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1.
Triclinic Fe2+ and Fe3+-chloritoid end members, as well as Fe2+-Fe3+-chloritoid solid solutions were synthesized in order to determine the location of the OH groups in the structure and to investigate the possibility of Fe3+ incorporation on the M1B site and the corresponding oxidation mechanism. The samples were analyzed using transmission electron microscopy, electron energy-loss and 57Fe Mössbauer spectroscopy, polarized single-crystal, KBr powder and in situ high-pressure infrared spectroscopy. The structure of a natural triclinic chloritoid was refined by single-crystal X-ray diffraction in order to locate the proton-accepting oxygens in the triclinic structure. The results of valence bond calculations, polarized single-crystal and in situ high-pressure IR spectroscopy revealed that the orientations of the OH dipoles are the same as those in monoclinic chloritoid. The annealing experiments in air show that the incorporation of Fe3+ on M1B increases with temperature. After 3?h at 530?°C all Fe2+ was oxidized to Fe3+ without decomposition of the structure. This also holds true for a heating duration of 24?h. The incorporation of Fe3+ at M1B sites is coupled with a dehydration process starting at about 350?°C during which the H1A protons leave first.  相似文献   

2.
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   

3.
57Fe-Mössbauer spectra of eleven Fe-Mg-bearing staurolite samples, synthesized at 5, 20 and 25 kbar and 680°C, ranging in composition from xFe?=1.00 to xFe?=0.15, and of two Zn-Fe-bearing staurolite samples, synthesized at 20 kbar and 700°C with xFe?=0.10 and xFe?=0.32 were collected at room temperature. The spectra reveal that about 80% of Fetot (in case of Fe-Mg-bearing staurolite) and about 70% of Fetot (in case of Fe-Zn-bearing staurolite) are located as Fe2+ at the three subsites Fe1, Fe2 and Fe3 of the tetrahedral T2-site. The refinement of the spectra results in almost identical values for the isomer shift (IS) (±1.0 mm/s) but significantly different values for the quadropole splitting (QS) for the three subsites which is in accordance with the different distortions of these sites. About 8% of Fetot (in case of Fe-Mg-bearing staurolite) and 13% of Fetot (in case of Fe-Zn-bearing staurolite) are located as Fe2+ at the octahedral M4 site, while the remainder percents of Fetot indistinguishably occur as Fe2+ at the octahedral M1 and M2 sites of the kyanite-like part of the structure. Within the whole Fe-Mg-staurolite solid solution series the Mössbauer parameters QS of the sites M4 and (M1, M2) vary systematically with composition whereas IS remains constant. There is a high negative correlation of the total Mg-content with Fe-occupation of all the Fe-bearing sites indicating a continuous substitution of Fe2+ by Mg on all these sites. Synthetic Fe-staurolites show no increasing occupation of the octahedral sites by two-valent cations with pressure, as was assumed by several authors.  相似文献   

4.
Electrical resistivity and 57Fe Mössbauer spectra are reported for three calcic amphiboles with different Fe concentrations. AC measurements (20?Hz–1?MHz) were performed, applying impedance spectroscopy between 100 and 785?°C in an N2 gas atmosphere. It was found that up to three semiconducting charge transport processes can be distinguished, which in part changed slightly when several runs were carried out to higher temperatures. The extrapolated DC resistivity is much smaller for an amphibole with high Fe content than for the two with lower Fe concentrations. The derived activation energies are between ～0.48 and ～1.06?eV. For temperatures ≤600?°C the results are compatible with a charge transport mechanism due to electron hopping between Fe2+ and Fe3+. Above 600?°C, dehydrogenation and/or beginning amphibole decomposition obviously alter the conduction mechanism. From Mössbauer spectra it was established that in all amphibole samples Fe2+ and Fe3+ are simultaneously present. Mössbauer parameters were derived by fitting the observed spectra to models taking the occupation of various M sites into account.  相似文献   

