite crystals equilibrated with fluid for up to one week in Pt capsules and a piston-cylinder apparatus. Grossular dissolves congruently over the entire salinity range and displays a large solubility increase of 0.0053 to 0.132 molal Ca3Al2Si3O12 with increasing NaCl mole fraction (XNaCl) from 0 to 0.4. There is thus a solubility enhancement 25 times the pure H2O value over the investigated range, indicating strong solute interaction with NaCl. The Ca3Al2Si3O12 mole fraction versus NaCl mole fraction curve has a broad plateau between XNaCl = 0.2 and 0.4, indicating that the solute products are hydrous; the enhancement effect of NaCl interaction is eventually overtaken by the destabilizing effect of lowering H2O activity. In this respect, the solubility behavior of grossular in NaCl solutions is similar to that of corundum and wollastonite. There is a substantial field of stability of grossular at 800 °C and 10 kbar in the system CaSiO3-Al2O3-H2O-NaCl. At high Al2O3/CaSiO3 bulk compositions the grossular + fluid field is limited by the appearance of corundum. Zoisite appears metastably with corundum in initially pure H2O, but disappears once grossular is nucleated. At XNaCl = 0.3, however, zoisite is stable with corundum and fluid; this is the only departure from the quaternary system encountered in this study. Corundum solubility is very high in solutions containing both NaCl and CaSiO3: Al2O3 molality increases from 0.0013 in initially pure H2O to near 0.15 at XNaCl = 0.4 in CaSiO3-saturated solutions, a >100-fold enhancement. In contrast, addition of Al2O3 to wollastonite-saturated NaCl solutions increases CaSiO3 molality by only 12%. This suggests that at high pH (quench pH is 11-12), the stability of solute Ca chloride and Na-Al ± Si complexes account for high Al2O3 solubility, and that Ca-Al ± Si complexes are minor. The high solubility and basic dissolution reaction of grossular suggest that Al may be a very mobile component in calcareous rocks in the deep crust and upper mantle when migrating saline solutions are present.  相似文献   

2.
Mantle peridotites from the Veneto Volcanic Province (VPP) have been investigated in order to constrain P-T conditions of mantle events, determine the style of the metasomatic reactions, and the compositions of the metasomatic agents. Studied rocks show dominant protogranular and transitional textures; only one sample shows effect of pyrometamorphism. Clinopyroxenes in protogranular lherzolites show depleted LREE patterns, while those of transitional rocks are characterised by spoon-shaped REE patterns (La up to 60 times chondrite), and variable enrichments in LILE. Two generations of fluid inclusions are recognised: 1) Type I (CO2 ± CO ± C fluid) found only in orthopyroxene of transitional xenoliths which may contain very small amphibole; 2) Type II (CO2-rich fluid) found in all minerals of all xenoliths. Most of inclusions homogenize to liquid, with ThL ranging between ?44 and 31°C. The densest CO2 fluid inclusions (d?=?1.13?g/cm3), indicates a trapping pressure of ~10?kbar at 800°C. We propose that the mantle beneath the VVP equilibrated at pressures of 10?kbar, at about 800°C. Traces of an aqueous fluid preserved as fluid inclusions in orthopyroxene suggest the existence of an older subduction related metasomatic event and the occurrence of two stages metasomatism in the lithosphere beneath the SE Alps.  相似文献   

3.
Solubility and solution mechanisms of H2O in depolymerized melts in the system Na2O-Al2O3-SiO2 were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na2Si4O9-Na2(NaAl)4O9] with Al/(Al+Si) = 0.00-0.25. The H2O solubility was fitted to the expression, XH2O=0.20+0.0020fH2O-0.7XAl+0.9(XAl)2, where XH2O is the mole fraction of H2O (calculated with O = 1), fH2O the fugacity of H2O, and XAl = Al/(Al+Si). Partial molar volume of H2O in the melts, , calculated from the H2O-solulbility data assuming ideal mixing of melt-H2O solutions, is 12.5 cm3/mol for Al-free melts and decreases linearly to 8.9 cm3/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H2O, , increases with Al/(Al+Si).Solution mechanisms of H2O were obtained by combining Raman and 29Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H2O content. The rate of NBO/T-change with H2O is negatively correlated with H2O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q4-species to form Q2 species. Steric hindrance appears to restrict bonding of H+ with nonbridging oxygen in Q3 species. The presence of Al3+ does not affect the water solution mechanisms significantly.  相似文献   

