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1.
A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe2+ at M1 as well as at M2, and in a first approach assigned Fe3+ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε i,tot = 65,000 ± 3,000 lmolH2O ?1 cm?2. Using this new ε i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H2O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe3+ (<0.1 Fe3+ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al3+ at the tetrahedral site (OH bands around 3,525 cm?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe3+-rich sample (0.2 Fe3+ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm?1 plus shoulder at 3,450 cm?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe3+ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe2+ and combined with increase in Fe3+. That dehydration is correlated with oxidation of Fe2+ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH? content and giving no indication of Fe2+-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe2+ at M2 and low-water concentrations, i.e., at a ratio of Fe2+ M2/H > 10 dehydration occurs by iron oxidation of Fe2+ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe2+ at M2 but high-water concentrations, i.e., ratio of Fe2+ M2/H < 5.0 dehydration occurs through oxidation of Fe2+ at M1.  相似文献   

2.
The new synthetic phase Mg2Al3O[BO4]2(OH) provisionally named “pseudosinhalite” is optically, chemically, and structurally similar to the mineral sinhalite, MgAl[BO4], isostructural with forsterite. It grows hydrothermally from appropriate bulk compositions in the range 4–40?kbar at temperatures that increase with pressure (～650?→?900?°C), and it breaks down at higher temperatures to sinhalite?+?corundum?+?H2O. At P?≥?20?kbar single-phase products of euhedral twinned crystals could often be obtained. Pseudosinhalite is monoclinic with a?=?7.455 (1) Å, b?=?4.330 (1) Å, c?=?9.825 (2) Å, β?=?110.68 (1)°, and space group P21/c. Crystal structure analysis reveals that pseudosinhalite is also based on hexagonal close packing (hcp) of oxygen atoms with Mg and Al in octahedral and B in tetrahedral coordination. In pseudosinhalite the winged octahedral chains in the plane of hcp are not straight as in sinhalite but have a zigzag, 3-repeat period (Dreierkette), and only 1/10 instead of 1/8 of all tetrahedral sites are filled by boron. Hydrogen is located at a split position between two oxygen atoms O5—O5, which are only 2.550 Å apart and thus generate strong hydrogen bonding. This may be responsible for the absence of an hydroxyl absorption band between 2800?cm?1 and 3500?cm?1 in the powder IR spectrum. The equilibrium breakdown curve of pseudosinhalite to form sinhalite, corundum, and water was determined by bracketing experiments to pass through 10?kbar, 745?°C and 35?kbar, 950?°C, giving a slope of about 8?°C/kbar, similar to dehydration curves of some silicates at high pressure. In nature pseudosinhalite could have been misidentified as sinhalite. A possible appearance, like sinhalite in boron-rich skarns, would require more aluminous bulk compositions than for sinhalite at relatively low temperatures. However, pseudosinhalite might also form as a hydrous alteration product of sinhalite at low temperatures, perhaps in association with szaibelyite, MgBO2(OH).  相似文献   

3.
4He accumulated in fluids is a well established geochemical tracer used to study crustal fluid dynamics. Direct fluid samples are not always collectable; therefore, a method to extract rare gases from matrix fluids of whole rocks by diffusion has been adapted. Helium was measured on matrix fluids extracted from sandstones and mudstones recovered during the San Andreas Fault Observatory at Depth (SAFOD) drilling in California, USA. Samples were typically collected as subcores or from drillcore fragments. Helium concentration and isotope ratios were measured 4?C6 times on each sample, and indicate a bulk 4He diffusion coefficient of 3.5?±?1.3?×?10?C8 cm2?s?C1 at 21°C, compared to previously published diffusion coefficients of 1.2?×?10?C18 cm2?s?C1 (21°C) to 3.0?×?10?C15 cm2?s?C1 (150°C) in the sands and clays. Correcting the diffusion coefficient of 4Hewater for matrix porosity (??3%) and tortuosity (??6?C13) produces effective diffusion coefficients of 1?×?10?C8 cm2?s?C1 (21°C) and 1?×?10?C7 (120°C), effectively isolating pore fluid 4He from the 4He contained in the rock matrix. Model calculations indicate that <6% of helium initially dissolved in pore fluids was lost during the sampling process. Complete and quantitative extraction of the pore fluids provide minimum in situ porosity values for sandstones 2.8?±?0.4% (SD, n?=?4) and mudstones 3.1?±?0.8% (SD, n?=?4).  相似文献   

