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1.
The data published earlier on zircon and sphene fission track ages and annealing are discussed in the light of different etching conditions used for age determination and annealing experiments in order to explain the age discordances of some zircon and sphene pairs, as well as numerous closing temperatures obtained for individual minerals. Using the new set of simple etching conditions, zircon (KOH melt) and sphene (HF+HCl), the annealing experiments indicate that tracks in sphene are annealed more easily than in zircon. The closing temperature of zircon and sphene have been calculated at 300° and 250° C respectively. The study reveals that both the fission track age and the closing temperature of a mineral can vary considerably if different etchants are used. For different etching conditions the closing temperatures (T) of sphene have the following order: T NaOH> T HF+HCl+HNO3+H2O> THF+HCl>THCl. An alternative method can be used to obtain thermal histories of rocks by selectively applying various etchants on the same mineral.  相似文献   

2.
The equilibrium position of the reaction $$\begin{gathered} 1.5 KAlSi_3 O_8 + HCl = 0.5 KAl_3 Si_3 O_{10} (OH)_2 \hfill \\ + 3SiO_2 + KCl \hfill \\ \end{gathered} $$ has been located at 1 and 2 kb pressure and temperatures between 600° and 670° C using the Ag-AgCl buffer. These data can be combined with information on the dissociation of KC1, HC1 and H2O to determine species abundances in supercritical aqueous fluids in equilibrium with muscovite — K-feldspar — quartz assemblages. Chloride species become increasingly associated with increasingT, increasing total molality, (m tot or \(m_{Cl_{tot} } \) ), and decreasing \(P_{H_2 O} \) . Master variable diagrams indicate that the pH of the solutions may vary from near neutral to quite acid. Published data on the paragonite-albite-quartz reaction and exchange reactions involving feldspars and micas were included to calculate speciation in mica-feldspar-NaCl-KCl-HCl-H2O fluids at 2kb pressure and temperatures between 300° and 600° C. The data are not accurate enough to distinguish different feldspar structural states. Concentration gradients were calculated for individual species between K-feldspar+quartz, muscovite+quartz and andalusite+quartz assemblages at 500° C, 2 kb. Assuming that the proton diffuses most rapidly and that there are no [H+] gradients, the molality of the solution must vary 30-fold, with feldspar+quartz at the more concentrated side. The data on mica-feldspar-chloride equilibria are used to interpret the spacial distribution of micas, feldspar and quartz in microfolds. This distribution can be accounted for by pressure solution, due to the fact that non-hydrostatic pressure affects congruently dissolving minerals, auch as quartz, differently from minerals which dissolve incongruently, such as micas and feldspars. We postulate, that during folding at constant \(P_{H_2 O} \) ,T and \(m_{Cl - } \) , gradients in KC1 and SiO2 are created by stress differences between hinge and limb of a microfold, such that both migrate to the hinge area where quartz precipitates and muscovite is converted to K-felspar, thus accounting for the observed mineral distribution.  相似文献   

3.
Experiments on the solubility of WO3 in HCl and KCl solutions at 200°C show that tungsten cannot migrate in the form of chloride in solutions. In Cl-rich hydrothermal solutions of moderate salinity, tungsten migrates mainly as alkali salts of HWO 4 ? and WO 4 2? . Determination of the solubility of WO3 in HF and KHF2 solutions at 100–300°C shows that tungsten migrates steadily as WO3F? and WO2F 3 ? in F-rich hydrothermal solutions. Experiments and thermodynamic calculations also indicate that silico-wolframic acid, polymeric wolframic acid and sulfoxy wolframic acid cannot extensively occur in hydrothermal solutions. In addition, the physicochemical conditions of formation of scheelite are also discussed in the present paper.  相似文献   