4.
Fluid inclusions and clusters of water molecules at nanometer-to submicron-scale in size have been investigated using transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) in jadeite, quartz and symplectite aegirine–augite, albite, taramite and magnetite corona minerals from ultrahigh-pressure (UHP) jadeite–quartzite at Shuanghe, the Dabie Mountains, China. Fluid inclusions from 0.003 μm to 0.78 μm in size occur in jadeite and quartz crystals, and a small number of fluid inclusions from 0.001 μm to 0.25 μm have also been detected in symplectite-forming minerals. Most of the fluid inclusions have round or negative crystal morphology and contain aqueous fluids, but some contain CO2-rich fluids. They are usually connected to dislocations undetectable at an optical scale. The dislocations represent favorable paths for fluid leakage, accounting for non-decrepitation of most fluid inclusions when external pressure decreased at later stages, although there was partial decrepitation of some fluid inclusions unconnected to defect microstructures resulting from internal overpressure. Non-decrepitation and partial decrepitation of fluid inclusions resulted in changes of original composition and/or density. It is clear that identification of hidden re-equilibration features has significant implications for the petrological interpretation of post-peak metamorphic processes. Micro-FTIR results show that all jadeite and quartz samples contain structural water occurring as hydroxyl ions (OH−) and free water (H2O) in the form of clusters of water molecules. The H2O transformed from OH− during exhumation and could have triggered and enhanced early retrograde metamorphism of the host rocks and facilitated plastic deformation of jadeite and quartz grains by dislocation movement, and thus the H2O released during decompression might represent early-stage retrograde metamorphic fluid. The nominally anhydrous mineral (NAM) jadeite is able to transport aqueous fluids in concentrations of at least several hundred ppm water along a subduction zone to mantle depths in the form of clusters of water molecules and hydroxyl ions within crystals.  相似文献   

5.
Armenite, ideal formula BaCa2Al6Si9O30·2H2O, and its dehydrated analog BaCa2Al6Si9O30 and epididymite, ideal formula Na2Be2Si6O15·H2O, and its dehydrated analog Na2Be2Si6O15 were studied by low-temperature relaxation calorimetry between 5 and 300 K to determine the heat capacity, Cp, behavior of their confined H2O. Differential thermal analysis and thermogravimetry measurements, FTIR spectroscopy, electron microprobe analysis and powder Rietveld refinements were undertaken to characterize the phases and the local environment around the H2O molecule.The determined structural formula for armenite is Ba0.88(0.01)Ca1.99(0.02)Na0.04(0.01)Al5.89(0.03)Si9.12(0.02)O30·2H2O and for epididymite Na1.88(0.03)K0.05(0.004)Na0.01(0.004)Be2.02(0.008)Si6.00(0.01)O15·H2O. The infrared (IR) spectra give information on the nature of the H2O molecules in the natural phases via their H2O stretching and bending vibrations, which in the case of epididymite only could be assigned. The powder X-ray diffraction data show that armenite and its dehydrated analog have similar structures, whereas in the case of epididymite there are structural differences between the natural and dehydrated phases. This is also reflected in the lattice IR mode behavior, as observed for the natural phases and the H2O-free phases. The standard entropy at 298 K for armenite is S° = 795.7 ± 6.2 J/mol K and its dehydrated analog is S° = 737.0 ± 6.2 J/mol K. For epididymite S° = 425.7 ± 4.1 J/mol K was obtained and its dehydrated analog has S° = 372.5 ± 5.0 J/mol K. The heat capacity and entropy of dehydration at 298 K are Δ = 3.4 J/mol K and ΔSrxn = 319.1 J/mol K and Δ = −14.3 J/mol K and ΔSrxn = 135.7 J/mol K for armenite and epididymite, respectively. The H2O molecules in both phases appear to be ordered. They are held in place via an ion-dipole interaction between the H2O molecule and a Ca cation in the case of armenite and a Na cation in epididymite and through hydrogen-bonding between the H2O molecule and oxygen atoms of the respective silicate frameworks. Of the three different H2O phases ice, liquid water and steam, the Cp behavior of confined H2O in both armenite and epididymite is most similar to that of ice, but there are differences between the two silicates and from the Cp behavior of ice. Hydrogen-bonding behavior and its relation to the entropy of confined H2O at 298 K is analyzed for various microporous silicates.The entropy of confined H2O at 298 K in various silicates increases approximately linearly with increasing average wavenumber of the OH-stretching vibrations. The interpretation is that decreased hydrogen-bonding strength between a H2O molecule and the silicate framework, as well as weak ion-dipole interactions, results in increased entropy of H2O. This results in increased amplitudes of external H2O vibrations, especially translations of the molecule, and they contribute strongly to the entropy of confined H2O at T < 298 K.  相似文献   

