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1.
We investigated a natural Brazilian Fe–Ti-containing andalusite and its thermal behavior by polarized infrared and optical spectroscopy. Polarized infrared spectra of the Brazilian andalusite and their evolution at thermal annealing in air clearly evidence that there are several types of OH-groups in the structure. Optical spectra and their evolution with temperature indicate that the incorporated iron (about 0.43 wt% calculated as FeO) is in the ferrous and ferric state. Incorporation of ferrous iron in the Al-sites of andalusite is discussed as a possible incorporation mechanism for hydrogen. The weakening and disappearance of the Fe2+/Ti4+ IVCT band in the andalusite spectra under annealing in air is caused by oxidization of Fe2+ to Fe3+ in Fe2+/Ti4+ IVCT pairs. The process of oxidation is accompanied by a rearrangement of the hydroxyl groups and dehydration of the sample, especially vivid at the final stage of the thermal annealing at 1,200 °C. During thermal annealing, structural hydroxyls of different types apparently transform into each other: the most distinct are the hydroxyls causing the doublet at 3,516 and 3,527 cm?1 (i.e., H bonded to O1) which seem to transform into the hydroxyls causing the line at 3,461 cm?1 (i.e., H bonded to O2). The infrared spectra scanned across differently colored zones of the crystal clearly show that some amount of hydroxyls is related to Fe2+/Ti4+ IVCT pairs which are the cause of the red-to-black coloration of the sample in E||c-polarized illumination: it is evident that in a part of the hydroxyl groups, OH-vector changes orientation aligning directly along crystallographic a-axis due to some kind of interaction with Fe2+/Ti4+ IVCT pairs.  相似文献   

2.
The effect of raising temperature on spin-allowed dd-transitions of octahedral Cr3+ was studied for various point symmetries of the Cr3+-bearing structural sites, i.e. 3 m and 3 with inversion center in spinel and garnets, respectively, or 32, 3, 2 and 1, lacking the inversion centre, in beryl, corundum, diopside and topaz, respectively. For this purpose, crystals of Cr3+-bearing spinel, pyrope, andradite, grossular, uvarovite, emerald, ruby, diopside and topaz were analyzed by microprobe, oriented, and measured in polarized radiation (except for the cubic minerals) in the spectral range 30 000 to 11 100 cm-1 and at temperatures between 77 and 797 K. The evaluation of the intensities, half widths, and energy positions of bands due to Cr3+-transitions derived from 4 A 2g 4 T 2g (F) and 4 T 1g (F) as well as of Dq- and B-values derived, had the following results:In all cases, red shift of the above bands and, hence, independent on the site symmetry of Cr3+, decreases in the Dq-values were obtained. The dependcies of Dq on T are nearly linear above room temperature and amount between -1.6% in topaz and -5.1% in pyrope in the temperature range studied. From this, values for the local thermal expansion of the Cr3+-centered octahedra, loc, were derived on the basis of the R M-0 -5 -proportionality of 10Dq. Such values are consistently higher than those obtained from X-ray refinements, a method averaging rm-o for all the respective octahedral positions.  相似文献   

3.
Geology of Ore Deposits - The composition and interrelations of oxides (minerals of the spinel supergroup, corundum, ilmenite, rutile) and silicates (garnet, sillimanite, orthopyroxene, cordierite)...  相似文献   

4.
The oxidation state of vanadium in natural and synthetic Fe–Ti oxides is determined using high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS). Eleven natural magnetite-bearing samples from a borehole of the Main Magnetite Layer of the Bushveld Complex (South Africa), five synthetic Fe oxide samples, and three natural hematite-bearing samples from Dharwar supergroup (India) are investigated. V K edge spectra were recorded on the ID26 beamline at the European Synchrotron Radiation Facility (Grenoble, France), and the pre-edge features were used to determine the local environment and oxidation state of vanadium. In the case of the magnetite samples (natural and synthetic), we show that vanadium is incorporated in the octahedral site of the spinel structure under two oxidation states: +III and +IV. The variations of the pre-edge area are interpreted as various proportions in V3+ and V4+ (between 9.5 and 16.3% of V4+), V3+ being the main oxidation state. In particular, the variations of the V4+/V3+ ratio along the profile of the Main Magnetite Layer seem to follow the crystallization sequence of the layer. In the case of the hematite samples from India, the pre-edge features indicate that vanadium is substituted to Fe and mainly incorporated as V4+ (between 40 and 72% of V4+). We also demonstrate the potentiality of HERFD-XAS for mineralogical studies, since it can filter out the unwanted fluorescence and give better resolved spectra than conventional XAS.  相似文献   