4.
The dehydration kinetics of serpentine was investigated using in situ high-temperature infrared microspectroscopy. The analyzed antigorite samples at room temperature show relatively sharp bands at around 3,655–3,660 cm?1 (band 1), 3,570–3,595 cm?1 (band 2), and 3,450–3,510 cm?1 (band 3). Band 1 corresponds to the Mg–OH bond, and bands 2 and 3 correspond to OH associated with the substitution of Al for Si. Isothermal kinetic heating experiments at temperatures ranging from 625 to 700 °C showed a systematic decrease of the OH band absorbance with heating duration. The one-dimensional diffusion was found to provide the best fit to the experimental data, and diffusion coefficients were determined with activation energies of 219 ± 37 kJ mol?1 for the total water band area, 245 ± 46 kJ mol?1 for band 1, 243 ± 57 kJ mol?1 for band 2, and 256 ± 53 kJ mol?1 for band 3. The results indicate that the dehydration process is controlled by one-dimensional diffusion through the tetrahedral geometry of serpentine. Fluid production rates during antigorite dehydration were calculated from kinetic data and range from 3 × 10?4 to 3 × 10?5  $ {\text{m}}_{\text{fluid}}^{ 3} \,{\text{m}}_{\text{rock}}^{ - 3} \,{\text{s}}^{ - 1} $ . The rates are high enough to provoke hydraulic rupture, since the relaxation rates of rocks are much lower than these values. The results suggest that the rapid dehydration of antigorite can trigger an intermediate-depth earthquake associated with a subducting slab.  相似文献   

5.
The in situ Raman spectra of a hydrous anorthoclase at temperatures of 20–800 °C have been measured using a LABRAM-HR spectrometer and Linkam TS 1500 heating stage. The frequencies of modes at 54, 99, 130 and 162 cm?1 related to M–O vibrations decrease sharply and then increase drastically or keep steady at temperatures above 200 °C. A knee point can be clearly seen at about 200 °C for those modes. The frequency of the mode at 282 cm?1 shows little temperature dependence. However, for the two strongest modes at 471 and 512 cm?1, the frequencies decrease linearly with increasing temperature. From evolution of the frequencies of modes at 54, 99, 130 and 162 cm?1 with temperature, the following conclusions can be drawn: (1) The distance of the local M–O bond shortens rather than lengthens at temperatures above 200 °C; (2) The abrupt changes of the local structure of M site induce a collapse of the framework structure and displacive phase transition at 200 °C; and (3) The H atoms incorporated in anorthoclase are located at the M site. These results are indicative for the structure and properties of anorthoclase at deep earth conditions.  相似文献   

6.
The incorporation of OH defects in quartz from the systems quartz–water, quartz–albite–water and granite–water at pressures between 5 and 25?kbar and temperatures between 800 and 1,000?°C was investigated by IR spectroscopy. The two most important OH absorption features can be assigned to hydrogarnet defects (absorption band at 3,585?cm?1) and coupled substitutions involving Al3+ (Al–H defects, absorption bands at 3,310, 3,378 and 3,430?cm?1). Al incorporation in quartz is controlled by mineral/melt partitioning (D Al Qz/Melt ?=?0.01) and exhibits a negative pressure dependence. This trend is not clearly reflected by the concentration of Al–H defects, which shows positive deviations from the theoretical 1:1 correlation of Al/H for some samples. In contrast to the Al–H defects, formation of hydrogarnet defects appears to be positively correlated to pressure and water activity, and may be used a petrological indicator. The overall water concentration exhibits only minor changes with pressure and temperature, but a clear correlation of water activity (controlled by various amounts of dissolved salts) and hydrogarnet substitution could be established.  相似文献   