5.
We determined the forward rate constant (K+) for the Fe2+–Mg order–disorder between the M2 and M1 sites of orthopyroxene (OPx), which is described by the homogeneous reaction Fe2+ (M2) + Mg(M1) ↔ Mg(M2) + Fe2+ (M1), by both ordering and disordering experiments at isothermal condition and also by continuous cooling experiments. The rate constant was determined as a function of temperature in the range of 550–750°C, oxygen fugacity between quartz–fayalite–iron and Ni–NiO buffers, and at compositions of 16 and 50 mol% ferrosilite component. The K+ value derived from disordering experiment was found to be larger than that derived from ordering experiment at 550°C, while at T>580°C, these two values are essentially the same. The fO2 dependence of the rate constant can be described by the relation K+ α (fO2) n with n=5.5–6.5, which is compatible with the theoretically expected relation. The Arrhenius relation at the WI buffer condition is given by
where C o represents the total number of M2 + M1 sites occupied by Fe2+ and Mg per unit volume of the crystal. The above relation can be used to calculate the cooling rates of natural OPx crystals around the closure temperature (T c) of Fe–Mg ordering, which are usually below 300°C for slowly cooled rocks. We determined the Fe–Mg ordering states of several OPx crystals (∼ Fs50) from the Central Gneissic Complex (Khtada Lake), British Columbia, which yields T c ∼290°C. Numerical simulation of the change of Fe2+-Mg ordering in OPx as a function of temperature using the above expression of rate constant and a non-linear cooling model yields quenched values of ordering states that are in agreement with the observed values for cooling rates of 11–17°C/Myr below 300°C. The inferred cooling rate is in agreement with the available geochronological constraints.  相似文献   

6.
 Ferrian magnesian spodumene was synthesized in the MLFSH system at P=0.4 GPa, T=700 °C, fO2=NNO+2.3. The space group at room T is P21/c [a=9.638(3) ?, b=8.709(2) ?, c=5.258(2) ?, β=109.83(3)∘, V=415.2 ?3]. The structure is topologically equivalent to that of ferrian spodumene, LiFeSi2O6, and has two symmetrically independent tetrahedral chains, A and B, and two independent octahedral sites, M1 and M2. The crystal-chemical composition was determined combining EMP, SIMS and single-crystal XRD analysis, yielding M2(Li0.85Mg0.09Fe2+ 0.06) M1(Fe3+ 0.85Mg0.15)Si2O6. Li is ordered at the M2 site and Fe3+ is ordered at the M1 site, whereas Mg (and Fe2+) distribute over both octahedral sites. Structure refinements done at different temperatures (25, 70, 95, 125, 150 and 200 °C) allowed characterization of a reversible displacive P21/c→C2/c transition at 106 °C. Previous HT-XRD studies of Li-clinopyroxenes had shown that the transition temperature is inversely related to the size of the M1 cation. For the crystal of this work, the aggregate ionic radius at M1 is longer than that of ferrian spodumene, for which the transition temperature is −44 °C. The higher transition temperature observed can only be explained on the basis of the shorter aggregate radius at the M2 site (due to the presence of Mg substituting after Li), in keeping with the results obtained for ferromagnesian P21/c pyroxenes. The effects of all the chemical substitutions must be considered when modelling transition temperatures and thermodynamic behaviour in clinopyroxenes. Received: 7 May 2002 / Accepted: 23 October 2002  相似文献   