4.
Stoichiometric anorthite, CaAl2Si2O8, Pˉ1, with sharp a, b, c, and d diffractions was grown, using a CaV2O6 solvent, by cooling at 2 ° C per hour from 1450 to 750 ° C in air. Euhedral crystals up to 5 × 3× 0.5 mm, with prominent {010} and well-developed {110} and {001}, were obtained by spontaneous nucleation. Nonstoichiometric anorthite with excess SiO2 (CaAl2Si2O8+Si2Si2O8) was grown on the join CaAl2Si2O8-SiO2. Chemical analysis of the synthetic anorthite, having the highest SiO2 content, with maximum vacancies on M-site gave □0.110 Na0.006Ca0.884Al1.80Si2.20O8, and X-ray diffraction showed a trend from stoichiometric Pˉ1 through diffuse Pˉ1 to body-centered Iˉ1 probably reflecting increasing disorder caused by a higher Si/Al ratio in the T-sites and the positional disorder accompanied by M-site vancancies. Annealing of the nonstoichiometric diffuse Iˉ1 anorthite in air at 1050 ° C for 14 days resulted in exsolution of minute SiO2 inclusions due to probable ordering in the T-sites and filling of M-sites by Ca. Stoichiometric Pˉ1 anorthite was not obtained by annealing at 1050 ° due to appreciable solubility of SiO2 in CaAl2Si2O8. Metastable hexagonal CaAl2Si2O8 was found to be a twinned monoclinic crystal with cell dimensions: a = 10.24 (2), b = 17.74 (3), c= 14.99 (5) ?, β = 92.05 (5) °, space group C2.  相似文献   

5.
In order to elucidate the solution behavior of carbon and hydrogen in iron-bearing magmatic melts in equilibrium with a metallic iron phase and graphite at oxygen fugacity (fO2) values 2–5 orders of magnitude below the iron-wustite buffer equilibrium, fO2 (IW), experiments were carried out at 4 GPa and 1550°C with melts of FeO-Na2O-SiO2-Al2O3 compositions. Melt reduction in response to an fO2 decrease was accompanied by a decrease in FeO content. The values of fO2 in the experiments were determined on the basis of equilibrium between Fe-C-Si alloy and silicate liquid. Infrared and Raman spectroscopy showed that carbon compounds are formed in FeO-Na2O-SiO2-Al2O3 melts: CH4 molecules, CH3 complexes (Si-O-CH3), and complexes with double C=O bonds. The content of CO2 molecules and carbonate ions (CO 3 2? ) is very low. In addition to carbon-bearing compounds, dissolved hydrogen occurs in melt as H2 and H2O molecules and OH? groups. The spectral characteristics of FeO-Na2O-SiO2-Al2O3 glasses indicate the occurrence of redox reactions in the melt, which are accompanied at decreasing fO2 by a significant decrease in H2O and OH?, a slight decrease in H2, and a significant concomitant increase in CH4 content. The content of species with the double C=O bond increases considerably at decreasing fO2 and reaches a maximum at ΔlogfO2(IW) = ?3. According to the obtained IR spectra, the total water content (OH? + H2O) in the glasses is 1.2–5.8 wt % and decreases with decreasing fO2. The high H2O contents are due largely to oxygen release related to FeO reduction in the melt. The total carbon content at high H2O (4.9–5.8 wt %) is approximately 0.4 wt %. The carbon content in liquid iron alloys depends on silicon content and, probably, oxygen solubility and ranges from 0.3 to 3.65 wt %. Low carbon contents were observed at a significant increase in Si content in liquid iron alloy, which may be as high as ～13 wt % at fO2 values 4–5 orders of magnitude below fO2(IW).  相似文献   

6.
Annealing experiments on natural olivine (Mg1-x Fe x )2SiO4 (with x≈0.11) crystals (San Carlos, Arizona, spinel-lherzolite context) have been performed between T=1,100° C and 1,500° C for oxygen partial pressures pO2=10?3 to 10?13 bar and times of 1 to 140 h in CO/CO2 or H2/H2O gas mixtures. Even specimens annealed within the T-pO2 theoretical stability field (TSF) calculated for stoichiometric olivine (Nitsan 1974) show systematic alterations developed within the first few microns of the surface of the crystals. Pyroxene crystals or melt form on the original olivine surface even at T=1,100° C, with preference of pyroxene when T<1,350° C and SiO2-rich glass if T>1,350° C. This glass (rhyolite-like) can concentrate calcium from the starting olivine, and aluminum when Cr-Al spinels are present as inclusions. These observations are in contradiction with the TSF. They are obviously due to the presence of platinum used as a container of our samples, even if the contact between olivine and platinum is very weak. Rapid surficial diffusion of iron toward platinum (or via the gas phase) induces a Fe-depleted surface. According to the TSF, this more forsteritic surface should have a wider pO2 range of stability. This is not the case, just because this situation is largely out of equilibrium. This iron loss induces a departure from cationic stoichiometry: (Mg, Fe)2(1?δ), SiO4 with δ small and positive. We extended the model that Nakamura and Schmalzried (1983) (N.S.) developed for fayalite (x=1) to our natural olivine composition, under the assumption that the majority defects are magnesium vacancies, Fe3+ occupying octahedral and tetrahedral sites, and the more complex neutral defect corresponding to Coulombic attraction between neighboring Fe3+ ions. We have recalculated the olivine stability field in pO2 vs. δ space at T=1,300° C using this model for x≈0.1 (its extreme limit of validity) and conclude that olivine is stable only in a very narrow range in pO2 which depends on δ. The calculation shows also that when olivine has nearly cationic stoichiometry (δ=0) as we believe for our starting material, the pO2 range of stability is narrower than indicated by the TSF. In particular, it explains why Fe precipitates from the olivine (δ=0) (in absence of any other precipitation of SiO2-rich phases) between 10?11 and 10?13 bar at 1,300° C; this was not predicted by the TSF. Magnetite or iron precipitates also coexist with SiO2-rich exsolutions or pyroxene when pO2 is close to the upper or lower boundaries of the TSF, respectively. The N.S. model may have important implications for the interpretation of the existence of partial melting and/or the low-viscosity/low velocity zone in the upper mantle.  相似文献   