7.
We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between ?194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm?1 display a small frequency lowering (<4 cm?1) and a moderate broadening (<10 cm?1) as temperature is increased from ?194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm?1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm?1 respectively) and broadening (~30 cm?1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm?1, three broad bands are identified at 3,151, 3,178 and 3,217 cm?1, at ?194 °C. They exhibit significant frequency increase (~20 cm?1) and broadening (~70 cm?1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm?1 (type (2); 3,550 cm?1 at room temperature). The contribution of OH bands of type (3), associated to (2H)Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.  相似文献   

8.
Oceanic upwelling results in the intermittent intrusion of cold ocean water enriched in nitrate, and to a lesser extent soluble reactive phosphorus (SRP), into the Kariega Estuary (South Africa). Laboratory measocosm experiments were conducted to determine the effects of such changes on fluxes of dissolved nutrients across the surface of a salt marsh within the estuary. When replicate mesocosms of the tidal creek and salt marsh were inundated with nonupwelled water (at 25°C and nitrate concentrations of 4.5 μmoll?1), nitrate fluxes in both regions were small, and the tidal creek exhibited net uptake (negative value) of nitrate from the water column (?85 μmol m?2 tide?1), and the marsh, net release (positive values; 113 μmol m?2 tide?1). When the mesocosms were inundated with upwelled water, at 16°C and with nitrate concentrations of 24.2 μmol l?1, both regions exhibited large net uptakes of nitrate (?514 μmol m?2 tide?1 and ?226 μmol m?2 tide?1 for the tidal creek and salt marsh, respectively). In contrast to nitrate, the fluxes of nitrite, ammonium, and SRP were not significantly different under upwelling and nonupwelling conditions, probably because initial concentrations in the two water types were similar. To determine the extent to which the nitrate uptakes were caused by decreased water temperatures or increased concentrations of nitrate, experiments were conducted in which mesocosms were inundated with water with a range of nitrate concentrations (1.8–25 μmol l?1), at two temperatures representative of summer upwelling (16°C) and nonupwelling conditions (25°C). In both regions, the net fluxes of nitrate were positively correlated with initial concentrations of nitrate in the water column. For any given concentration, the fluxes at 16°C fell within the range of values at 25°C, indicating that the shifts in fluxes caused by upwelling occurred in response to increased concentrations in the water column and not reduced temperatures.  相似文献   

9.
The structure of a single crystal hydrous ringwoodite, Mg1.89Si0.98H0.30O4 synthesized at conditions of 1300?°C and 20?GPa has been analyzed. Crystallographic data for hydrous ringwoodite obtained are; Cubic with Space group: Fd3m (no. 227). a= 8.0693(5)?Å, V=526.41(9)?Å3, Z=8, Dcalc= 3.48?g?cm?3. The results of site occupancy refinement using higher angle reflections showed the existence of a small degree of Mg2+-Si4+ disorder in the structure such as (Mg1.84Si0.05□0.11)(Si0.93Mg0.05□0.02)H0.30O4. The IR and Raman spectra were measured and OH vibration spectra were observed. A broad absorption band was observed in the IR spectrum and the maxima were observed at 3160?cm?1 in the IR and at 3165?cm?1 and 3685?cm?1 in relatively sharp Raman spectra, which suggest that locations between O-O pairs around the octahedral 16c and 16d sites are possible sites for hydrogen.  相似文献   

