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1.
The orientation dependence of the luminescence of a well-characterized plagioclase crystal at room temperature and 40 K is reported. A beam of H + ions was used to provide the excitation. Ion beam luminescence provides emissions effectively from the bulk of the material, and therefore minimizes the contribution to the luminescence from atypical regions. The intensity of the luminescence is strongly orientation-dependent. The intensity and photon energy, particularly of the red/infrared and yellow emission bands, vary significantly. We interpreted this as resulting from Fe 3+ and Mn 2+ activator ions, respectively, on crystallographic sites with low point symmetry. An emission at 860 nm was also significantly orientation-dependent. The blue luminescence showed the least variability. At room temperature, a 350 nm near-UV emission was noted, whereas at 40 K, emissions were at 240, 260, 300 and 340 nm. UV emissions may result from Na + diffusion along interfaces within the plagioclase, notably albite-law (010) twins. This variability has significant consequences for the use of single-crystal quantitative luminescence techniques. We have also studied the dependence of the peak intensities and profiles during prolonged ion beam bombardment with heavier (He +) ions. Broadening of the red-infrared emission is interpreted as reflecting growing amorphization of the sample.  相似文献   

2.
We have determined Fe–Mg diffusion coefficients in olivines from different sources (Nanga Parbat, Pakistan and San Carlos, Arizona, USA) at atmospheric pressure as a function of composition, oxygen fugacity (10−5–10−12 Pa) and temperature (700–1200°C) using thin films produced by pulsed laser deposition and RBS to analyze the concentration profiles. We have characterized the nano-scale structure and composition of the thin films annealed at various conditions and shown that the nature of the film (e.g. crystallinity, wetting behavior) depends strongly on the annealing conditions. If these variations are not taken into account in the form of boundary conditions for modeling the diffusion profiles, artifacts would result in the diffusion data. The diffusion coefficients obtained from 75 experiments reveal that (i) between fO2 of 10−5 and 10−10 Pa, diffusion along all three principal crystallographic directions in olivine, [100], [010] and [001], are described by a constant activation energy of ∼200 kJ/mol, precluding any temperature dependence of diffusion anisotropy and change of mechanism of diffusion at temperatures between 950 and 1200°C, (ii) diffusion coefficients increase with oxygen fugacity at fO2 > 10−10 Pa, with an fO2 exponent that lies between 1/4 and 1/7, and (iii) at fO2 below 10−10 Pa, and consequently at temperatures below ∼900°C, diffusion becomes weakly dependent/independent of fO2, indicating a change of diffusion mechanism. Activation energy of diffusion at these conditions is slightly higher, ∼220 kJ/mol. The data, including the change of mechanism, are analyzed in terms of point defect chemistry in Part II of this work to derive an equation that allows calculation of diffusivities in olivine over its entire field of stability. Availability of directly measured data at temperatures down to 700°C imply that for the first time diffusion coefficients can be interpolated, rather than extrapolated, for modeling most natural systems.  相似文献   

3.
 Using a combination of dielectric spectroscopy and atomistic computer simulation techniques, the dynamical behaviour of the loosely bound (Na+ and K+) channel ions in nepheline has been investigated. The low-frequency dielectric properties of a natural Bancroft nepheline have been studied from room temperature to 1100 K. At each temperature, the dielectric constant, conductivity and dielectric loss were determined over a range of frequencies from 100 Hz to 10 MHz. At high temperatures a distinct Debye-type relaxation in the dielectric loss spectrum was observed; the activation energy for this process was determined to be 1.38 ± 0.02 eV. Atomistic simulation techniques were used to elucidate the mechanism and energetics of cation migration. A mechanism involving the hopping of Na+ ions between oval sites and partially occupied hexagonal (K+) sites, via a bottleneck consisting of a distorted sixfold ring of (Al,Si)O4 tetrahedra, was found to give a calculated energy barrier in very good agreement with the experimentally determined activation energy. These results confirm the nature of the process responsible for the observed dielectric behaviour. Overall, this study demonstrates the intrinsic, microscopic control of cation diffusion processes in rock-forming minerals. Identifying specific energy barriers and preferred diffusion pathways is fundamental to the prediction of diffusion energetics. Received: 8 May 2000 / Accepted: 21 July 2000  相似文献   