5.
The thermal stability of sideronatrite, ideally Na2Fe3+(SO4)2(OH)·3(H2O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na3Fe(SO4)3 compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe3+(SO4)2(OH)] 2? chains and the formation of an intermediate transient amorphous phase precursor of Na3Fe(SO4)3. (d) for T > 500 °C, the Na3Fe(SO4)3 compound is replaced by the Na-sulfate thenardite, Na2SO4, plus Fe-oxides, according to the Na3Fe3+(SO4)3 → 3/2 Na2(SO4) + 1/2 Fe2O3 + SOx reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.  相似文献   

6.
Abundant Fe–Ti oxide inclusions in cumulus olivine (Fo77–81) from the Panzhihua and Hongge intrusions, Emeishan large igneous province, SW China, document the first evidence for early crystallization of Fe–Ti oxides in ferrobasaltic systems in nature. The intrusions also contain significant stratiform Fe–Ti–V oxide ores. The oxide inclusions are sub-rounded or irregular, range from ∼5 to 50 μm in diameter, and are dominated by either titanomagnetite or ilmenite. The fact that the inclusions are either titanomagnetite- or ilmenite-dominant suggests that they are trapped crystals, instead of immiscible oxide melt, formed during growth of the host olivine. The absence of other silicate phases in the inclusion-bearing olivine is difficult to reconcile with a possible xenocrystic origin of the oxide inclusions. These oxide inclusions are thus interpreted to be cumulus minerals crystallized together and trapped in olivine from the same parental magma. In addition to Fe–Ti oxides, some inclusions contain amphibole + biotite ± fluorapatite that might have formed by reaction of trapped hydrous liquid with the host olivine. Numerical modeling of high-Ti Emeishan basalts using the MELTS program successfully simulates early crystallization of olivine (∼Fo81) and Fe–Ti spinel in the presence of a moderate amount of H2O (∼1.5 wt%) under pressure and fO2 conditions generally pertinent to the Panzhihua and Hongge intrusions. The modal mineralogy of the oxide inclusions is in good agreement with the bulk compositions of the ore, as inferred from whole-rock data, in a given intrusion. This is consistent with the interpretation that the stratiform oxide ores in the intrusions formed by accumulation of Fe–Ti oxide crystals that appeared on the liquidus with olivine and clinopyroxene.  相似文献   

7.
The structure of a natural melilite with chemical composition (Ca1.87Sr0.02Na0.10K0.02)2.01(Mg0.96Al0.07)1.03(Si1.98Al0.02)2.00O7 has been investigated by X-ray single-crystal diffraction methods within the temperature range 298–773 K. The values of the coefficient of the modulation wave vector were determined at 298 K, 323 K, 348 K, and 358 K. These values show a continuous linear decrease from 0.2833(6) at 298 K to 0.2763(9) at 358 K. The incommensurate phase undergoes a phase transition to the normal phase at 359 K. The refinements of the structure, carried out at 298 K, 348 K, 359 K, 373 K, 413 K, 463 K, 513 K, 573 K, 673 K, and 773 K, showed that the normal phase (high-temperature phase) does not significantly differ from the basic structure (the average structure of the incommensurate structure). This study confirms that in natural melilites with chemical composition close to that of åkermanite the wavelength of the incommensurate modulation increases when the temperature rises. The different behaviour of the q-vector as a function of temperature in natural and synthetic åkermanite is discussed.  相似文献   

