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1.
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   

2.
High temperature infrared spectra of hydrous microcrystalline quartz   总被引：1，自引：0，他引：1  
A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm?1 at 50?°C toward 3590?cm?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm?1 (3740?cm?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H2O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H2O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.  相似文献   

3.
ABSTRACT

Equilibrium thermodynamic modelling, quartz in garnet (QuiG) Raman geobarometry, and modelling of garnet nucleation at overstepped conditions were applied to three garnet-bearing blueschists from a 1.5 km-long transect across the eclogite-blueschist unit in Sifnos, Greece, in order to evaluate the accuracy of P?T conditions calculated via equilibrium thermodynamics. QuiG barometry uses the Raman shift of quartz inclusions in garnet to estimate the pressure of garnet nucleation and is independent of chemical equilibrium. Garnet nucleation temperatures were estimated by determining the stability field of the palaeo-assemblage inferred from garnet inclusion suites on mineral assemblage diagrams calculated in the MnNCKFMASH system and on temperatures obtained from Zr in rutile thermometry. These conditions were then compared to P?T conditions calculated at the equilibrium garnet isograd, and the method of intersecting isopleths. The P?T conditions calculated with intersecting garnet isopleths over- and underestimated the temperature of nucleation in samples SPH99-1a and SPH99-7, respectively, whereas they significantly underestimated nucleation pressure in SPH99-5. Nucleation of garnet in SPH99-1a at 12 kbar and ~484°C requires overstepping of ~6 kbar and a reaction affinity of 2.2 kJ mol?1 O. SPH99-5 requires overstepping of ~8 kbar with garnet reaction affinities of at least 2.0 kJ mol?1 O at 15 kbar and ~520°C. SPH99-7 requires overstepping of approximately 15 kbar and affinities of about 2.0–2.4 kJ mol?1 O at ~23 kbar and ~530°C. The geotherms calculated from SPH99-7 (~6.7°C km?1) and SPH99-5 (9.8°C km?1) are in accordance with previous studies. The geotherm calculated from SPH99-1a, however, is warmer (11.3°C km?1), and could reflect changes in the rate of subduction or differences in structural position within the down-going slab. The 10 kbar pressure difference between SPH99-7 and SPH99-1a can be explained by thrusting and accretion of thin slices of underplated wedge material facilitated by slab rollback and gravitational collapse.  相似文献   

4.
Recently, the thermal fluid loop has been established and continuosly operated for 7 days at the geothermal in situ laboratory in Groß Schönebeck (North German Basin). During this initial phase of fluid production, the fluid temperature, measured at the surface, continuously increased until a stable value of about 98 °C was established. Fluid physicochemical properties (pH, redox, density, temperature, and pressure) were measured online and in situ with a newly developed fluid monitoring system (FluMo). Additionally, fluid samples have been collected at various temperatures (in 5–10 °C steps) directly at the production well at about 10 bar pressure. From the pressurized sampling tool, the fluid was directly transferred into a heated autoclave, which allowed filtration (0.2 μm) in the absence of oxygen. Physicochemical parameters [pH, redox, electric conductivity, total dissolved solids (TDS)] as well as acid capacity (K S 4.3) of these samples have been measured onsite at atmospheric conditions. Concentrations of anions, total organic carbon, and metals were analyzed later in the laboratory. Both, measurements in collected samples or in situ (FluMo) analysis of most the parameters density, electric conductivity, or TDS indicated relatively constant values over the whole production time (1.17–1.18 g · cm?3, 215–221 mS · cm?1, 241–260 g · L?1, respectively). Good correlation was also found for pH values (pH = 6.6–6.9), whereas the redox values varied between ?1 and 46 mV when determined at 25 °C and decreased strongly when measured in situ with increasing temperature (?110 mV at 90 °C). The elemental composition of collected samples remained also relatively constant for most compounds and was clearly higher as compared with samples collected in 2011. Results of this study demonstrate that realistic, comprehensive, and time-resolved physicochemical data can be obtained by FluMo. These detailed data sets can be crucial to understand the complex geochemical processes in a thermal water loop and eventually to take required measures on time.  相似文献   