10.
Analysis of experimental data reported by Lagache (1965, 1976), Evans (1965), Busenberg (1975), Busenberg and Clemency (1976), Holdren and Berner (1979), Siegel and Pfannkuch (1984), and Chou and Wollast (1984) with the aid of irreversible thermodynamics and transition state theory (Aagaard and Helgeson, 1977, 1982) suggests that at temperatures at least up to 650°C, the rate of both congruent and incongruent feldspar hydrolysis in aqueous solutions far from equilibrium at pH ? 10.6 ? (2300/T), where T stands for temperature in kelvins, is a function solely of effective surface area and pH at constant pressure and temperature. At higher pH, the rate is apparently pH-independent up to ~pH 8 at 25°C, where it again becomes pH-dependent at higher pH. Observations of scanning electron micrographs indicate that the cross-sectional area of etch pits on hydrolyzed feldspar grains is of the order of 10?9 to 10?8 cm2 and that the ratio of the effective to total surface area (which may or may not change with reaction progress) ranges from <0.01 to 1, depending on the grain size, dislocation density, and the extent of comminution damage on the surfaces of the grains. Apparent rate constants retrieved from experimental data reported in the literature for feldspar hydrolysis in the lower pH-dependent range extend from ~10?13 to ~10?7 moles cm?2 sec?1 at temperatures from 25° to 200°C, which is consistent with activation enthalpies for albite and adularia of the order of 20 kcal mole?1. In contrast, the apparent rate constants for the pH-independent rate law range from ~10?16 to ~10?11 moles cm?2 sec?1 at temperatures from 25° to 650°C, which requires an activation enthalpy for adularia of ~ 9 kcal mole?1. These observations are consistent with surface control of reaction rates among minerals and aqueous solutions. The rate-limiting step in the pH-dependent case apparently corresponds at the lower end of the pH scale to breakdown of a protonated configuration of atoms on the surface of the reactant feldspar, but at higher pH the rate is limited by decomposition of an activated surface complex corresponding in stoichiometry to hydrous feldspar. In highly alkaline solutions, an activated complex containing hydroxyl ions apparently controls the rate of feldspar hydrolysis. Nevertheless, near equilibrium, regardless of pH the rate is proportional to the chemical affinity of the overall hydrolysis reaction.  相似文献   

11.
Fe-Ti-oxides may reach hundreds ppm in I-type granitoids and close to microgranular mafic enclaves (MME) up to several thousands ppm. Western Carpathian I-type granitoids have magnetic susceptibility above 3?×?10?4 SI units, whereas S-type granites are lower. Associated MMEs reach up to 160?×?10?4 SI. The measurement of magnetic susceptibility in field appears a useful tool for regional mapping of I-type granites and searching enclaves. The increased contents of Fe-oxides around MME within host I-type granitoids are interpreted as result of hybridization with mafic magma. The hybridisation is manifested by occurrence of two Fe-Ti-oxide generations: (1) orthomagmatic titanomagnetite from pre-mixing stage, (2) late-magmatic magnetite of post-mixing stage. The titanomagnetites show composite textures with exsolved ilmenite. The oxybarometry (Sauerzapf et al. 2008; Ghiorso Evans 2009) yields temperatures 700?C750°C at fO2 about NNO, and 650?C700°C below FMQ, respectively. Post-mixing pure magnetites originated from early titanomagnetite, annite and anorthite associated with titanite and apatite. The late oxidation seems to be responsible for high magnetic susceptibility of metaluminous I-type tonalites. Both post- and pre- mixing Fe-Ti oxides are locally converted to hematite.  相似文献   

12.
Oxygen isotopic fractionation in the system quartz-albite-anorthite-water   总被引：1，自引：0，他引：1  
Oxygen isotopic fractionations have been determined between quartz and water, albite and water, and anorthite and water at temperatures from 300 to 825°C, and pressures from 1.5. to 25 kbar. The equilibrium quartz-feldspar fractionation curves can be approximated by the following equations: 1000ln αQ?PI = (0.46 + 0.55β)106T?2 + (0.02 + 0.85β) between 500 and 800°C 1000ln αQ?PI = (0.79 + 0.90β)106T?2 — (0.43 ? 0.30β) between 400 and 500°C where β is the mole-fraction of anorthite in plagioclase.Application of these isotopic thermometer calibrations to literature data on quartz and feldspar gives temperatures for some metamorphic rocks which are concordant with quartz-magnetite temperatures. Plutonic igneous rocks typically have quartz-feldspar fractionations which are substantially larger than the equilibrium values at solidus temperatures, indicating substantial retrograde exchange effects.  相似文献   