7.
《Geochimica et cosmochimica acta》1999,63(13-14):2009-2018
Oxygen and hydrogen isotope fractionation factors between brucite and water were experimentally determined by chemical synthesis techniques at low temperatures of 15° to 120°C. MgCl2, Mg3N2, and MgO were used as reactants, respectively, to produce brucite in aqueous solutions. All of the synthesis products were identified by x-ray diffraction (XRD) for crystal structure and by scanning electron microscope (SEM) for morphology. It is observed that oxygen isotope fractionations between brucite and water are temperature dependent regardless of variations in aging time, the chemical composition, and pH value of solutions. Brucites derived from three different starting materials yielded consistent fractionations with water at the same temperatures. These suggest that oxygen isotope equilibrium has been achieved between the synthesized brucite and water, resulting in the fractionation equation of 103lnα=1.56×106/T2−14.1. When the present results for the brucite–water system are compared with those for systems of gibbsite–water and goethite–water, it suggests the following sequence of 18O-enrichment in the M−OH bonds of hydroxides: Al3+ − OH > Fe3+ − OH > Mg2+ − OH.Hydrogen isotope fractionations between brucite and water obtained by the different synthesis methods have also achieved equilibrium, resulting in the fractionation equation of 103lnα=−4.88×106/T2−22.5. Because of the pressure effect on hydrogen isotope fractionations between minerals and water, the present calibrations at atmospheric pressure are systematically lower than fractionations extrapolated from hydrothermal exchange experiments at high temperatures of 510° to 100°C and high pressures of 1060 to 1000 bar. Comparison of the present results with existing calibrations involving other low-temperature minerals suggests the following sequence of D-enrichment in hydroxyl-bearing minerals: Al3+ − OH > Mg2+ − OH > Fe3+ − OH.  相似文献   

8.
Applying Fe2+–Mg exchange geothermometers to natural samples may lead to incorrect temperature estimates if significant Fe3+ is present. In order to quantify this effect, high-pressure experiments were carried out in a belt apparatus in a natural system close to CFMAS at 5 GPa and 1,100–1,400 °C. The oxygen fugacity in the experiments was at or below the Re–ReO2 buffer. This is at significantly more oxidized conditions than in previous experiments, and, as consequence, higher Fe3+/Fe2+ ratios were generated. The Fe3+ content of garnet in the experiments was quantified by electron microprobe using the flank method. Making the usual assumption that Fetotal = Fe2+, the two-pyroxene thermometer of Brey and Köhler (J Pet 31:1353–1378, 1990) reproduced the experimental temperature to ±35 °C and the garnet–clinopyroxene Fe2+–Mg exchange thermometer of Krogh (Contrib Miner Pet 99:44–48, 1988) overestimated the temperatures on average by only 25 °C. On the other hand, application of the garnet–olivine (O’Neill and Wood in Contrib Miner Pet 70:59–70, 1979) and garnet–orthopyroxene (Harley in Contrib Miner Pet 86:359–373, 1984) exchange geothermometers yielded an underestimation in calculated temperatures of >200 °C. However, making explicit accounting for Fe3+ in garnet (i.e. using only measured Fe2+) leads to a vast improvement in the agreement between calculated and experimental temperatures, generally to within ±70 °C for the garnet–orthopyroxene geothermometer as well as noticeable improvement of calculated temperatures for the garnet–olivine geothermometer. Our results demonstrate that the two-pyroxene and garnet–clinopyroxene thermometers are rather insensitive to the presence of Fe3+ whilst direct accounting of Fe3+ in garnet is essential when applying the garnet–olivine and garnet–orthopyroxene thermometers.  相似文献   

9.
Crystallographic determinations on natural olivine single crystals of mantle composition and origin, carried out by in situ neutron diffraction at high temperature, show that the octahedrally co-ordinated Fe2+ and Mg cations undergo two successive trends of cation ordering with increasing temperature. An initial slight preference of Fe2+ for site M1, up to a temperature of about 850?°C, is followed by a reverse-ordering reaction with a site preference exchange between the two cations. The cross-over between the two regimes of ordering, corresponding to a situation of complete disorder, occurs at about 900?°C. Above this temperature Fe2+ progressively and strongly segregates into site M2 up to 1300?°C, the practical limit of the experimental setup utilized in the experiments. Care was taken to ensure that no chemical changes occurred in the crystals (i.e. oxidation), as testified by Mössbauer spectroscopy determinations carried out before and after the heat treatment. The cation-ordering behaviour is reflected in temperature-dependent changes of geometrical and atomic displacement parameters occurring in the octahedral sites M1 and M2. A thermodynamical explanation of this behaviour is proposed in terms of a prevailing vibrational contribution to entropy.  相似文献   