8.
The ~1.74 Ga Damiao anorthosite complex, North China, is composed of anorthosite and leuconorite with subordinate melanorite, mangerite, oxide-apatite gabbronorite, perthite noritic (i.e., jotunitic) and ferrodioritic dykes. The complex hosts abundant vein-, pod- and lens-like Fe–Ti–P ores containing variable amounts of apatite (10–60 modal%) and Fe–Ti oxides. In addition to Fe–Ti–P ores, there are also abundant Fe–Ti ores which are closely associated with Fe–Ti–P ores in the deposit. Most of Fe–Ti–P ores are dominated by Fe–Ti oxides and apatite, devoid of silicate minerals, mineralogically similar to the common nelsonites elsewhere. In contrast, Fe–Ti ores are dominated by Fe–Ti oxides with minor apatite (<5 modal %). The parental magma of these ores, estimated from olivine and apatite compositions using mineral-melt partition coefficients, has composition similar to the ferrodioritic dykes. Fe–Ti–P ores have variable Fe–Ti oxides and apatite proportions, indicating that they are cumulates. Their simple assemblage of Fe–Ti oxides and apatite and local net-texture suggest that the Fe–Ti–P ores in Damiao have formed from nelsonitic melts immiscibly separated from the ferrodioritic magma during late-stage differentiation. Fe–Ti ores are also cumulates and have mineral compositions similar to Fe–Ti–P ores. The close association between Fe–Ti and Fe–Ti–P ores indicates that the Fe–Ti ores may have also formed from the nelsonitic melts. We proposed that differentiation of nelsonitic melts accompanied by gravity settling is responsible for the formation of Fe–Ti and Fe–Ti–P ores. Such a differentiation process in nelsonitic melts is well supported by variations of Sr, Y, Th, U, REE and Eu/Eu* of apatite in Fe–Ti–P ores. Using oxides/apatite ratio of 2:1 and compositions of apatite and calculated primary oxides, we estimate the composition of the nelsonitic melt as ~52.0 wt% Fe2O3t, ~18.5 wt% CaO, ~14.2 wt% P2O5, ~8.7 wt% TiO2, ~4.0 wt% Al2O3 and ~1.1 wt% MgO with minor SiO2, K2O, Na2O and F. Such a nelsonitic melt is suggested to be possibly conjugated with Si-rich melts compositionally similar to the Damiao jotunitic dykes (~50 wt% SiO2 and ~15 wt% Fe2O3t) which may subsequently evolve to mangeritic rocks in Damiao. Our modeling also indicates that the onset of immiscibility occurs at a time when the evolved melt has ~44 wt% SiO2, ~21 wt% Fe2O3t, ~3.0 wt% TiO2 and ~2.6 wt% P2O5. High oxygen fugacity and phosphorous content in magmas may play important roles in the immiscibility of nelsonitic magmas, including promoting iron enrichments and widening the two-liquid field.  相似文献   

9.
The Baima layered intrusion is located in the central part of the Emeishan Large Igneous Province (ELIP). The N–S striking intrusion is ~ 24 km long and ~ 2 km thick and dips to the west. Based on variations in modal proportions and cumulus mineral assemblages, the intrusion from the base to the top is simply subdivided into a lower zone (LZ) with most of the economic magnetite layers, and an upper zone (UZ) with apatite-bearing troctolite and gabbro. The rock textures suggest crystallization of the Fe–Ti oxide slightly later than plagioclase (An67-54) but relatively earlier than olivine (Fo74-55), followed by clinopyroxene and finally apatite.Relatively low olivine forsterite content and abundant ilmenite exsolution lamellae in clinopyroxene indicate that the Baima parental magma is a highly evolved Fe–Ti-rich magma. Via MELTS model, it demonstrates that under a closed oxygen system, extensive silicate mineral fractionation of a picritic magma might lead to Fe and Ti enrichment and oxygen fugacity elevation in the residual magma. When such Fe–Ti-rich magma ascends to the shallower Baima intrusion, the Fe–Ti oxides may become an early liquidus phase. Well-matched olivine and plagioclase microprobe data with the results of MELTS calculation, combined with relatively low CaO content in olivine (0.02–0.08 wt.%) indicate that wall-rock contamination probably plays a weak role on oxygen fugacity elevation and the early crystallization of Fe–Ti oxides. Several reversals in whole-rock chromium and plagioclase anorthite contents illustrate that multiple recharges of such Fe–Ti-rich magma mainly occurred along the lower part of the Baima magma chamber. Frequent Fe–Ti-rich magma replenishment and gravitational sorting and settling are crucial for the development of thick Fe–Ti oxide layers at the base of the Baima layered intrusion.  相似文献   