7.
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   

8.
Dongping Lake is an important regulator for the Eastern Route of South-to-North Water Diversion Project in China, and the water quality assurance of it is of great importance. To investigate the distribution characteristics and burial process of phosphorus (P) in Dongping Lake as well as their relationship with regional economic development and human activities, 33 spatially distributed surface sediment samples and one lake sediment core were extracted from Dongping Lake. A harmonized procedure for the P forms in freshwater sediments developed by the European Programme, Standards, Measurements, and Testing was used in this paper. The results show that NaOH–P (P bound to Al, Fe, Mn oxides or hydroxides), HCl–P (Ca-bound P), inorganic phosphorus (IP), organic phosphorus (OP), and total phosphorus (TP) in the surface sediments show a strong spatial variability. The highest NaOH–P and OP concentrations were observed in the eastern and south-eastern region of the lake and decreased gradually away from the mouth area of Dawen River. We deduced that anthropogenic input via the Dawen River is the main contributor. The higher concentration of HCl–P occurred in the north-west region of the lake and increased in a gradient away from the mouth area of Dawen River, and this pattern of distribution could be related to grain-size effects and higher transport energies close to riverine inlets. Pollution reflected by phosphorus in the core sediments of Dongping Lake is well consistent with the economic development history of Dongping County. From the beginning of the 20th century to the middle 1970s, the concentrations of each P speciation did not vary largely and runoff of the Yellow River mainly contributed to the P accumulation in the sediment, which might reflect the background values of them in the lake in pre-industrial period. The stable Mz (mean grain size), low loss-on-ignition (LOI), and high sedimentary flux also support this. The rapid increase of NaOH–P and OP at 10–0 cm (especially 5–0 cm) indicates the enhancing anthropogenic eutrophication since the middle 1970s. The LOI peak period and a coarsening of particle size also support this interpretation. However, the decreasing of TP and HCl–P was attributed to the change in sediment supply. As due to construction of dams around the lake, runoff of the Dawen River mainly contributed to the P accumulation in the sediment during this period.  相似文献   

9.
A sample preparation method of total sulphur measurement of reactive mine tailings was optimized. The total sulphur was measured by inductively coupled plasma optical emission spectroscopy, and ultrasound technique was used for sample digestion. The optimization process was adopted by a combined approach of experimental design and response surface methodology. The digestion time, temperature and acid-oxidant combination (i.e. effect of H2O2 with a fixed amount of acid mixture) were investigated. A two-level and three-factor (23) full factorial design of experiment was applied to identify the most significant factors, and a central composite design was used to optimize the digestion procedure. KZK-1, a sericite schist, was selected as the certified reference material. The optimum methodology at 95 % confidence level (P < 0.05) was identified to be 10 min of digestion at 77 °C, with a solution of 1 ml HNO3:1 ml HCl:1.35 ml H2O2. This combination resulted in 100 % sulphur recovery. The investigated method was verified by X-ray diffraction analysis. The optimum digestion level was applied to a reactive mine tailings, which achieved satisfactory results with a percentage relative standard deviation < 3 %.  相似文献   