10.
Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5–Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least ~?1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot?=?~?0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+?+?[6]Mg2+?=?2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298?=???1981.5 kJ mol??1. Solid solution is complete across the Fe4O5–Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg–Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.  相似文献   

11.
Lithian ferrian enstatite with Li2O = 1.39 wt% and Fe2O3 7.54 wt% was synthesised in the (MgO–Li2O–FeO–SiO2–H2O) system at P = 0.3 GPa, T = 1,000°C, fO2 = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å3. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula M2(Mg0.59Fe 0.21 2+ Li0.20) M1(Mg0.74Fe 0.20 3+ Fe 0.06 2+ ) Si2O6. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe3+ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe3+ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe2+) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe3+, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe2+-Mg ordering process in octahedral sites.  相似文献   

12.
The Mössbauer spectra of natural megacrystal clinopyroxene are usually fitted by 4 sets of symmetric doublets, A‐A', B‐B', C‐C' and D‐D', respectively, in terms of increasing Qs value in literature. But the assignments of those doublets are quite different, except the D‐D' doublet assigned to Fe3+at the lattice site M***1 in previous papers. Particularly, the assignment and interpretation of the C‐C' doublet are diverse. The oxidation experiments of natural megacrystal clinopyroxene collected from the Hannuoba basalt, North China, were performed under controlled conditions of temperature at 1000°C and oxygen fugacity of FMQ buffer in 1, 2, ***3 and 5 days respectively. The oxidized samples were then measured by X‐ray diffraction spectrometry and Mössbauer spectrometry. The oxidation of clinopyroxene is characterized by Fe2+ → Fe3+at M1 under the subsolidus conditions, which is consistent with the increase of the area of the D‐D' doublet when the heating time increases. Accordingly, the area of the A‐A' and B‐B' doublets decreases with the increasing heating time. However, the area of C‐C' keeps almost constant. Therefore, the 4 sets of doublets can be assigned correctly as follows: A‐A' doublet to Fe+2at M1, B‐B' Fe2+at M1, C‐C' Fe2+at M2, and D‐D' Fe3+at M1. The M1 site splitting is due to the NNN (Next Nearest Neighbour) effect of the M2 site. The amount of Fe3+at the tetrohedral site of megacrystal clinopyroxene is negligible according to this study.  相似文献   

13.
Summary Pyroxene samples, from the Greek island of Syros, taken from a blueschist-eclogite facies Mg-rich metagabbro, were investigated by chemical and XRD analyses and M?ssbauer spectroscopy. Single-crystal XRD and microprobe analysis showed that the natural sample is a typical omphacite of intermediate composition in the Ca–Na pyroxene solid solutions. The space group P2/n was confirmed and the cations Mg, Al and Ca, Na were found to be ordered in the M1 and M2 positions, respectively. M?ssbauer spectroscopy showed that there is both ferrous and ferric iron in the structure, with the ratio 1.38:1. The M2 sites are fully occupied by Ca and Na, thus the iron (Fe2+ and Fe3+) can substitute only for Mg and Al in the M1 sites. Partial disorder was attained by annealing the sample at 850 °C, 20 kbar for 7 days, as confirmed by decrease of intensity of reflections affected by the C-type extinction.  相似文献   

14.
The partitioning of Fe and Mn between the large M(4) site and the octahedral sites, M(1,2,3) in the amphibole structure has been investigated in two natural manganogrunerites of compositions Ca0.1Mn1.9 Mg1.25Fe2+ 3.56Fe3+ 0.38Si7.81O22(OH)2 and Ca0.24Mn1.57 Mg2.27 Fe2+ 2.76Fe3+ 0.32Si7.84O22(OH)2. The long-range cation distribution in the two samples has been elucidated by in situ neutron powder diffraction revealing that Mn is preferentially ordered onto M(4) ? M(2) >M(1) >M(3) in both samples. Partitioning of Mn from M(4) into the octahedral sites begins at 350 °C, with site exchange energies of ?16.6 kJ mol?1 and ?14.9 kJ mol?1, in samples containing 1.90 and 1.57 Mn apfu, respectively. Mössbauer and infrared spectroscopy have been used to study the samples at room temperature, and Mössbauer data agree well with the diffraction results, confirming that high-temperature cation distributions are retained during cooling. The fine structure in the hydroxyl-stretching region of the IR absorption spectra has been used to discuss qualitatively the site occupancies of the coordinating M(1)M(3)M(1) triplet, linked by O(3). On the basis of such modelling, we conclude that a degree of local clustering is present in both samples.  相似文献   