5.
Polarized optical absorption spectra of natural olivine, Fa10Fo90, were measured before and after annealing/quenching experiments performed at 650, 800, 1,000 and 1,200°C under controlled oxygen fugacity. It was found that the annealing induces weak but definite changes in the olivine spectra. The intensity of the spin-allowed Z > X-polarized band at 9,560 cm?1 and shoulder at ～8,300 cm?1 attributed to Fe2+(M2), continuously decreases with annealing temperature, whereas a weaker band at ～11,600 cm?1 assigned to electronic spin-allowed transitions of Fe2+(M1), increases. This evidently shows that annealing treatments cause a redistribution of Fe2+ from M2 to M1. The fractionation increases with increasing temperature. This observation is in good correspondence with many diffraction structural studies of natural and synthetic olivines, as well as with recent Raman and Mössbauer investigations by Kolesov and Geiger (Mitt Österr Mineral Ges 149:48, 2004) and Morozov et al. (Eur J Mineral 17:495–500, 2005) evidencing a weak tendency of Fe to order into the M1 site with increasing temperature. However, this deduction is incompatible with the results of the in situ neutron power diffraction study of synthetic FeMgSiO4 by Redfern et al. (Phys Chem Minerals 27:630–637, 2000). Polarization properties of the UV absorption edge, attributed to ligand-to-metal charge-transfer transitions in Fe3+, changes from Y > X ? Z in natural samples to a weak Y ≥ X ≥ Z-pleochroism in annealed ones. This may be due to redistribution of a small content of Fe3+ among M1 and M2 structural sites.  相似文献   

6.
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   

7.
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   

8.
Aquifer thermal energy storage in urban and industrial areas can lead to an increase in subsurface temperature to 70 °C and more. Besides its impacts on mineral and sorption equilibria and chemical reaction kinetics in an aquifer, temperature sensitively influences microbial activity and thus redox processes, such as sulphate reduction. Microorganism species can only operate within limited temperature ranges and their adaptability to temperature is a crucial point for the assessment of the environmental consequences of subsurface heat storage. Column experiments with aquifer sediment and tap water at 10, 25, 40, and 70 °C showed that under the constant addition of acetate sulphate reduction could be initiated after 26–63 pore volumes exchanged at all temperatures. Fastest initiation of sulphate reduction with the highest reduction rates was found at 40 °C. Maximum rate constants during experimental run-time were 0.56 h?1 at 40 °C and 0.33, 0.36, and 0.25 h?1 at 10 and, 25, and 70 °C, respectively. Hence, microbial activity was enhanced by a temperature increase to 40 °C but was significantly lowered at 70 °C. At 25 °C methane was found in solution, indicating the presence of fermenting organisms; at 10, 40, and 70 °C no methane production was observed. It could be shown that redox processes in an aquifer generally can adapt to temperatures significantly higher than in situ temperature and that the efficiency of the reduction process can be enhanced by temperature increase to a certain limit. Enhancement of sulphate reduction in an aquifer due to temperature increase could also allow enhanced degradation of organic ground water contaminants such as BTEX, where sulphate is an important electron acceptor.  相似文献   