10.
Viridine containing the highest amounts of Mn2O3 detected thus far (up to 20.5 mol % “Mn2SiO5”) coexists in a metasedimentary hornfels with spessartine, Mn-phlogopite (mangan-ophyllite), Mn-phengite (alurgite), hematite, quartz and probably some primary braunite. In layers poorer in viridine spessartine is absent but piemontite appears as an additional phase. Microprobe analyses of all these phases are presented which indicate very strong fractionation of Mg and Mn in coexisting phlogopite and garnet, and of Fe and Mn in coexisting hematite and braunite. Sericitic aggregates consisting of phengitic muscovite and braunite are interpreted as retrograde alteration products of viridine, but might partly be pinitic alterations of a former Mg-rich cordierite. Due to the occurrence of the assemblage spessartine-viridine-quartz Mn-cordierite cannot have been a stable phase prior to retrograde alterations. In general the stability field of viridine is extended towards higher temperatures as compared to that of pure andalusite, Al2SiO5. Due to the coexistence of phlogopite and muscovite (phengite) the temperature of contact metamorphism cannot have exceeded some 550°–650° C depending on the prevailing water pressure.  相似文献   

11.
Reversal experiments at 1,150–1,300°C on the reaction forsterite+cordierite=aluminous orthopyroxene+spinel in the system MgO-Al2O3-SiO2 show the equilibrium to have a negativedT/dP. The slope andT-P location of this equilibrium have been modelled using available heat capacity data and various structural models which explore the configurational entropy contributions to the totalΔS. The experimental data are consistent with the aluminous orthopyroxene model of Ganguly and Ghose (1979) where limited Al disorder occurs between theM1 andM2 sites, Al-Si mixing occurs on the tetrahedralB site with the ‘aluminum avoidance’ principle maintained, and Mg-Al disorder occurs in spinel with an interchange enthalpy of 9–12 kcal mol?1. Additionally, Al-Si disordering which occurs in the indialite structure of cordierite is inconsistent with the experimental data and all pyroxene and spinel mixing models; consequently, Si and Al in anhydrous cordierites to 1,300°C in the system MgO-Al2O3-SiO2 must be largely ordered.  相似文献   

12.
The P-T path of magma associated with the 1944 Vesuvius eruption has been outlined on the basis of probe mineralogy and the relationships between the crystallising phases. Equilibrium P-T values, obtained from the reactions:
  1. CaMgSi2O6(liq) = CaMgSi2O6(cpx)
  2. NaAlSi3O8 (liq) = NaAlSi3O8 (plag)
  3. CaAl2Si2O8 (plag)=CaAl2SiO6(cpx)+SiO2(liq) have been established for three intracrustal crystallisation stages: I) 8.0 kbar and 1255 °C; II) 4.0 kbar and 1178 °C; III) 0.5 kbar and 1105 °C.
The H2O content in the magma has been estimated from an experimental calibration of \(a_{^{CaMgSi_2 O_6 } }^{liq}\) as a function of \(X_{H_2 O}^{liq}\) at P tot = 2 kbar. The estimated water contents of the magma for the three stages, I) 0.7%; II) 0.9%; III) 1.1%, are consistent with the pattern of activity of the 1944 Vesuvius eruption and with the relationship between the lavas. The shallow depth of H2O-saturation of the magma, 0.24 kbar at 1100 °C, is consistent with the eruption sequence of lava flows followed by lava fountain activity.  相似文献   

13.
Enthalpies of solution in molten 2 PbO · B2O3 at 974 K were measured for four spinelloids, phases I (0.75 NiAl2O4 · 0.25 Ni2SiO4), II (0.60 NiAl2O4 · 0.40 Ni2SiO4), III and IV (0.50 NiAl2O4 · 0.50 Ni2SiO4) in the system NiAl2O4 · Ni2SiO4. The enthalpies (in cal per 4-oxygen mol) of formation from NiAl2O4 and Ni2SiO4 spinels are: phase I, 945±366; phase II, 1072±360; phase III, 2253±390; phase IV, 3565±544. Using these enthalpy data in combination with phase relations at high pressure at 1373 K, positive entropies of formation of the spinelloids from NiAl2O4 and Ni2SiO4 spinels were estimated (in cal mol?1 K?1): phase I, 1.2; phase II, 1.5; phase III, 2.0–2.3; phase IV, 3.0–3.1. The thermochemical data obtained above suggest that the spinelloids are “entropy-stabilized” phases with partially disordered cation distributions. The configurational entropies of the spinelloids were calculated based on the observed cation distribution in each spinelloid phase. The positive entropies of formation of the spinelloids from the spinel endmembers are due primarily to the configurational entropies although small positive vibrational entropy changes may also exist.  相似文献   