6.
By taking advantage of having depth profiles between contrasting lithologies from core samples of the Chinese Continental Scientific Drilling (CCSD) project, a combined study was carried out to examine changes in mineral H isotope, total water and hydroxyl contents in garnet and omphacite across the contacts between ultrahigh-pressure (UHP) eclogite and gneiss in the Sulu orogen, east-central China. The samples of interest were from two continuous core segments from the CCSD main hole at depths of 734.21-737.16 and 929.67-932.86 m, respectively. The results show δD values of −116‰ to  − 64‰ for garnet and −104‰ to −82‰ for omphacite, consistent with incorporation of meteoric water into protoliths of UHP metamorphic rocks by high-T alteration. Both equilibrium and disequilibrium H isotope fractionations were observed between garnet and omphacite, suggesting fluid-assisted H isotope exchange at local scales during amphibolite-facies retrogression. While bulk water analysis gave total H2O concentrations of 522-1584 ppm for garnet and 1170-20745 ppm for omphacite, structural hydroxyl analysis yielded H2O contents of 80-413 ppm for garnet and 228-412 ppm for omphacite. It appears that significant amounts of molecular H2O are present in the minerals, pointing to enhanced capacity of water storage in the UHP eclogite minerals. Hydrogen isotope variations in the transition between eclogite and gneiss show correlations with variations in their water contents. Petrographically, the degree of retrograde metamorphism generally increases with decreasing distance from the eclogite-gneiss boundary. Thus, retrograde metamorphism results in mineral reactions and H isotope variation. Because hydroxyl solubility in nominally anhydrous minerals decreases with dropping pressure, significant amounts of water are expected to be released from the minerals during decompression exhumation. Decompression exsolution of structural hydroxyl from 1 m3 volume of eclogite composed of only garnet and omphacite results in release of a quantitative estimate of 3.07-3.44 kg water that can form 140-156 kg amphibole during exhumation. Therefore, it is concluded that fluid for retrogression of the eclogites away from the eclogite-gneiss boundary was derived from the decompression exsolution of structural hydroxyl and molecular H2O in nominally anhydrous minerals. For the eclogites adjacent to gneiss, in contrast, the retrograde metamorphism was principally caused by aqueous fluid from the gneiss which is relatively rich in water. Consequently, both the origin and availability of metamorphic fluid during exhumation of deeply subducted continental crust are deciphered by this combined study focusing on the transitions and the retrograde processes between the felsic and mafic UHP rocks.  相似文献   

7.
Raman spectroscopy is a powerful method for the determination of CO2 densities in fluid inclusions, especially for those with small size and/or low fluid density. The relationship between CO2 Fermi diad split (Δ, cm−1) and CO2 density (ρ, g/cm3) has been documented by several previous studies. However, significant discrepancies exist among these studies mainly because of inconsistent calibration procedures and lack of measurements for CO2 fluids having densities between 0.21 and 0.75 g/cm3, where liquid and vapor phases coexist near room temperature.In this study, a high-pressure optical cell and fused silica capillary capsules were used to prepare pure CO2 samples with densities between 0.0472 and 1.0060 g/cm3. The measured CO2 Fermi diad splits were calibrated with two well established Raman bands of benzonitrile at 1192.6 and 1598.9 cm−1. The relationship between the CO2 Fermi diad split and density can be represented by: ρ = 47513.64243 − 1374.824414 × Δ + 13.25586152 × Δ2 − 0.04258891551 × Δ3 (r2 = 0.99835, σ = 0.0253 g/cm3), and this relationship was tested by synthetic fluid inclusions and natural CO2-rich fluid inclusions. The effects of temperature and the presence of H2O and CH4 on this relationship were also examined.  相似文献   

8.
Understanding mechanisms and kinetics of mineral carbonation reactions relevant to sequestering carbon dioxide as a supercritical fluid (scCO2) in geologic formations is crucial to accurately predicting long-term storage risks. Most attention so far has been focused on reactions occurring between silicate minerals and rocks in the aqueous dominated CO2-bearing fluid. However, water-bearing scCO2 also comprises a reactive fluid, and in this situation mineral carbonation mechanisms are poorly understood. Using in situ high-pressure X-ray diffraction, the carbonation of brucite [Mg(OH)2] in wet scCO2 was examined at pressure (82 bar) as a function of water concentration and temperature (50 and 75 °C). Exposing brucite to anhydrous scCO2 at either temperature resulted in little or no detectable reaction over three days. However, addition of trace amounts of water resulted in partial carbonation of brucite into nesquehonite [MgCO3·3H2O] within a few hours at 50 °C. By increasing water content to well above the saturation level of the scCO2, complete conversion of brucite into nesquehonite was observed. Tests conducted at 75 °C resulted in the conversion of brucite into magnesite [MgCO3] instead, apparently through an intermediate nesquehonite step. Raman spectroscopy applied to brucite reacted with 18O-labeled water in scCO2 show it was incorporated into carbonate at a relatively high concentration. This supports a carbonation mechanism with at least one step involving a direct reaction between the mineral and water molecules without mediation by a condensed aqueous layer.  相似文献   