9.
Polarized Raman spectra were collected for single crystal buergerite (NaFe3Al6(BO3)3Si6O18(O0.92(OH)0.08)3F) from room temperature to near 1,375°C. Vibrational assignments to features in the room temperature spectra were determined by lattice dynamics calculations, where internal BO3 motions dominate modes near 1,300 cm−1, internal SiO4 displacements dominate modes between 900 and 1,200 cm−1, while less localized displacements within the isolated Si6O18 ring mix with motions within Na, Fe, Al, F, and BO3 environments for fundamental modes below 780 cm−1. At elevated temperatures, most buergerite Raman features broaden and shift to lower frequencies up to 900°C. Above this temperature, the lattice mode peaks evolve into broad bands, while OH stretch modes near 3,550 cm−1 disappear. According to Raman spectroscopy, X-ray diffraction, differential thermal analysis, and scanning electron microscopy, buergerite undergoes a complex transition that starts near 700°C and extends over a 310°C interval, where initially, Al and Fe probably become disordered within the Y- and Z-sites, and most F and all OH are later liberated. A reversible crystal-to-amorphous transition is seen by Raman for buergerite fragments heated as high as 930°C. Buergerite becomes permanently altered when heated to temperatures greater than 930°C; after cooling to room temperature, these altered fragments are comprised of mullite and Fe-oxide crystals suspended in an amorphous borosilicate matrix.  相似文献   

10.
 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   

11.
Deformation experiments on olivine aggregates were performed under hydrous conditions using a deformation-DIA apparatus combined with synchrotron in situ X-ray observations at pressures of 1.5–9.8 GPa, temperatures of 1223–1800 K, and strain rates ranging from 0.8 × 10?5 to 7.5 × 10?5 s?1. The pressure and strain rate dependencies of the plasticity of hydrous olivine may be described by an activation volume of 17 ± 6 cm3 mol?1 and a stress exponent of 3.2 ± 0.6 at temperatures of 1323–1423 K. A comparison between previous data sets and our results at a normalized temperature and a strain rate showed that the creep strength of hydrous olivine deformed at 1323–1423 K is much weaker than that for the dislocation creep of water-saturated olivine and is similar to that for diffusional creep and dislocation-accommodated grain boundary sliding, while dislocation microstructures showing the [001] slip or the [001](100) slip system were developed. At temperatures of 1633–1800 K, a much stronger pressure effect on creep strength was observed for olivine with an activation volume of 27 ± 7 cm3 mol?1 assuming a stress exponent of 3.5, water fugacity exponent of 1.2, and activation energy of 520 kJ mol?1 (i.e., power-law dislocation creep of hydrous olivine). Because of the weak pressure dependence of the rheology of hydrous olivine at lower temperatures, water weakening of olivine could be effective in the deeper and colder part of Earth’s upper mantle.  相似文献   

12.
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13.
Changes in water chemistry along the High Arctic fluvial–lacustrine system located in Wedel Jarlsberg Land in the SW Spitsbergen (Svalbard) were investigated during the summer season of 2010 and 2011. The newly formed river–lake system consists of three lakes connected with the Brattegg River. The first bathymetric measurements of these lakes were made by the authors in 2010. The Brattegg River catchment represents a partly glaciered Arctic water system. The studied lakes are characterized by low mineralization and temperature of water. The value of the electrolytic conductivity (EC) ranges from 30.2 to 50.5 μS cm?1 and the temperature of surface water from 1.5 to 7.8 °C. The temperature increase takes place downstream starting from Upper Lake to the outflow from Myrktjørna Lake. The waters of lakes have higher temperatures than the stream. The predominant ions are HCO3 ? (up to 16.5 mg L?1), Cl? (6.66–8.53 mg L?1), Ca2+ (2.40–4.45 mg L?1) and Na+ (2.65–3.36 mg L?1). The highest values of ammonium and DOC found in the lowest Myrktjørna Lake seem to be related to the presence of aquatic organisms and also birds. From the group of 10 analyzed microelements, increased concentrations of aluminum, up to almost 500 μg L?1, are present in the lakes’ water. Water isotopic composition ranges for δ18O and δ2H, from ?10.6 to ?10.9‰ and from ?70.8 to ?72.3‰, respectively. The vertical zonality of lake waters is manifested in a decrease in the temperature and increase in EC and chemical elements concentrations.  相似文献   