4.
The thermally induced reductive decomposition of a natural near end-member almandine [VIII(Fe2.85Mg0.11Ca0.05Mn0.02)VI(Al1.99)IV(Si2.99)O12] and possible hydrogen diffusion into its structure have been carried out at temperatures up to 1,200°C, monitored by simultaneous thermogravimetric analysis and differential scanning calorimetry (DSC), infrared and 57Fe Mössbauer spectroscopy and X-ray powder diffraction. Below 1,000°C, evidence for hydrogen diffusion into almandine structure was not observed. At temperatures above 1,000°C, reductive decomposition sets in, as displayed by a sharp endothermic peak at 1,055°C on the DSC curve accompanied by a total mass loss of 3.51%. We observe the following decomposition mechanism: almandine + hydrogen → α-Fe + cristobalite + hercynite + water. At higher temperatures, fayalite and sekaninaite are formed by consecutive reaction of α-Fe with cristobalite and water, and cristobalite with hercynite, respectively. The metallic α-Fe phase forms spherical and isolated particles (~1 μm).  相似文献   

5.
The kinetics of calcite dissolution in aqueous KCl-solutions far from equilibrium, between 1 and 62°C in the pH-range 2.7 to 8.4 have been investigated using a rotating disc apparatus. At neutral and alkaline pH in the mixed kinetic regime the empirical apparent activation energy (EAAE) for the surface chemical reaction rate constant is 54 ± 4 kJ mole?1 for Carrara marble and 46 ± 4 kJ mole?1 for Iceland spar. Under similar conditions the EAAE of the transport rate constant increases with decreasing temperature, but has a mean value of 27 ± 2 kJ mole?1. The corresponding diffusion coefficient has a mean EAAE of 37 ± 3 kJ mole?1 and this high EAAE is consistent with transport dependence on product diffusion in this H+-independent regime.In contrast, in acid solutions, where the rate approaches end-member transport control, the EAAE of the diffusion coefficient is 16 kJ mole?1, also decreasing with increasing temperature. This is compatible with H+-diffusion to the surface being rate-controlling.In inhibitor-free natural systems, calcite dissolution kinetics far from equilibrium can be described in terms of three regimes: an H+-dependent regime (pH < 4 at 25°C), a transition regime (4 < pH < 5.5 at 25°C) and an H+-independent regime (pH > 5.5 at 25°C). At lower temperatures these boundaries move to higher pH values. The presence of inhibitors in natural systems may enhance surface controlled kinetics.  相似文献   

6.
Measurements on 170 carbonate rocks show decreasing δO18 of similar magnitude for both limestones and dolomites over a time span of ~ 2800 m.y. The Proterozoic dolomites are on average heavier by ~5%. in δO18 than their coeval limestones. The data may indicate displacement in δC13 of about 3%. at approximately 570 m.y. ago, with Precambrian carbonates being heavier in δC13 at a given δO18 level than their Phanerozoic counterparts. The compilation of the previously published data is consistent with the above described features.  相似文献   

7.
As a part of the safety assessment of the geological disposal of high-level radioactive waste, the effects of dry density and exchangeable cations on the diffusion process of Na+ ions in compacted bentonite were studied from the viewpoint of the activation energy for diffusion. The apparent self-diffusion coefficients of Na+ ions in compacted Na-montmorillonite and in a Na- and Ca-montmorillonite mixture were determined by one-dimensional, non-steady diffusion experiments at different temperatures and dry densities. A unique change in activation energy as a function of dry density was found for the Na+ ions in compacted Na-montmorillonite. The activation energy suddenly decreased from 18.1 to 14.1 kJ mol− 1 as the dry density increased from 0.9 to 1.0 Mg m− 3, whereas it increased to 24.7 kJ mol− 1 as the dry density increased to 1.8 Mg m− 3. Examination of the effect of exchangeable cations on the activation energies determined that the activation energies were almost constant, approximately 25 kJ mol− 1, for the montmorillonite specimens at a dry density of 1.8 Mg m− 3. However, three different activation energy values were obtained at a dry density of 1.0 Mg m− 3. These findings cannot be explained by the conventional diffusion model (the pore water diffusion model), which suggests that the predominant diffusion process alternates among pore water diffusion, interlayer diffusion, and external surface diffusion.  相似文献   