13.
 Cordierite precursors were prepared by a sol-gel process using tetraethoxysilane, aluminum sec.-butoxide, and Mg metal flakes as starting materials. The precursors were treated by 15-h heating steps in intervals of 100 °C from 200 to 900 °C; they show a continuous decrease in the analytical water content with increasing preheating temperatures. The presence of H2O and (Si,Al)–OH combination modes in the FTIR powder spectra prove the presence of both H2O molecules and OH groups as structural components, with invariable OH concentrations up to preheating temperatures of 500 °C. The deconvolution of the absorptions in the (H2O,OH)-stretching vibrational region into four bands centred at 3584, 3415, 3216 and 3047 cm−1 reveals non-bridging and bridging H2O molecules and OH groups. The precursor powders remain X-ray amorphous up to preheating temperatures of 800 °C. Above this temperature the precursors crystallize to μ-cordierite; at 1000 °C the structure transforms to α-cordierite. Close similarities exist in the pattern of the 1400–400 cm−1 lattice vibrational region for precursors preheated up to 600 °C. Striking differences are evident at preheating temperatures of 800 °C, where the spectrum of the precursor powder corresponds to that of conventional cordierite glass. Bands centred in the “as-prepared” precursor at 1137 and 1020 cm−1 are assigned to Si–O-stretching vibrations. A weak absorption at 872 cm−1 is assigned to stretching modes of AlO4 tetrahedral units and the same assignment holds for a band at 783 cm−1 which appears in precursors preheated at 600 °C. With increasing temperatures, these bands show a significant shift to higher wavenumbers and the Al–O stretching modes display a strong increase in their intensities. (Si,Al)–O–(Si,Al)-bending modes occur at 710 cm−1 and the band at 572 cm−1 is assigned to stretching vibrations of AlO6 octahedral units. A strong band around 440 cm−1 is essentially attributed to Mg–O-stretching vibrations. The strongly increasing intensity of the 872 and 783 cm−1 bands demonstrates a clear preference of Al for a fourfold-coordinated structural position in the precursors preheated at high temperatures. The observed band shift is a strong indication for increasing tetrahedral network condensation along with changes in the Si–O and Al–O distances to tetrahedra dimensions similar to those occurring in crystalline cordierite. These structural changes are correlated to the dehydration process starting essentially above 500 °C, clearly demonstrating the inhibiting role of H2O molecules and especially of OH groups. Received: 1 March 2002 / Accepted: 26 June 2002  相似文献   

14.
Infrared absorption spectra (400–4000 cm?1) were measured on dehydrated and partially dehydrated powder of the zeolite harmotome Ba2[(AlO2)4(SiO2)12]·12H2O. Whereas the disappearance of the bending mode at ～1640 cm?1 proved the absence of water molecules after dehydration, the O-H stretching mode at 3200 cm?1 showed the presence of hydroxyl groups. The vibrational modes of the framework are only slightly influenced by dehydration.  相似文献   

15.
Structural changes of synthetic opal by heat treatment   总被引：1，自引：0，他引：1  
The structural changes of synthetic opal by heat treatment up to 1,400 °C were investigated using scanning electron microscopy, X-ray diffraction, and Fourier transform infrared and Raman spectroscopies. The results indicate that the dehydration and condensation of silanol in opal are very important factors in the structural evolution of heat-treated synthetic opal. Synthetic opal releases water molecules and silanols by heat treatment up to 400 °C, where the dehydration of silanol may lead to the condensation of a new Si–O–Si network comprising a four-membered ring structure of SiO4 tetrahedra, even at 400 °C. Above 600 °C, water molecules are lost and the opal surface and internal silanol molecules are completely dehydrated by heat effect, and the medium-temperature range structure of opal may begin to thermally reconstruct to six-membered rings of SiO4 tetrahedra. Above 1,000 °C, the opal structure almost approaches that of silica glass with an average structure of six-membered rings. Above 1,200 °C, the opal changes to low-cristobalite; however, minor evidence of low-tridymite stacking was evident after heat treatment at 1,400 °C.  相似文献   