14.
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   

15.
Cylinders of synthetic periclase single crystals were annealed at 0.15–0.5 GPa and 900–1200 °C under water-saturated conditions for 45 min to 72 h. Infrared spectra measured on the quenched products show bands at 3,297 and 3,312 cm?1 indicating V OH ? centers (OH-defect stretching vibrations in a half-compensated cation vacancy) in the MgO structure as a result of proton diffusion into the crystal. For completely equilibrated specimens, the OH-defect concentration, expressed as H2O equivalent, was calculated to 3.5 wt ppm H2O at 1,200 °C and 0.5 GPa based on the calibration method of Libowitzky and Rossmann (Am Min 82:1111–1115, 1997). This value was confirmed via Raman spectroscopy, which shows OH-defect-related bands at identical wavenumbers and yields an H2O equivalent concentration of about 9 wt ppm using the quantification scheme of Thomas et al. (Am Min 93:1550–1557, 2008), revised by Mrosko et al. (Am Mineral 96:1748–1759, 2011). Results of both independent methods give an overall OH-defect concentration range of 3.5–9 (+4.5/?2.6) ppm H2O. Proton diffusion follows an Arrhenius law with an activation energy E a = 280 ± 64 kJ mol?1 and the logarithm of the pre-exponential factor logDo (m2 s?1) = ?2.4 ± 1.9. IR spectra taken close to the rims of MgO crystals that were exposed to water-saturated conditions at 1,200 °C and 0.5 GPa for 24 h show an additional band at 3,697 cm?1, which is related to brucite precipitates. This may be explained by diffusion of molecular water into the periclase, and its reaction with the host crystal during quenching. Diffusion of molecular water may be described by logDH2O (m2 s?1) = ?14.1 ± 0.4 (2σ) at 1,200 °C and 0.5 GPa, which is ~ 2 orders of magnitude slower than proton diffusion at identical P-T conditions.  相似文献   

16.
《International Geology Review》2012,54(10):1226-1245
Monzogabbro stocks including felsic enclaves (monzosyenite) around the Bafra (Samsun) area at the western edge of the Eastern Pontides cut Eocene-aged volcanic and sedimentary units. The monzogabbros contain plagioclase, alkali feldspar, clinopyroxene, olivine, hornblende, biotite, apatite, and iron-titanium oxides, whereas the felsic enclaves contain alkali feldspar, plagioclase, hornblende, biotite, clinopyroxene, and iron-titanium oxides. Mineral chemistry data suggest that magmas experienced hydrous and anhydrous crystallization in deep and shallow crustal magma chambers. Several thermobarometers were used to estimate temperatures of crystallization and emplacement for the mafic and felsic magmas. Clinopyroxene thermobarometry yielded 1100–1232 C and 5.9–8.1 kbar for monzogabbros, and 931–1109 C and 1.8–6.9 kbar for felsic enclaves. Hornblende thermobarometry and oxygen fugacity estimates reveal 739–971°C, 7.0–9.2 kbar and 10?9.71 for monzogabbros and 681–928°C, 3.0–6.1 kbar and 10?11.34 for felsic enclaves. Biotite thermobarometry shows elevated oxygen fugacity varying from 10?18.9–10?11.07 at 632–904°C and 1.29–1.89 kbar for monzogabbros, to 10?15.99 –10?11.82 at 719–873°C and 1.41–1.77 kbar for felsic enclaves. The estimated zircon and apatite saturation temperatures are 504–590°C and 693–730°C for monzogabbros and 765–775°C and 641–690°C for felsic enclaves, respectively. These data imply that several phases in the gabbroic and syenitic magmas did not necessarily crystallize simultaneously and further indicate that the mineral compositions may register intervals of disequilibrium crystallization. Besides, thermobarometry contrasts between monzogabbro and felsic enclave may be partly a consequence of extended interactions between the mafic and felsic magmas by mixing/mingling and diffusion. Additionally, the hot felsic magma was close to liquidus conditions (crystallinity < 30%) when injected into cooler mafic magma (crystallinity > 50%), and thus, the monzogabbro stocks reflect hybrid products from the mingling and incomplete mixing of these two magmas.  相似文献   