8.
《Atmósfera》2014,27(3):227-237
The O+ ion density measured by the SROSS-C2 satellite during solar minima (year 1995, F10.7 = 77) and maxima (year 2000, F10.7 = 181) has been analyzed for studying diurnal, seasonal, latitudinal and geomagnetic variations. The study region covers an area encompassed between 5-3 5° N latitude and 65-95° E longitude over India at a ~500 km altitude (F2 region). The year 2000 shows significant enhancement in the annual average of O+ ion density and attainment of post sunset secondary enhancement compared to 1995. Attributed to photoionization, daytime shows a maximum ionization compared to nighttime. However, attainment of post sunset secondary maxima is attributed to the strong pre-reversal enhancement in the vertical E x B drift. The effect of geomagnetic activity Kp through the E x B drift dynamic movement on O+ ion density distribution studies indicates periodicities of seven and nine days in 1995 and 2000, respectively, and polynomial dependency of the O+ ion density on geomagnetic activity Kp. Further on, stratification of the O+ ion density according to latitude (5-35° N) indicates high density in mid-latitudes (12-24° N) compared to high and low latitudes, except in the winter of 1995, which shows a distinct trend (i.e., density decreases with increasing latitude).  相似文献   

9.
Experiments have been carried out to determine the temperature, oxygen fugacity (fO2) and compositional dependence of the tracer diffusion coefficient (D) of calcium in olivine. These data constrain the diffusion coefficient over the temperature range 900 to 1500°C for the three principal crystallographic axes. Well constrained linear relationships between the reciprocal of the absolute temperature and log(D) exist at any given oxygen fugacity. There is a strong dependence of the diffusion coefficient on oxygen fugacity with D ∝ fO2(1/3). This makes a knowledge of the T-fO2 path followed by geological samples a prerequisite for modelling Ca diffusion in olivine. The best fitting preexponential factor (Do) and activation energy (E) to the Arrhenius equation log (D) = log [Do exp(−E/RT)] + 0.31Δ log fO2 for Ca diffusion in olivine at a given oxygen fugacity (fO2*) are given by:diffusion along [100]: log [Do (m2/s)] = −10.78 ± 0.43; E = 193 ± 11 kJ/moldiffusion along [010]: log [Do (m2/s)] = −10.46 ± 0.37; E = 201 ± 10 kJ/moldiffusion along [001]: log [Do (m2/s)] = −10.02 ± 0.29; E = 207 ± 8 kJ/molwhere Δ log fO2 = log[fO2*] − log[10−12] with fO2* in units of bars. There is no measurable compositional dependence of the diffusion coefficient between Fo83 and Fo92. Diffusion in Fo100 has a much higher activation energy than in Fe-bearing olivine and has a weaker fO2 dependence.  相似文献   

10.
Any oxide and silicate mineral which is nominally anhydrous but crystallized in the presence of H2O incorporates traces of H2O in solid solution. In the case of MgO it can be shown that OH? pairs convert into H2+O 2 2? . If the H2 molecules are lost, the O 2 2? remain in the lattice as excess oxygen stabilized by excess cation vacancies. When the O 2 2? anions decay either thermally or by decompression unbound O? states (positive holes) are generated which lead to surface charges and subsurface space charge layers. Calculated space charge profiles are presented. O? concentrations as small as 10–20 ppm suffice to create electric surface fields of the order of 4·107 V·m?1. The diffusion mechanism which derives from these premises incorporates novel features: the cation diffusion is coupled to the counterdiffusion of unbound and vacancy-bound O? states. The cation diffusion is predicted to be very fast because first, it is field-enhanced (electrochemically driven) and second, it is not rate-limited by the intrinsic cation vacancy concentration nor by the counter-diffusion of other cations. The model may apply to cases of inverse zoning and diffusion rim formation in minerals under certain P-T conditions.  相似文献   