16.
The incorporation of OH defects in quartz as a function of Li content in the bulk system and pressures was investigated. Quartz crystals were grown in water-saturated granitic systems, containing various amounts Li, B and P, supplied as accessory phases such as spodumene, tourmaline or apatite in the starting mixtures. High pressure experiments were performed at temperatures between 900 and 1100 °C, and pressures between 5 and 20 kbar with a piston cylinder apparatus, and the synthesized quartz crystals were analyzed by IR spectroscopy, electron microprobe and LA-ICP-MS spectroscopy. All IR absorption spectra revealed absorption features that can be assigned to AlOH (3313, 3379 and 3431 cm?1) and (4H)Si defects (3585 cm?1), whereas quartz grown in the Li and B systems exhibited two additional bands related, respectively, to LiOH (3483 cm?1) and BOH defects (3596 cm?1). It was further observed that LiOH incorporation increases with higher spodumene content in the starting material and decreases with pressure, until no LiOH defects are observed at pressure higher than 15 kbar. Specifically, the most pronounced reduction of LiOH defects occurs in a rather narrow pressure interval (10–15 kbar) close to the high-quartz/low-quartz transition. However, the link between the transition and the defect incorporation remains unclear. Li total concentrations always exceed the Li-coupled LiOH defects, suggesting the simultaneous presence of dry AlLi defects. Results of this study suggest that LiOH defects are detectable only in quartz crystals grown from middle and upper crustal sections (such as hydrothermal quartz) and not in quartz from deep roots of orogenic granitoids.  相似文献   

17.
Tracer diffusion coefficients of 153Gd and 152Eu in olivine tholeiite have been determined at temperatures between 1150 and 1440°C. The results are identical for both tracers within experimental error. Between 1440 and 1320°C the diffusion coefficients are given by D(Eu, Gd) = 0.058 exp(?40,600/ RT). Between 1320 and 1210°C, the diffusion coefficients are constant at D = (1.4 ± 0.4) × 10?7 cm2s?1 and between 1210 and 1150°C, the D values drop irregularly to 4 × 10?9 cm2s?1. The liquidus temperature (1270°C) lies within the region of constant D. Such anomalous behavior has not been encountered in previous studies of Ca, Sr, Ba and Co diffusion in basalt. To explain the constant D value near the liquidus, we speculate that the structure of the melt changes as a function of temperature in such a way that the normal temperature dependence of the diffusivity is compensated. For example, the rare earth ions may be displaced from their (high temperature) octahedral coordination sites to other sites where they are more readily dissociated and therefore become progressively more mobile. The behavior below 1210°C may be the result of relatively stable complexes or molecules in the melt or of the formation of a REE bearing crystalline phase that has so far escaped detection. Preliminary results for Eu diffusion in obsidian are D (Eu, 800°C) = 5 × 10?13 cm2 s?1 and D (Eu, 950°C) = 1.5 × 10?11 cm2 s?1. These data are consistent with an activation energy of 59 Kcal mole?1. These low diffusivities indicate that the partitioning of REE in crystallizing intermediate and acidic melts may be controlled by diffusion in the melt rather than equilibrium between the crystal surface and the bulk melt.The diffusion data are applied to partial melting in the mantle, in an attempt to explain how LREE enriched tholeiites may be derived from a LREE depleted mantle source. In this model LREE diffuse from garnet bearing regions that have small melt fractions into garnet free regions that have relatively large melt fractions. REE diffusion is so slow that this process is quantitatively significant only in small partially molten bodies (diameter ～1 km or less) or in larger, but strongly flattened bodies. Internal convective motion during diapiric rise would also increase the efficiency of the process.  相似文献   

18.
Diagenetic transformation of clay minerals, zeolites and silica minerals in Cretaceous and Tertiary argillaceous rocks from deeply drilled wells in Japan were studied. Transformations of these minerals during diagenesis were as follows: in clay minerals, montmorillonite → montmorillonite-illite mixed-layer mineral → illite; in zeolites, volcanic glass → clinoptilolite → heulandite and/or analcite → laumontite and/or albite; in silica minerals, amorphous silica → low-cristobalite → low-quartz. Maximum overburden pressures and geothermal temperatures corresponding to these transformations in each well studied were calculated. For clay minerals, a pressure of approximately 900 kg cm?2 and a temperature of about 100°C are necessary for the transformation from montmorillonite to mixed-layer mineral and 920 kg cm?2 and 140°C for mixed-layer mineral to illite. Transformation from kaolinite to other minerals requires much higher pressures and temperatures than from montmorillonite to mixed-layer mineral. For zeolites, 330 kg cm?2 and 60°C are required for the transformation from volcanic glass to clinoptilolite, 860 kg cm?2 and 120°C for clinoptilolite to heulandite and/or analcite, and 930 kg cm?2 and 140°C for heulandite and/or analcite to laumontite and/or albite. For silica minerals, 250 kg cm?2 and 50°C are necessary for the transformation from amorphous silica to low-cristobalite and 660 kg cm?2 and 70°C for low-cristobalite to low-quartz. Based on these diagenetic mineral transformations, seven mineral zones are recognized in argillaceous sediments. On the other hand, from the porosity studies of argillaceous sediments in Japan, the process of diagenesis is classified into the following three stages. The early compaction stage is marked by shallow burial and viscous rocks with more than 30% porosity. The late compaction stage is characterized by intermediate burial and plastic rocks with 30-10% porosities. The transformation stage is marked by deep burial and elastic rocks with less than 10% porosity.  相似文献   