9.
This work reports the application of thermodynamic models, including equations of state, to binary (salt-free) CH4-H2O fluid inclusions. A general method is presented to calculate the compositions of CH4-H2O inclusions using the phase volume fractions and dissolution temperatures of CH4 hydrate. To calculate the homogenization pressures and isolines of the CH4-H2O inclusions, an improved activity-fugacity model is developed to predict the vapor-liquid phase equilibrium. The phase equilibrium model can predict methane solubility in the liquid phase and water content in the vapor phase from 273 to 623 K and from 1 to 1000 bar (up to 2000 bar for the liquid phase), within or close to experimental uncertainties. Compared to reliable experimental phase equilibrium data, the average deviation of the water content in the vapor phase and methane solubility in the liquid phase is 4.29% and 3.63%, respectively. In the near-critical region, the predicted composition deviations increase to over 10%. The vapor-liquid phase equilibrium model together with the updated volumetric model of homogenous (single-phase) CH4-H2O fluid mixtures (Mao S., Duan Z., Hu J. and Zhang D. (2010) A model for single-phase PVTx properties of CO2-CH4-C2H6-N2-H2O-NaCl fluid mixtures from 273 to 1273 K and from 1 to 5000 bar. Chem. Geol.275, 148-160), is applied to calculate the isolines, homogenization pressures, homogenization volumes, and isochores at specified homogenization temperatures and compositions. Online calculation is on the website: http://www.geochem-model.org/.  相似文献   

10.
Solubilities of corundum (Al2O3) and wollastonite (CaSiO3) were measured in H2O-NaCl solutions at 800 °C and 10 kbar and NaCl concentrations up to halite saturation by weight-loss methods. Additional data on quartz solubility at a single NaCl concentration were obtained as a supplement to previous work. Single crystals of synthetic corundum, natural wollastonite or natural quartz were equilibrated with H2O and NaCl at pressure (P) and temperature (T) in a piston-cylinder apparatus with NaCl pressure medium and graphite heater sleeves. The three minerals show fundamentally different dissolution behavior. Corundum solubility undergoes large enhancement with NaCl concentration, rising rapidly from Al2O3 molality (mAl2O3) of 0.0013(1) (1σ error) in pure H2O and then leveling off to a maximum of ∼0.015 at halite saturation (XNaCl ≈ 0.58, where X is mole fraction). Solubility enhancement relative to that in pure H2O, , passes through a maximum at XNaCl ≈ 0.15 and then declines towards halite saturation. Quenched fluids have neutral pH at 25 °C. Wollastonite has low solubility in pure H2O at this P and T(mCaSiO3=0.0167(6)). It undergoes great enhancement, with a maximum solubility relative to that in H2O at XNaCl ≈ 0.33, and solubility >0.5 molal at halite saturation. Solute silica is 2.5 times higher than at quartz saturation in the system H2O-NaCl-SiO2, and quenched fluids are very basic (pH 11). Quartz shows monotonically decreasing solubility from mSiO2=1.248 in pure H2O to 0.202 at halite saturation. Quenched fluids are pH neutral. A simple ideal-mixing model for quartz-saturated solutions that requires as input only the solubility and speciation of silica in pure H2O reproduces the data and indicates that hydrogen bonding of molecular H2O to dissolved silica species is thermodynamically negligible. The maxima in for corundum and wollastonite indicate that the solute products include hydrates and Na+ and/or Cl− species produced by molar ratios of reactant H2O to NaCl of 6:1 and 2:1, respectively. Our results imply that quite simple mechanisms may exist in the dissolution of common rock-forming minerals in saline fluids at high P and T and allow assessment of the interaction of simple, congruently soluble rock-forming minerals with brines associated with deep-crustal metamorphism.  相似文献   

11.
The Red Lake greenstone belt is one of the foremost Au mining camps in Canada and hosts the world-class Campbell-Red Lake Au deposit. Belt-scale hydrothermal alteration is characterized by proximal ferroan dolomite zones associated with Au mineralization surrounded by distal calcite zones, both being accompanied by potassic alterations (sericite, muscovite, and biotite). At the Campbell-Red Lake and Cochenour deposits Au mineralization (in particular high-grade ore) is associated with silica and sulfides (especially arsenopyrite) that replace carbonate ± quartz veins and the host rocks. The prevalence of carbonic fluid inclusions and rare occurrence of aqueous-bearing inclusions in carbonate–quartz–Au veins in the Campbell-Red Lake deposit, and the consistency of homogenization temperatures of carbonic inclusions within individual fluid inclusion assemblages (FIA), have been interpreted to indicate that H2O-poor, CO2-dominated fluids were responsible for the carbonate veining and Au mineralization. Further studies of fluid inclusions in carbonate–quartz veins within and outside the deformation zone hosting the Campbell-Red Lake deposit (the Red Lake Mine trend) including the Cochenour Au deposit, the Redcon Au prospect, and outcrops in the distal calcite zone also reveal the dominance of carbonic fluid inclusions in vein minerals. These studies indicate that CO2-dominated fluids were flowing through fractures during carbonate vein formation and Au mineralization both within and outside major structures. The carbonic fluid may have been initially undersaturated with water, or it may have resulted from phase separation of an H2O–CO2–NaCl fluid. In the latter case, phase separation modeling indicates that the initial fluid likely had XCO2XCO2 values larger than 0.8. Calculations based on hydrothermal mineral assemblages indicate XCO2XCO2 values in the host rocks from 0.025 to 0.85, reflecting a change from CO2-dominated fluids in the fractures (veins) to H2O-dominated fluids in the host rocks away from the fractures. The CO2-dominated fluids were likely advected from granulite facies in the deeper crust, whereas the H2O-dominated fluids were derived from the ambient host rocks of amphibole to greenschist facies. Calculations based on CO2 requirements and source constraints indicate that the mineralizing fluids were likely two orders of magnitude more enriched in Au than the commonly assumed values of a few μg/L, which may explain why the Campbell-Red Lake deposit has a very high-grade of Au (average 21 g/t for the whole deposit and 81 g/t for the Goldcorp High-Grade zone). Fluid inclusion data suggest that the carbonate veining and Au mineralization likely took place at depths from 7 to 14 km. The development of crustiform–colloform structures in the carbonate ± quartz veins, which was previously interpreted to indicate relatively shallow environments, may alternatively have been related to extremely high fluid pressures and the CO2-dominated nature of the fluids, which could have enhanced the brittle properties of the rocks due to their high wetting angles.  相似文献   