15.
Natural and synthetic olivines with ferrous and ferric iron have been studied by Mössbauer spectroscopy. Their spectra exhibit three superimposed quadrupole-split doublets corresponding to Fe2+ at M1 and M2 sites and Fe3+ at an unidentified position, which is probably M2. The hyperfine parameters of Fe3+ at temperatures between 300°C and 450°C are: Δ=0.67–1.23 mm/s, δ=0.04–0.23 mm/s relative to metallic iron, and the full width at half height, HW=0.15–0.43 mm/s. The Fe2+ populations of M2 decrease with increasing Fe3+ content. However, Fe2+ prefers M1 in synthetic olivines, even at high temperatures (800°–1,400°C). In kirschsteinite, Fe2+ and Fe3+ are exclusively in M1. Fe2+/Fe3+ ratios estimated from the peak areas are consistent with chemical analyses.  相似文献   

16.
Ti-andradites were synthesized at a pressure of P(H2O)=3 kbar and temperatures of 700–800° C. Oxygen fugacities were controlled by solid state buffers (Ni/NiO; SiO2 + Fe/Fe2SiO4). The Fe2+-and Fe3+-distribution was determined by low temperature Mössbauer spectroscopy. The water content was measured by a solid's moisture analyzer. The chemical composition of the synthetic and the natural sample has been determined by electron microprobe. Ti-andradites from runs at high oxygen fugacities have Fe3+ on octahedral and tetrahedral sites; Ti-andradites from runs at low oxygen fugacities have tetrahedrally and octahedrally coordinated Fe2+ as well. These “reduced” garnets must also contain Ti3+ on octahedral sites. Charge balance is maintained due to substitution of O2? by (OH)? by two mechanisms: (SiO4)4? ? (O4H4)4? and (Fe3+O6)9? ? (Fe2+O5OH)9?. FTIR spectra of the synthetic samples do show the presence of structurally bound (OH)?. In a natural sample tetrahedrally and octahedrally coordinated Fe3+ are observed together with Fe2+ on all three cation sites of the garnet structure.  相似文献   

17.
Synthetic melilites on the join Ca2MgSi2O7 (åkermanite) — Ca2FeSi2O7 (iron åkermanite) with Fe/(Fe+Mg) from 0.0 to 0.7 exhibit, at room temperature, an incommensurate phase with a rectangular modulation of a wavelength of about 19 Å in the [110] direction. Upon increase of temperature, they transform to a commensurate melilite structure at about 80° C for Fe/(Fe+Mg)=0.0 and about 250° C for Fe/(Fe+Mg)=0.6. In addition to the T(2) positions of the melilite structure filled by Si, the incommensurate phase exhibits two distinguishable T(1) sites containing the Mg and Fe2+. These two sites merge into one site during the phase transition from the incommensurate to the commensurate phase. A structural model for the incommensurate phase is based on the misfit between the tetrahedral (Mg, Fe2+)Si2O 7 4? sheets and the Ca2+ ions.  相似文献   