19.
The dehydration rate of hydrous rhyolitic glasses at 475–875 °C was measured by in situ infrared (IR) spectroscopy in order to determine the diffusion coefficient of water in rhyolitic glasses. The IR spectra of glass thin sections were obtained at 90-s intervals during 90 min at high temperatures, and the change in absorbance at 3550 cm–1 corresponding to total water was monitored. The diffusion coefficients obtained from dehydration rates of the rhyolitic glasses are considered to be averaged value over the water-concentration profile in the sample. The averaged apparent diffusion coefficients increase with the initial total water content from 0.20 m2 s–1 for 0.7 wt% to 0.37 m2 s–1 for 2.8 wt% at 700 °C. The apparent activation energy for the diffusion of total water decreases with increasing initial water content from 112 ± 6 kJ mol–1 for 0.7 wt% to 60 ± 17 kJ mol–1 for 4.1 wt%. Assuming a linear relation between the diffusion coefficient of total water and the total water content, the diffusion coefficients at each initial total water content were also determined. The diffusion coefficients of total water at the water contents of 0.7 and 1.9 wt% and at 0.1 MPa were best fitted by ln D=[(12.9 ± 0.8) – (111 500 ± 6400)/RT] and ln D=[(10.6 ± 0.4) – (86 800 ± 2800)/RT], respectively, and are in agreement with previous data (D in m2 s–1, T in K). The present in situ IR dehydration experiment is a rapid and effective method for the determination of water diffusivity at high temperatures.  相似文献   

20.
Creation of pathways for melt to migrate from its source is the necessary first step for transport of magma to the upper crust. To test the role of different dehydration‐melting reactions in the development of permeability during partial melting and deformation in the crust, we experimentally deformed two common crustal rock types. A muscovite‐biotite metapelite and a biotite gneiss were deformed at conditions below, at and above their fluid‐absent solidus. For the metapelite, temperatures ranged between 650 and 800 °C at Pc=700 MPa to investigate the muscovite‐dehydration melting reaction. For the biotite gneiss, temperatures ranged between 850 and 950 °C at Pc=1000 MPa to explore biotite dehydration‐melting under lower crustal conditions. Deformation for both sets of experiments was performed at the same strain rate (ε.) 1.37×10?5 s?1. In the presence of deformation, the positive ΔV and associated high dilational strain of the muscovite dehydration‐melting reaction produces an increase in melt pore pressure with partial melting of the metapelite. In contrast, the biotite dehydration‐melting reaction is not associated with a large dilational strain and during deformation and partial melting of the biotite gneiss melt pore pressure builds more gradually. Due to the different rates in pore pressure increase, melt‐enhanced deformation microstructures reflect the different dehydration melting reactions themselves. Permeability development in the two rocks differs because grain boundaries control melt distribution to a greater extent in the gneiss. Muscovite‐dehydration melting may develop melt pathways at low melt fractions due to a larger volume of melt, in comparison with biotite‐dehydration melting, generated at the solidus. This may be a viable physical mechanism in which rapid melt segregation from a metapelitic source rock can occur. Alternatively, the results from the gneiss experiments suggest continual draining of biotite‐derived magma from the lower crust with melt migration paths controlled by structural anisotropies in the protolith.  相似文献   

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