14.
Raman spectra of Ni2SiO4 spinel (O h 7 Z=8) have been measured in the temperature range from 20 to 600 °C and the Raman active vibrations (A 1g +E g +3F 2g ) have been assigned. A calculation of the optically active lattice vibrations of this spinel has been made, assuming a potential function which combines general valence and short range force constants. The values of the force constants at 20 and 500 °C have been calculated from the vibrational frequencies of the observed Raman spectra and infrared (IR) spectral data. The Ni spinel at 20 °C has a prominently small Si-O bond stretching force constant of K(SiO)=2.356 ～ 2.680 md/Å and a large Ni-O bond stretching constant of K(NiO)=0.843 ～ 1.062 md/Å and these force constants at 500 °C decrease to K(SiO)=2.327 ～ 2.494 md/Å and K(NiO)=0.861 ～ 0.990 md/Å. The Si-O bond is noticeably weakened at high temperatures, despite the small thermal expantion from 1.657 Å (20 °C) to 1.660 Å (500 °C). These changes of the interatomic force constants of the spinel at high temperatures are in accord with the thermal structure changes observed by X-ray diffraction study. The weakened Si-O bond is consistent with the fact that Si atoms in the spinel lattice can diffuse at significant rates at elevated temperature.  相似文献   

15.
In the lattice energy expression of forsterite, based on a Born-Mayer (electrostatic+repulsive+dispersive) potential, the oxygen charge z o, the hardness parameter ρ and the repulsive radii r Mg and r Si appear as unknown parameters. These were determined by calculating the first and second partial derivatives of the energy with respect to the cell edges, and equalizing them to quantities related to the crystal elastic constants; the overdetermined system of equations was solved numerically, minimizing the root-mean-square deviation. To test the results obtained, the SiO 4 4? ion was assumed to move in the unit-cell, and the least-energy configuration was sought and compared with the experimental one. By combining the two methods, the optimum set of parameters was: z o=?1.34, ρ=0.27 Å, r Mg=0.72 Å, r Si=0.64 Å. The values ?8565.12 and ?8927.28 kJ mol?1 were obtained, respectively, for the lattice energy E Land for its ionic component E L 0 ,which accounts for interactions between Mg2+ and SiO 4 4? ions only. The charge distribution calculated on the SiO 4 4? ion was discussed and compared with other results. Using appropriate thermochemical cycles, the formation enthalpy and the binding energy of SiO 4 4? were estimated to be: ΔH f(SiO 4 4? )=2117.6 and E(SiO 4 4? )=708.6 kJ mol?1, respectively.  相似文献   

16.
The otoliths of 200 postlarval spot (Leiostomus xanthurus) were marked by immersing the fish for 24 hr in a solution of 0.4 g tetracycline HCl l?1 of salt water (15 ‰). The resulting time-mark could later be identified under ultraviolet (UV) light with an epifluorescence microscope. Spot were held in the laboratory or in the field for up to 30 d. Two validation methods were employed to document daily increment formation. The total number of increments per otolith, or the number of increments formed after the time-mark, were regressed against days held in an experiment. The hypothesis of one increment per day would result in a regression coefficient not significantly different from 1.0. In the field both the total count method (b=1.05) and the time-mark method (b=0.90) supported a one-increment-per-day hypothesis and were not significantly different from each other (p>0.05). In the laboratory the total count method (b=0.56) and the time-mark method (b=0.36) were significantly different from 1.0 (p<0.05), and thus did not support the one-increment-per-day hypothesis. Failure to resolve a one-increment-per-day deposition rate in the laboratory was primarily attributed to food limitation in the experiments.  相似文献   