17.
Cobalt and magnesium interdiffusion coefficients in synthetic crystals of olivine have been determined by a method of couple annealing. These coefficients increase with temperature and Co concentration. The coefficients in forsterite along the c crystallographic axis range from 1.13 × 10?12 to 6.85 × 10?11 cm2sec?1 at temperatures ranging from 1150 to 1400°C. The calculated activation energies for Co-Mg interdiffusion in forsterite are 526 kJmol?1 above approximately 1300°C and 196 kJmol?1 at lower temperatures. These results indicate that the Co-Mg mobility in olivine is relatively low compared to published results for Fe-Mg interdiffusion.  相似文献   

18.
The validity of the thermodynamic cBΩ model is tested in terms of the experimentally determined diffusion coefficients of He in a natural Fe-bearing olivine (Fo90) and a synthetic end-member forsterite (Mg2SiO4) over a broad temperature range (250–950 °C), as reported recently by Cherniak and Watson (Geochem Cosmochim Acta 84:269–279, 2012). The calculated activation enthalpies for each of the three crystallographic axes were found to be (134 ± 5), (137 ± 13) and (158 ± 4) kJ mol?1 for the [100], [010] and [001] directions in forsterite, and (141 ± 9) kJ mol?1 for the [010] direction in olivine, exhibiting a deviation of <1 % with the corresponding reported experimental values. Additional point defect parameters such as activation volume, activation entropy and activation Gibbs free energy were calculated as a function of temperature. The estimated activation volumes (3.2–3.9 ± 0.3 cm3 mol?1) of He diffusion in olivine are comparable with other reported results for hydrogen and tracer diffusion of Mg cations in olivine. The pressure dependence of He diffusion coefficients was also determined, based on single experimental diffusion measurements at 2.6 and 2.7 GPa along the [001] direction in forsterite at 400 and 650 °C.  相似文献   

19.
The relationships between egg production (spawning behavior), larval growth and survival, and environmental conditions that larvae encounter were investigated in the Patuxent River tributary of Chesapeake Bay in 1991. Striped, bass (Morone saxatilis) eggs and larvae occurred predominantly above the salt front where conductivity was ≤800 μmhos cm?1. There were three prominent peaks in egg production, each coinciding with increasing temperatures. Estimated growth rates of 6-d, otolith-aged cohorts, which ranged from 0.15 mm d?1 to 0.22 mm d?1 (mean=0.17 mm d?1), were not demonstrated to differ significantly from each other. Observed zooplankton densities and temperature did not significantly affect growth rates. Stage-specific cumulative mortalities of combined cohorts were calculated for eggs (Zstage=0.20=18.1%), yolk-sac larvae (Zstage=5.80=99.7%), and first-feeding larvae (Zstage=2.95=94.8%). The very high mortality of yolk-sac larvae suggests that dynamic during this stage may have had a major impact on subsquent recruitment. Cohort-specific mortality rates of larvae were variable, ranging from Z=0.045 d?1 to 0.719 d?1, and were strongly temperature-dependent. Cohorts that experiented average temperature <15°C or >20°C during the first 25 d after hatching had significantly higher mortality rates than those which experienced intermediate temperatures. Estimated hatch-date frequencies of larvae ≥8 mm SL indicated goo, very good, and very low potential recruitments for cohorst spawned during early-season (April 2–11), mid-season (April 12–24) and late-season (April 25–May 5), respectively. Because seasonal temperature trends and fluctuations are unpredictable, striped bass females cannot select a spawning time that guarantees their offspring will be exposed to optimum temperatures. Consequently, selection may have occured for spawning over a broad range of temperatures and dates, a behavior insuring that some larval cohorts will encounter favorable temperatures.  相似文献   

20.
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   

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