10.
This study aims at understanding the physico-chemical interactions between the saturated brine and the rocks enclosing the underground salt workings in Lorraine (eastern France). These anhydrite-rich and argillaceous rocks were characterized in terms of mineralogy, micro-texture and connected porosity. Then, the two main lithofacies, massive anhydrite and anhydrite-rich argillite, were immersed in brine during more than 1 year. During this batch experiment, the argillites were affected by macroscopic splitting, contrarily to the massive anhydrite. Micro-texture and brine chemical analyses clearly show the swelling due to the hydration of anhydrite into gypsum inside the argillites, whereas hydration occurs superficially on the massive anhydrite, due to its very low permeability. Anhydrite–gypsum transformation is promoted by the presence of dissolved strontium and potassium in saturated brine. The low activity of water in saturated brine does not allow the clay fraction to swell significantly during the experiment. Thus, the expansion resulting from the hydration of anhydrite into gypsum might be responsible of the splitting of argillite in a saturated brine environment. The superficial anhydrite hydration on massive anhydrite can be explained by the low amount of connected porosity (less than 1%).  相似文献   

11.
Doklady Earth Sciences - New data on the minerals of the Fe–Ni–Co–Cu–S system in the differentiated intrusions of the Southern Urals are presented. Based on a detailed study...  相似文献   

12.
The first chromatography–mass spectroscopy data on volatiles in diamonds synthesized in the Fe–S–C system with 5 wt % S at 1400–1450°C and 5.0–5.5 GPa indicate the evolution of volatile composition during the diamond growth and, correspondingly, the variation in redox conditions of the reaction cell. A significant role is played by various hydrocarbons (HCs) and their derivatives, the content of which can reach 87%. Our data on possible abiogenic synthesis of HCs (components of natural gas and oil) can result in global recalculations (including climate) related to the global C cycle.  相似文献   

13.
The current formulations of the Fe–Ti oxide thermobarometer (titanomagnetite–ilmenitess) fail to reproduce experimental results, in particular at the high temperatures that are relevant for basaltic assemblages. With the aim of improving the experimental basis of the calibration in the Fe–Ti–O system, we have synthesised assemblages of titanomagnetite–ilmenitess (Tmt–Ilmss), ilmenitess–pseudobrookitess (Ilmss–Psbss) and single-phase samples under a wide range of fO2 (fixed with CO/CO2 mixtures or by solid oxygen buffers) in sub-solidus conditions (1,000–1,300°C) at 1 bar. Runs lasted 24 h at 1,300°C and up to 240 h at 1,000°C and were terminated by quenching in water. All run products are polycrystalline, roughly equigranular aggregates, with grain sizes of 10–50 m. They were examined and analysed with the SEM and EMP. Tmt compositions are broadly in accordance with the current models at moderate fO2, but significantly richer in Ti at low fO2 and high T, due to cationic vacancies. Ilmss compositions depart from the predicted values practically at all fO2 and T conditions, which is related to unsatisfactory thermodynamic models for the rhombohedral oxide. For Ilmss–Psbss assemblages the best agreement between our data and current calculations is at 1,000°C and moderately high fO2. Otherwise, experimental and calculated data strongly disagree. The experimental data set on the three Fe–Ti oxide solid solutions presented here is intended to support new versions of both the titanomagnetite–ilmenitess thermo-oxybarometer and the ilmenitess–pseudobrookitess oxybarometer.  相似文献   

14.
Calibrations are presented for an independent set of four equilibria between end-members of garnet, hornblende, plagioclase and quartz. Thermodynamic data from a large internally-consistent thermodynamic dataset are used to determine the ΔG° of the equilibria. Then, with the known mixing properties of garnet and plagioclase, the non-ideal mixing in amphibole is derived from a set of 74 natural garnet–amphibole–plagioclase–quartz assemblages crystallised in the range 4–13 kbar and 500–800 °C. The advantage of using known thermodynamic data to calculate ΔG° is that correlated variations of composition with temperature and pressure are not manifested in fictive derived entropies and volumes, but are accounted for with non-ideal mixing terms. The amphibole is modelled using a set of ten independent end-members whose mixing parameters are in good agreement with the small amount of data available in the literature. The equilibria used to calibrate the amphibole non-ideal mixing reproduce pressures and temperatures with average absolute deviations of 1.1 kbar and 35 °C using an average pressure–temperature approach, and 0.8 kbar with an average pressure approach. The mixing data provide not only a basis for thermobarometry involving additional phases, but also for calculation of phase diagrams in complex amphibole-bearing systems. Received: 8 November 1999 / Accepted: 7 July 2000  相似文献   