12.
The solubility and incorporation mechanisms of water in synthetic and natural MgAl2O4 spinel have been investigated in a series of high-pressure/temperature annealing experiments. In contrast to most other nominally anhydrous minerals, natural spinel appears to be completely anhydrous. On the other hand, non-stoichiometric Al-rich synthetic (defect) spinel can accommodate several hundred ppm water in the form of structurally-incorporated hydrogen. Infrared (IR) spectra of hydrated defect spinel contain one main O-H stretching band at 3343-3352 cm−1 and a doublet consisting of two distinct O-H bands at 3505-3517 cm−1 and 3557-3566 cm−1. IR spectra and structural refinements based on single-crystal X-ray data are consistent with hydrogen incorporation in defect spinel onto both octahedral and tetrahedral O-O edges. Fine structure of O-H bands in IR spectra can be explained by partial coupling of interstitial hydrogen with cation vacancies, or by the effects of Mg-Al disorder on the tetrahedral site. The concentration of cation vacancies in defect spinel is a major control on hydrogen affinity. The commercial availability of large single crystals of defect spinel coupled with high water solubility and similarities in water incorporation mechanisms between hydrous defect spinel and hydrous ringwoodite (Mg2SiO4) suggests that synthetic defect spinel may be a useful low-pressure analogue material for investigating the causes and consequences of water incorporation in the lower part of Earth’s mantle transition zone.  相似文献   

13.
Dunite, wehrlite and websterite are rare members of the mantle xenolith suite in the Kimberley kimberlites of the Kaapvaal Craton in southern Africa. All three types were originally residues of extensive melt extraction and experienced varying amounts and types of melt re-enrichment. The melt depletion event, dated by Re-Os isotope systematics at 2.9 Ga or older, is evidenced by the high Mg# (Mg/(Mg + Fe)) of silicate minerals (olivine (0.89-0.93); pyroxene (0.88-0.93); garnet (0.72-0.85)), high Cr# (Cr/(Cr + Al)) of spinel (0.53-0.84) and mostly low whole-rock SiO2, CaO and Al2O3 contents. Shortly after melt depletion, websterites were formed by reaction between depleted peridotites and silica-rich melt (>60 wt% SiO2) derived by partial melting of eclogite before or during cratonization. The melt-peridotite interaction converted olivine into orthopyroxene.All three xenolith types have secondary metasomatic clinopyroxene and garnet, which occur along olivine grain boundaries and have an amoeboid texture. As indicated by the preservation of oxygen isotope disequilibrium in the minerals and trace-element concentrations in clinopyroxene and garnet, this metasomatic event is probably of Mesozoic age and was caused by percolating alkaline basaltic melts. This melt metasomatism enriched the xenoliths in CaO, Al2O3, FeO and high-field-strength-elements, and might correspond to the Karoo magmatism at 200 Ma. The websterite xenoliths experienced both the orthoyproxene-enrichment and clinopyroxene-garnet metasomatic events, whereas dunite and wehrlite xenoliths only saw the later basaltic melt event, and may have been situated further away from the source of melt migration channels.  相似文献   