17.
Experiments on the join Al2SiO5-“Mn2SiO5” of the system Al2O3-SiO2-MnO-MnO2 in the pressure/temperature range 10–20 kb/900–1050° C with gem quality andalusite, Mn2O3, and high purity SiO2 as starting materials and using /O2-buffer techniques to preserve the Mn3+ oxidation state had following results: At 20 kb/1000°C orange-yellow kyanite mixed crystals are formed. The kyanite solid solubility is limited at about (Al1.88Mn 0.12 3+ )SiO5 and, thus, equals approximately that on the join Al2SiO5-“Fe2SiO5” (Langer and Frentrup, 1973) indicating that there is no Jahn-Teller stabilisation of Mn3+ in the kyanite matrix. 5 mole % substitution causes the kyanite lattice constants a o, b o, c o, and V o to increase by 0.015, 0.009, 0.014 Å, and 1.6 Å3, resp., while α, β, γ, remain unchanged. Between 10 and 18 kb/900°C, Mn3+-substituted, strongly pleochroitic (emeraldgreen-yellow) andalusitess (viridine) was obtained. At 15 kb/900°C, the viridine compositional range is about (Al1.86Mn 0.14 3+ )SiO5-(Al1.56Mn 0,44 3+ )SiO5. Thus, Al→Mn3+ substitutional degrees are appreciably higher in andalusite than in kyanite, proving a strong Jahn-Teller effect of Mn3+ in the andalusite structure, which stabilises this structure type at the expense of kyanite and sillimanite and, thus, enlarges its PT-stability range extremely. 17 mole % substitution cause the andalusite constants a o, b o, c o, and V o to increase by 0.118, 0.029, 0.047 Å and 9.4 Å3, resp. At “Mn2SiO5”-contents smaller than about 7 mole %, viridine coexists with Mn-poor kyanite. At “Mn2SiO5”-concentrations higher than the maximum kyanite or viridine miscibility, braunite (tetragonal, ideal formula Mn2+Mn3+[O8/Si04]), pyrolusite and SiO2 were found to coexist with the Mn3+-saturated ky ss or and ss, respectively. In both cases, braunites were Al-substituted (about 1 Al for 1 Mn3+). Pure synthetic braunites had the lattice constants a o 9.425, c o, 18.700 Å, V o 1661.1 Å3 (ideal compn.) and a o 9.374, c o 18.593 Å3, V o 1633.6 Å3 (1 Al for 1 Mn3+). Stable coexistence of the Mn2+-bearing phase braunite with the Mn4+-bearing phase pyrolusite was proved by runs in the limiting system MnO-MnO2-SiO2.  相似文献   

18.
Reedmergnerite (NaBSi3O8) has been synthesised hydrothermally from gels containing 10 wt.% excess SiO2. The degree of B, Si order increases with time at constant temperature and pressure. Complete order is achieved in 250 h at 400° C, P fluid=1 kbar and in 700 h at 300° C, 1 kbar. Lower pressures and/ or low water contents greatly reduce the rate of ordering. The ordering behaviour of reedmergnerite is insensitive to the composition of the co-existing fluid and this contrasts with the behaviour of albite. It is suggested that ordering takes place by a process of solution and re-precipitation.  相似文献   

19.
X-ray structure refinements of Ni2SiO4 and Fe2SiO4 spinels have been made as a function of temperature and heating duration by intensity measurements at high temperatures and room pressure. The lattice parameters of Ni2SiO4 spinel linearly increased with temperature up to 1,000° C. However, Fe2SiO4 spinel exhibited a nonlinear thermal expansion and was converted to a polycrystalline mixture of spinel and olivine by heating of less than one-hour at 800° C. The ratios between the octahedral and tetrahedral bond lengths D oct/D tetr and between the shared and unshared edge distances (O-O)sh/(O-O)unsh in Fe2SiO4 spinel were both much larger than those in Ni2SiO4. These ratios increase with temperature. The Fe2SiO4 spinel more readily approached a activation state which facilitated the transition to the olivine structure than the Ni2SiO4 spinel. The lattice parameter of Ni2SiO4 spinel decreased with heating period at constant temperatures of 700° C and 800° C. The parameter of the quenched sample after heating for 52 h at 700° C was smaller than that of the nonheated sample. The refinements of the site occupancies at each heating duration indicated an increase in the cation deficiency in both tetrahedral and octahedral sites. Electron microprobe analysis, however, proved no significant difference in the chemical compositions between the quenched and nonheated samples. Si and Ni atoms displaced from normally occupied spinel lattice sites are assumed to settle in vacant sites defined by the cubic close packed oxygen sublattice in a manner which preserves the electric neutrality of the bulk crystal.  相似文献   

20.
Polarized infrared (IR) spectroscopy of olivine crystals from Zabargad, Red Sea shows the existence of four pleochroic absorption bands at 3,590, 3,570, 3,520 and 3,230 cm?1, and of one non pleochroic band at 3,400 cm?1. The bands are assigned to OH stretching frequencies. Transmission electron microscopy (TEM) shows no oriented intergrowths in this olivine; it is concluded that OH is structural. On the basis of the pleochroic scheme of the absorption spectra it is proposed that [□O(OH)3] and [□O2(OH)2] tetrahedra occur as structural elements, assuming that the vacancies are on Si sites. If M2 site vacancies were assumed [SiO3(OH)] and [SiO2(OH)2] tetrahedra occur as structural elements.  相似文献   

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