11.
Mead axisymmetric distortions in the geomagnetic field and uniform electrostatic field parallel to geomagnetic field have been assumed to derive an expression for the inhomogeneity parameter, αd. Consequent change in the pitch angle diffusion of charged particles has been obtained. Using these parameters, the variations in the precipitating electron influx with varying stand-off distances and parallel electrostatic fields have been computed.  相似文献   

12.
The weathering rates and mechanisms of three types of glassy rocks were investigated experimentally at 25 °C, pH 1.0 to 6.2, and reaction times as much as to 3 months. Changes in major element chemistry were monitored concurrently as a function of time in the aqueous solution and within the near surface region of the glass. Leach profiles, obtained by a HF leaching technique, displayed near-surface zones depleted in major cations. These zones increased in depth with increasing time and decreasing pH of reactions. Release rates into the aqueous solution were parabolic for Na and K and linear for Si and Al. A coupled weathering model, involving surface dissolution with concurrent diffusion of Na, K, and Al, produced a mass balance between the aqueous and glass phases. Steady state conditions are reached at pH 1.0 after approximately 3 weeks of reaction. Steady-state is not reached even after 3 months at pH 6.2.An interdiffusion model describes observed changes in Na diffusion profiles for perlite at pH 1.0. The calculated Na self-diffusion coefficient of 5 × 10?19 cm2·s?1 at 25°C approximates coefficients extrapolated from previously reported high temperature data for obsidian. The self-diffusion coefficient for H3O+, 1.2 × 10?20 cm2·s?1, is similar to measured rates of water diffusion during hydration of obsidian to form perlite.  相似文献   

13.
Ar40 diffusion in a natural, non-perthitic orthoclase has been studied isothermal heating experiments between 500° and 800°C under both vacuum and hydrothermal (2 kbar) conditions. The sample is a one-phase K-feldspar without detectable chemical of structural inhomogeneities as verified by heating experiments, chemical and microprobe analyses, and cell refinements. The orthoclase does not disorder detectably and is stable for the duration of the heating interval. Diffusion coefficients were calculated using an isotropic model for spherical grains. Agreement of diffusion coefficients obtained on grain-sizes which differed by a factor of four indicate that the effective dimension for Ar40 diffusion is the actual particle size. A series of experiments at 700°C show that Ar40 loss may be described by the ideal spherical model and that the diffusion coefficient does not change with time. The Arrhenius relation is obeyed with a single activation energy and the diffusion coefficients are described by: D = (0·00982) exp — (43800/RT). Agreement of experiments conducted under vacuum and hydrothermally (up to 2 kbar) indicate that pressure and H2O do not significantly affect Ar40 loss. Relatively small amounts of alkali exchange between the feldspar and hydrothermal salt solutions do not affect the loss behavior.The simple behavior obtained for this orthoclase is attributed of the use of a simple technique within the region of sample stability and to the homogeneous nature of the feldspar. Effects due to sample instability and to the use of perthites are discussed. The new data are compared to those for homogeneous feldspars showing that the orthoclase gives diffusion coefficients which are as low as those sanidine. It is suggested that perthitization of feldspars in nature may reduce the effective grain size for diffusion and thereby allow diffusional loss of Ar40 at relatively low temperatures.  相似文献   

14.
Marine organisms must possess strategies enabling them to initiate calcite precipitation despite the unfavorable conditions for inorganic precipitation in surface seawater. These strategies are poorly understood. Here we compare two potential strategies of marine calcifyers to manipulate seawater chemistry in order to initiate calcite precipitation: Removal of Mg2+ and H+ ions from seawater solutions. An experimental setup was used to monitor the onset of inorganic precipitation on seed crystals as a function of the Mg2+ concentration and pH in artificial seawater. We focused on precipitation rates typical for biogenic calcification in planktonic foraminifera (∼10−3 mol m−2 h−1) and time scales typical for the initiation of calcification in these organisms (minutes to hours). We find that the carbonate ion concentration has to increase by a factor of ∼13 when [Mg2+] increases from 0 to 53 mmol kg−1 in order to maintain a typical biogenic precipitation rate. Model calculations for the energy requirement for various scenarios of Mg2+ and H+ removal including Ca2+ exchange and CO2 diffusion are presented. We conclude that the more cost-effective strategy to initiate calcite precipitation in foraminifera is H+ removal, rather than Mg2+ removal.  相似文献   