14.
The present study illustrates the interest of using the elastic recoil detection analysis (ERDA) method to characterize any geological sample matrix with respect to hydrogen. ERDA is combined with Rutherford back scattering (RBS) and particle induced X-ray emission (PIXE), allowing the simultaneous characterization of the matrix with respect to major and trace elements (Z > 15). Analyses are performed by mapping of a 4 × 16 μm2 incident beam of 4He+ on large areas (50 × 200 μm2). The method is almost not destructive and requires no calibration with respect to well known hydrous samples. Hydrous and nominally anhydrous phases in contact with each other in the same sample may both be characterized. The depth of the analyses is limited to several μm beneath the surface, allowing tiny samples to be investigated, provided their sizes are larger than the incident beam. Our setup has been improved in order to allow H determination on a micrometric scale with a 5-15% relative uncertainty and a detection limit of 94 wt ppm H2O. We present multi-elemental mappings on a large panel of samples: (1) natural and analogue synthetic glasses from Stromboli volcano (0.44-4.59 wt% H2O), natural rhyolitic glasses (1466-1616 wt ppm H2O); (2) magmatic rhyolitic melt inclusions from Guadeloupe Island (4.37-5.47 wt% H2O) and their quartz host crystal (2020 ± 230 wt ppm H2O); (3) nominally anhydrous natural (82-260 wt ppm H2O) and experimentally hydrated (240-790 wt ppm H2O) olivines; natural clinopyroxenes (159-716 wt ppm H2O); natural orthopyroxenes (201-452 wt ppm H2O); a natural garnet (90 wt ppm H2O). Results show that ERDA is a strong and accurate reference method that can be used to characterize geological sample from various matrix compositions from high to low water contents. It can be used to calibrate other methods of microanalysis such as Fourier Transform Infrared Spectroscopy (FTIR) or secondary ion mass spectrometry (SIMS).  相似文献   

15.
Fluid inclusions in quartz globules and quartz veins of a 3.8-3.7 Ga old, well-preserved pillow lava breccia in the northeastern Isua Greenstone Belt (IGB) were studied using microthermometry, Raman spectrometry and SEM Cathodoluminescence Imaging. Petrographic study of the different quartz segregations showed that they were affected by variable recrystallization which controlled their fluid inclusion content. The oldest unaltered fluid inclusions found are present in vein crystals that survived dynamic and static recrystallization. These crystals contain a cogenetic, immiscible assemblage of CO2-rich (+H2O, +graphite) and brine-rich (+CO2, +halite, +carbonate) inclusions. The gas-rich inclusions have molar volumes between 44.8 and 47.5 cm3/mol, while the brine inclusions have a salinity of ∼33 eq. wt% NaCl. Modeling equilibrium immiscibility using volumetric and compositional properties of the endmember fluids indicates that fluid unmixing occurred at or near peak-metamorphic conditions of ∼460 °C and ∼4 kbar. Carbonate and graphite were precipitated cogenetically from the physically separated endmember fluids and were trapped in fluid inclusions.In most quartz crystals, however, recrystallization obliterated such early fluid inclusion assemblages and left graphite and carbonate as solid inclusions in recrystallized grains. Intragranular fluid inclusion trails in the recrystallized grains of breccia cementing and crosscutting quartz veins have CO2-rich assemblages, with distinctly different molar volumes (either between 43.7 and 47.5 cm3/mol or between 53.5 and 74.1 cm3/mol), and immiscible, halite-saturated H2O-CO2-NaCl(-other salt) inclusions. Later intergranular trails have CH4-H2 (XH2 up to ∼0.3) inclusions of variable density (ranging from 48.0 to >105.3 cm3/mol) and metastable H2O-NaCl(-other salt?) brines (∼28 eq. wt% NaCl). Finally, the youngest fluid inclusion assemblages are found in non-luminescent secondary quartz and contain low-density CH4 (molar volume > 105.33 cm3/mol) and low-salinity H2O-NaCl (0.2-3.7 eq. wt% NaCl). These successive fluid inclusion assemblages record a retrograde P-T evolution close to a geothermal gradient of ∼30 °C/km, but also indicate fluid pressure variations and the introduction of highly reducing fluids at ∼200-300 °C and 0.5-2 kbar. The quartz globules in the pillow fragments only contain sporadic CH4(+H2) and brine inclusions, corresponding with the late generations present in the cementing and crosscutting veins. We argue that due to the large extent of static recrystallization in quartz globules in the pillow breccia fragments, only these relatively late fluid inclusions have been preserved, and that they do not represent remnants of an early, seafloor-hydrothermal system as was previously proposed.Modeling the oxidation state of the fluids indicates a rock buffered system at peak-metamorphic conditions, but suggests a change towards fluid-graphite disequilibrium and a logfH2/fH2O above the Quartz-Fayalite-Magnetite buffer during retrograde evolution. Most likely, this indicates a control on redox conditions and on fluid speciation by ultramafic rocks in the IGB.Finally, this study shows that microscopic solid graphite in recrystallized metamorphic rocks from Isua can be deposited inorganically from a fluid phase, adding to the complexity of processes that formed reduced carbon in the oldest, well-preserved supracrustal rocks on Earth.  相似文献   