18.
The interdiffusion coefficient of Mg–Fe in olivine (D Mg–Fe) was obtained at 1,400–1,600 °C at the atmospheric pressure with the oxygen fugacity of 10?3.5–10?2 Pa using a diffusion couple technique. The D Mg–Fe shows the anisotropy (largest along the [001] direction and smallest along the [100] direction), and its activation energy (280–320 kJ/mol) is ~80–120 kJ/mol higher than that estimated at lower temperatures. The D Mg–Fe at temperatures of >1,400 °C can be explained by the cation-vacancy chemistry determined both by the Fe3+/Fe2+ equilibrium and by the intrinsic point defect formation with the formation enthalpy of 220–270 kJ/mol depending on the thermodynamical model for the Fe3+/Fe2+ equilibrium in olivine. The formation enthalpy of 220–270 kJ/mol for the point defect (cation vacancy) in olivine is consistent with that estimated from the Mg self-diffusion in Fe-free forsterite. The increase in the activation energy of D Mg–Fe at >1,400 °C is thus interpreted as the result of the transition of diffusion mechanism from the transition metal extrinsic domain to the intrinsic domain at the atmospheric pressure.  相似文献   

19.
Structural and compositional data as well as 57Fe Mössbauer parameters were determined on a natural Mn-rich monoclinic ilvaite crystal (ideal composition CaFe 2 2+ Fe3+Si2O8(OH)) which was used for electrical conductivity and thermopower measurements (part 2 of this paper). A zonar structure was found by electron microprobe analysis with a strong decrease in Mn concentration from the rim to the centre of the crystal in a plane perpendicular to the [001] direction. X-ray powder diffraction analysis of the most Mn-rich composition was performed. Mn2+ cations populate preferentially M2 sites of the ilvaite unit cell (space group P21/a), to a lower extent they reside on M1 and a reduced part is on Ca sites. The monoclinic angle was determined to β=90.178(4)°. The structural results are compared to literature data for other natural Mn-rich as well as low-impurity ilvaites; this concerns in particular the lattice b parameter and the undecided issue of the varying β angle. In the literature, the order parameter σ, which describes the varying degree of ordering of Fe2+–Fe3+ pairs on M11 and M12 sites in chains running parallel to the [001] direction, and structural defects are thought to be related to β. The interrelationship between β and σ with respect to a possible twin domain structure is discussed. Various 57Fe Mössbauer spectra were recorded between 151 K and 327 K. Mössbauer parameters and Fe2+/Fe3+ concentration ratios were determined from the fits to the spectra. Fitting of subspectra was accomplished with the idea to find assignments of Fe2+ and Fe3+ doublets in agreement with X-ray results. The fraction of Mn2+ substituting Fe2+ on M1 sites could be estimated.  相似文献   

20.
Experimentally reversed portlandite and brucite solubilities were determined between 300° and 600°C and 1 to 3 kbar. In the portlandite runs the molality of Ca decreases with increasing pressure at constant temperature. For instance, at 2 kbar log molalities at 300°, 400°, 500° and 600°C give values of −2.34, −2.71, −3.18 and −4.18, respectively. At 500°C, pressures of 1, 2 and 3 kbar yield values of −4.40, −3.18 and −2.65. Distribution of species in solution can be calculated with the aid of data from Helgeson and co-workers assuming Ca++ is the dominant Ca species. These calculated Ca concentrations are within ± 0.2 log units of experimental values in most cases. The solubility reaction is, in all likelihood: 2H+ + Ca(OH)2 ↔a3 Ca++ + 2H2O.Although the computed pH's are close to 2 units greater than neutral, the solutions apparently contained no significant Ca(OH)+ or Ca(OH)2sq.Concentrations of Mg in the brucite runs show a sigmoidal behavior at 2 kbar as a function of temperature with log molalities of Mg of −4.00, −4.28, −4.14 and −4.60 at 350°, 450°, 550° and 600°C, respectively. Values at 1 kbar are lower and decrease monotonically from 350° to 550°C. Based on available thermodynamic data for Mg++ it appears that Mg(OH)+ is the dominant Mg species in solution. The solubility reaction is proposed to be: H+ + Mg(OH)2↔a3 Mg(OH)+ + H2O.With the aid of data of Helgeson and co-workers values of the equilibrium constant for H2O + Mg++ ↔a3 Mg(OH)+ + H+ necessary to account for the measured solution compositions can be calculated. These calculations indicate Mg(OH)+ becomes dominant at temperatures above 450°C at 2 kbar and above 360°C at 1 kbar at neutral pH.  相似文献   

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