15.
The distribution and dynamics of water molecules and monovalent cations (Li+, Na+, K+, Cs+, and H3O+) on muscovite surfaces were investigated by molecular dynamics (MD) simulations. The direct comparison of calculated X-ray reflectivity profiles and electron density profiles with experiments revealed the precise structure at the aqueous monovalent electrolyte solutions/muscovite interface. To explain the experimentally observed electron density profiles for the CsCl solution-muscovite interface, the co-adsorption of Cs+ and Cl− ion pairs would be necessary. Two types of inner-sphere complexes and one type of outer-sphere complex were observed for hydrated Li+ ions near the muscovite surface. For Na+, K+, Cs+, and H3O+ ions, the inner-sphere complexes were stable on the muscovite surface. The density oscillation of water molecules was observed to approximately 1.5 nm from the muscovite surface. The number of peaks and the locations for the density of water oxygen atoms were almost similar among the water molecules coordinated to Li+, Na+, K+, and H3O+ ions adsorbed on the muscovite surfaces. The water molecules around Cs+ ions that were adsorbed to muscovite surfaces seemed to avoid coordinating with Cs+ ions on the surface, and the density of water oxygen near the muscovite surface decreased relative to that in a bulk state. There was no significant difference in self-diffusion, viscosity, retention time, and reorientation time of water molecules among different cations adsorbed to muscovite surfaces. These translational and rotational motions of water molecules located at less than 1 nm from the muscovite surfaces were slower than those in a bulk state. A significant difference was observed for the exchange times of water molecules around monovalent cations. The exchange time of water molecules was long around Li+ ions and decreased with an increase in the ionic radius.  相似文献   

16.
Ions and water molecules mobilities were studied by the 7Li, 23Na, 1H nuclear magnetic resonance in the framework aluminosilicate mineral analcime and in its cation-exchanged (lithium) form. It has been found that cation exchange as well as dehydration alter radically dynamics of particles interposed in channels of the zeolite framework. The highest mobility of alkali cations with the diffusion activation energy of 0.52 eV was detected in hydrated Li-analcime. The ion diffusion increase with temperature is accompanied by an increase in the dynamic orientational disordering of water sublattice. The energy of formation of structural defects responsible for ion diffusion and water disordering was deduced to be 0.2 eV. As a possible defect, the occupation of water positions by cations is discussed (model of bridging-type ion diffusion).  相似文献   

17.
The relationship between the redox ratio Fe+2/(Fe+2+Fe+3) and the K2O/(K2O + Al2O3) ratio (K2O*) were experimentally investigated in silicate melts with 78 mol% SiO2 in the system SiO2-Al2O3-K2O-FeO-Fe2O3, in air at 1,400° C. Quenched glass compositions were analyzed by electron microprobe and wet chemical microtitration techniques. Minimum values of the redox ratio were obtained at K2O*0.5. The redox ratio in peralkaline melts (K2O*>0.5) increases slightly with K2O* whereas this ratio increases dramatically in peraluminous melts (K2O*<0.5) as K2O is replaced by Al2O3. These data indicate that all Fe+3 (and Al+3) occur as tetrahedral species charge balanced with K+ in peralkaline melts. In peraluminous melts, Fe+3 (and Al+3) probably occur as both tetrahedral species using Fe+2 as a charge-balancing cation and as network-modifying cations associated with non-bridging oxygen.  相似文献   