16.
H2O diffusion in dacitic melt was investigated at 0.48-0.95 GPa and 786-893 K in a piston-cylinder apparatus. The diffusion couple design was used, in which a nominally dry dacitic glass makes one half and is juxtaposed with a hydrous dacitic glass containing up to ∼8 wt.% total water (H2Ot). H2O concentration profiles were measured on quenched glasses with infrared microspectroscopy. The H2O diffusivity in dacite increases rapidly with water content under experimental conditions, similar to previous measurements at the same temperature but at pressure <0.15 GPa. However, compared with the low-pressure data, H2O diffusion at high pressure is systematically slower. H2O diffusion profiles in dacite can be modeled by assuming molecular H2O (H2Om) is the diffusing species. Total H2O diffusivity DH2Ot within 786-1798 K, 0-1 GPa, and 0-8 wt.% H2Ot can be expressed as: where DH2Ot is in m2/s, T is temperature in K, P is pressure in GPa, K = exp(1.49 − 2634/T) is the equilibrium constant of speciation reaction (H2Om+O?2OH) in the melt, X = C/18.015/[C/18.015 + (100 − C)/33.82], C is wt.% of H2Ot, and 18.015 and 33.82 g/mol correspond to the molar masses of H2O and anhydrous dacite on a single oxygen basis. Compared to H2O diffusion in rhyolite, diffusivity in dacite is lower at intermediate temperatures but higher at superliquidus temperatures. This general H2O diffusivity expression can be applied to a broad range of geological conditions, including both magma chamber processes and volcanic eruption dynamics from conduit to the surface.  相似文献   

17.
Aqueous fluids in sedimentary basins often contain dissolved methane, particularly in petroleum environments. PVTX (Pressure-Volume-Temperature-Composition) reconstructions performed using fluid inclusion data are largely based on the assumption that inclusions do not change from the time of trapping until the present. Many authors, however, consider that fluid inclusions can re-equilibrate, particularly in fragile minerals like calcite. In order to understand this re-equilibration phenomenon in the metamorphic domain, previous experiments have been performed under high PT conditions, but few have been performed at low to medium PT conditions such as those associated with sedimentary burial diagenesis, and no previous studies have examined CH4-bearing aqueous inclusions in calcite.An experimental study of the preservation/modification of CH4-rich synthetic fluid inclusions in calcite during isothermal decompression was conducted. An autoclave was used for accurate PTX control allowing equilibrium between liquid and vapour in the CH4-H2O system. PTX conditions were maintained at four stages of decreasing pressure, with each stage held for 7 days to simulate an isothermal pressure drop. In order of decreasing pressure, the pressure-temperature conditions monitored were 276 ± 10 bar at 180 ± 7 °C, 176 ± 10 bar at 180 ± 7 °C, 76 ± 10 bar at 180 ± 7 °C and 10 ± 3 bar at 180 ± 15 °C. At the end of the experiment, the calcite was recovered and analyzed by microthermometry and Raman microspectroscopy for PTX reconstruction. A careful procedure was adopted to limit re-equilibration of inclusions during analytical procedures. Four types of inclusion shapes and four types of strain patterns were differentiated. Classification of the petrographic strain patterns was carried out. These strain patterns were associated with inclusion stretching and/or leakage regarding CH4, Th and Ph compared to experimental conditions. Factors controlling the preservation or acquisition of strain patterns included the initial shape and size of the inclusion, and the pressure differential (ΔP) between the confining pressure (Pcf) and the internal pressure (Pi) within the inclusion. Most fluid inclusions seemed to be trapped during the first 7 days of the experiment, although few (4%) of these preserved the initial PT conditions of 276 ± 10 bar, whereas 8% preserved the second and third run of PT conditions. Overall, the majority of inclusions (88%) did not reflect accurately the PTX trapping conditions. A petrographic guide to the inclusions is presented here that allows strain identification for PVT reconstructions. Re-equilibration patterns and evidence for preferential methane leakage from aqueous inclusions in calcite are important findings revealed by this study, and may be useful for the reconstruction of post-trapping events in investigations of natural samples, and in other experiments using synthetic inclusions in calcite.  相似文献   

18.
Dissolution rates of limestone covered by a water film open to a CO2-containing atmosphere are controlled by the chemical composition of the CaCO3-H2O-CO2 solution at the water-mineral interface. This composition is determined by the Ca2+-concentration at this boundary, conversion of CO2 into H+ and in the solution, and by diffusional mass transport of the dissolved species from and towards the water-limestone interface. A system of coupled diffusion-reaction equations for Ca2+, , and CO2 is derived. The Ca2+ flux rates at the surface of the mineral are defined by the PWP-empirical rate law. These flux rates by the rules of stoichiometry must be equal to the flux rates of CO2 across the air-water interface. In the solution, CO2 is converted into H+ and . At low water-film thickness this reaction becomes rate limiting. The time dependent diffusion-reaction equations are solved for free drift dissolution by a finite-difference scheme, to obtain the dissolution rate of calcite as a function of the average calcium concentration in the water film. Dissolution rates are obtained for high undersaturation. The results reveal two regimes of linear dissolution kinetics, which can be described by a rate law F = αi(miceq − c), where c is the calcium concentration in the water film, ceq the equilibrium concentration with respect to calcite. For index i = 0, a fast rate law, which here is reported for the first time, is found with α0 = 3 × 10−6 m s−1 and m0 = 0.3. For c > m0ceq, a slow rate law is valid with α1 = 3 × 10−7 m  s−1 and m1 = 1, which confirms earlier work. The numbers given above are valid for film thickness of several tenths of a millimetre and at 20 °C. These rates are proven experimentally, using a flat inclined limestone plate covered by a laminar flowing water film injected at an input point with known flow rate Q and calcium concentration. From the concentration measured after flow distance x the dissolution rates are determined. These experiments have been performed at a carbon-dioxide pressure of 0.00035 atm and also of 0.01 atm. The results are in good agreement to the theoretical predictions.  相似文献   

19.
The solubilities of the assemblages albite + paragonite + quartz and jadeite + paragonite + quartz in H2O were determined at 500 and 600 °C, 1.0-2.25 GPa, using hydrothermal piston-cylinder methods. The three minerals are isobarically and isothermally invariant in the presence of H2O, so fluid composition is uniquely determined at each pressure and temperature. A phase-bracketing approach was used to achieve accurate solubility determinations. Albite + quartz and jadeite + quartz dissolve incongruently in H2O, yielding residual paragonite which could not be retrieved and weighed. Solution composition fixed by the three-mineral assemblage at a given pressure and temperature was therefore bracketed by adding NaSi3O6.5 glass in successive experiments, until no paragonite was observed in run products. Solubilities derived from experiments bounding the appearance of paragonite thus constrain the equilibrium fluid composition. Results indicate that, at a given pressure, Na, Al, and Si concentrations are higher at 600 °C than at 500 °C. At both 500 and 600 °C, solubilities of all three elements increase with pressure in the albite stability field, to a maximum at the jadeite-albite-quartz equilibrium. In the jadeite stability field, element concentrations decline with continued pressure increase. At the solubility maximum, Na, Al, and Si concentrations are, respectively, 0.16, 0.05, and 0.48 molal at 500 °C, and 0.45, 0.27, and 1.56 molal at 600 °C. Bulk solubilities are 3.3 and 10.3 wt% oxides, respectively. Observed element concentrations are everywhere greater than those predicted from extrapolated thermodynamic data for simple ions, monomers, ion pairs, and the silica dimer. The measurements therefore require the presence of additional, polymerized Na-Al-Si-bearing species in the solutions. The excess solubility is >50% at all conditions, indicating that polymeric structures are the predominant solutes in the P-T region studied. The solubility patterns likely arise from combination of the large solid volume change associated with the albite-jadeite-quartz equilibrium and the rise in Na-Al-Si polymerization with approach to the hydrothermal melting curves of albite + quartz and jadeite + quartz. Our results indicate that polymerization of Na-Al-Si solutes is a fundamental aspect of fluid-rock interaction at high pressure. In addition, the data suggest that high-pressure metamorphic isograds can impose unexpected controls on metasomatic mass transfer, that significant metasomatic mass transfer prior to melting should be considered in migmatitic terranes, and that polymeric complexes may be an important transport agent in subduction zones.  相似文献   

20.
Spinel peridotite xenoliths in alkali basalts at Tok, SE Siberian craton range from fertile lherzolites to harzburgites and wehrlites; olivine-rich (70-84%) rocks are dominant. REE patterns in the lherzolites range from nearly flat for fertile rocks (14-17% cpx) to LREE-enriched; the enrichments are positively correlated with modal olivine, consistent with high-permeability of olivine-rich rocks during melt percolation. Clinopyroxene in olivine-rich Tok peridotites typically has convex-upward trace element patterns (La/NdPM < 1 and Nd/YbPM ? 1), which we consider as evidence for equilibration with evolved silicate liquids (with higher REE and lower Ti contents than in host basalts). Whole-rock patterns of the olivine-rich xenoliths range from convex-upward to LREE-enriched (La/NdPM > 1); the LREE-enrichments are positively correlated with phosphorus abundances and are mainly hosted by accessory phosphates and P-rich cryptocrystalline materials. In addition to apatite, some Tok xenoliths contain whitlockite (an anhydrous, halogen-poor and Na-Mg-rich phosphate), which is common in meteorites and lunar rocks, but has not been reported from any terrestrial mantle samples. Some olivine-rich peridotites have generations of clinopyroxene with distinct abundances of Na, LREE, Sr and Zr. The mineralogical and trace element data indicate that the lithospheric mantle section represented by the xenoliths experienced a large-scale metasomatic event produced by upward migration of mafic silicate melts followed by percolation of low-T, alkali-rich melts and fluids. Chromatographic fractionation and fractional crystallisation of the melts close to the percolation front produced strong LREE-enrichments, which are most common in the uppermost mantle and are related to carbonate- and P2O5-rich derivatives of the initial melt. Reversal and gradual retreat of the percolation front during thermal relaxation to ambient geotherm (“retrograde” metasomatism) caused local migration and entrapment of small-volume residual fluids and precipitation of volatile-rich accessory minerals. A distinct metasomatic episode, which mainly produced “anhydrous” late-stage interstitial materials was concomitant with the alkali basaltic magmatism, which brought the xenoliths to the surface.  相似文献   

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