18.
The thermal decomposition of ammonium-exchanged natural analcime is characterized by gas chromatography, IR spectroscopy and X-ray diffraction. The de-ammoniation and dehydroxylation proceed in parallel throughout the decomposition, which evidences the instability of the protonated analcime framework. The mechanism of degassing of NH4-analcime changes throughout its decomposition. At the initial step, the mechanism of de-ammoniation consists in thermal dissociation of NH4+ molecule onto NH3 and proton (framework OH group) and diffusion of NH3 out of the structure. Subsequent decomposition and removal of the OH groups lead to a progressive loss of crystallinity. At this step, an apparent activation energy for NH3 desorption is estimated to be 145(±13) kJ mol–1. This value is within the upper limit of the activation energy characteristic for the NH3 desorption from proton centres in large-pore zeolites. At the final step, the adsorption of NH3 and protons onto the defect centres in the amorphosed aluminosilicate framework results in a significant increase of an apparent activation energy for the de-ammoniation and dehydroxylation up to 270(±20) kJ mol–1.  相似文献   

19.
Diffusion experiments with HTO, 36Cl−, Br−, I−, 22Na+, 85Sr2+ and 134Cs+ at trace concentrations in a single sample of Opalinus Clay are modeled with PHREEQC’s multicomponent diffusion module. The model is used first in a classical approach to derive accessible porosities, geometrical factors (the ratio of pore tortuosity and constrictivity) and sorption behavior of the individual tracers assuming that the clay is homogeneous. The accessible porosity for neutral species and cations is obtained from HTO, the anion exclusion volume from 36Cl− and Br−, and the cation exchange capacity from 22Na+. The homogeneous model works well for tritium, the anions and 22Na+. However, the 85Sr2+ and 134Cs+ experiments show an early arrival of the tracer and a front-form that suggest a dual porosity structure. A model with 10% dead-end pores, containing 19% of the total exchange capacity, can satisfactorily calculate all the experimental data. The Cs+ diffusion model builds on a 3-site exchange model, constructed from batch sorption data. The excellent agreement of modeled and measured data contradicts earlier reports that the exchange capacity for Cs+ would be smaller in diffusion than in batch experiments.The geometrical factors for the anions are 1.5 times larger than for HTO, and for the cations 2-4 times smaller than for HTO. The different behavior is explained by a tripartite division of the porespace in free porewater, diffuse double layer (DDL) water, and interlayer water in montmorillonite. Differences between estimated and observed geometrical factors for cations are attributed to increased ion-pairing of the divalent cations in DDL water as a result of the low relative dielectric permittivity. Interlayer and/or surface diffusion contributes significantly to the diffusive flux of Cs+ but is negligible for the other solutes. The geometrical factors for anions are higher than estimated, because pore constrictions with overlapping double layers force the anions to take longer routes than HTO and the cations. Small differences among the anions can also be attributed to different ion-pairing in DDL water.  相似文献   

20.
Cathodoluminescence (CL) spectra of unirradiated, He+ ion-implanted and electron-irradiated plagioclase minerals contain the following emission bands: (1) below 300 nm due to Pb2+, (2) at ~320 and ~350 nm to Ce3+, (3) at 380–420 nm to Eu2+, Ti4+ and/or Al–O?–Al/Ti defects, (4) at 560–580 nm to Mn2+ and (5) at 720–760 nm to Fe3+. During the implantation of He+ ion, much of their energy may be dissipated by partial destruction and strain of the feldspar framework, resulting in quenching of CL. Deconvolution of CL spectra acquired from albite and oligoclase reveals an emission component at 1.86 eV (666 nm) assigned to a radiation-induced defect center associated with Na+ atoms. As its intensity increases with radiation dose, this emission component has potential for geodosimetry and geochronometry. Electron irradiation causes Na+ migration in plagioclase, and then a considerable reduction in intensity of emissions assigned to impurity centers, which is responsible for an alteration in the energy state or a decrease in luminescence efficiency following the change of activation energy. Emission intensity at 1.86 eV positively correlates with electron irradiation time for unimplanted and He+ ion-implanted albite and oligoclase, but negatively for the implanted albite above 1.07 × 10?4 C/cm2. It implies that radiation halo produced by α-particles should not be measured using CL spectroscopy to estimate β radiation dose on albite in the high radiation level.  相似文献   

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