15.
Two methods for obtaining information on the fractional composition of organic matter in natural waters (membrane filtration and oxythermography) are combined in this study. The method has a number of indisputable advantages, which distinguish it among the currently available methods of analytical chemistry. In earth science, the fractional composition of organic materials in natural waters is estimated by the concentration of organic carbon (Corg) in fractions. In our opinion, an indicator of chemical consumption of oxygen (CCO) for ecological estimation of water reservoir state is more informative, because this indicator carries specific ecological information on the necessary oxygen consumption for oxidation of pollutants coming into the natural water environment. Therefore, estimation of the CCO parameter in fractions provides real information on the availability of organic matter and the probable danger from its content in water. This is the principal novelty of the information obtained and our study. The method was tested in the study of variation of the fractional composition of water matter during passage of Volga water through the waterworks (upon removal of water from the storage reservoir through the dam of the Ivan’kovskaya hydro power plant in the Dubna area). Analogous results are almost absent in earth science literature. There is a lack of data on the influence of water release through the dam even with respect to the major-component chemical composition. Variation of the fractional composition of matter (both organic and inorganic) upon water release through a waterworks is not discussed in literature. Thus, this study is of fundamental character.  相似文献   

16.
The results of 19-year optical monitoring of ON 231 are presented. Photographic B-band observations were obtained during 123 nights from April 1972 to March 1990 as part of the quasar monitoring program carried out the Astronomical Institute of St. Petersburg State University. The new combined B-band light curve for ON 231 (1892–1999) is appreciably improved by our data, enabling us to identify a number of previously undetected high-amplitude events with time scales of weeks to months. On two nights, intraday variability with amplitudes \( \sim 0\mathop .\limits^m 8 - 0\mathop .\limits^m 9\) was observed. A number of conclusions are drawn about variability components with time scales from hours to decades. There are cases when very similar behavior on time scales from several weeks to several months was observed in the presence of substantially different base brightness levels. Both the amplitudes (\( \sim 1\mathop .\limits^m 5\)) and the characteristic shapes and overall durations of these events were the same. The constancy of the amplitudes of these events in magnitudes (i.e., the proportionality of the luminosity in rapid outbursts to the underlying level of the slowly varying component) can be explained in models that associate the variability with changes in the Doppler boosting factor due to variations in the inclination of the relativistic jet to the line of sight, if the slow and rapid components of the optical variability are associated with a steady component of the relativistic jet and shock waves (superluminal components) moving in the jet, respectively. Evidence for such a connection has been found for several superluminal sources. At the same time, there is evidence that in typical IDV events for ON 231, with durations of ~1.5–2 hr, the amplitudes depend on the base brightness level of the objects, suggesting that the IDV events and less rapid components of the variability have different natures and/or occur in different locations in the source.  相似文献   

17.
18.
Using the long-term ground temperature monitoring data of the permafrost zone along the Qinghai-Tibet Railway from 2006 to 2020,three types of typical roadbed structures were analyzed. Traditional embankment(TE),U-shaped crushed rock embankment(UCRE)and crushed rock revetment embankment(CRRE)were included the three types of typical roadbed,which were selected to the long-term monitoring sections within the warm permafrost zones. The evolution of ground temperature field,mean annual ground temperature (MAGT)and annual maximum ground temperature(AMGT)in the depth range of 20 m under the embankment were analyzed and studied since 15 years of operation. The monitoring and analysis results show that:the growth rate of MAGT under the left and right shoulders of the TE is always higher than that of the same depth in the natural site. The MAGT under the UCRE is always lower than the natural site and always maintains a certain difference,whereas,the difference in ground temperature under the left and right shoulders is also not negligible. The MAGT of the left shoulder in the CRRE is not much different from that of the natural hole,while the MAGT of the right shoulder is always lower than that of the natural hole,and the differ in ground temperature between the left and right shoulders is smaller than that of the UCRE. The artificial permafrost table(APT)under the TE is always lower than that of in the natural site. Both the UCRE and CRRE,the APT in the left and right shoulders of them has been elevated into the embankment,and the differ of APT between the left and right shoulders is about 1. 0~1. 5 m. the differ of APT between the left and right shoulders in the CRRE is slightly lower than that of UCRE. Overall,because of the influence of thermal disturbance about engineering and climate warming,the TE in the warm permafrost zones cannot keep the thermal stability of permafrost under the embankment. Some active-cooling and reinforcement measures need to be taken. Both of the UCRE and CRRE,have a certain active-cooling effect on the permafrost under embankment,but the differ in ground temperature between the left and right shoulders still needs to be taken seriously. © 2022 Science Press (China).  相似文献   

19.
Astronomy Reports - The observed characteristics of the spectral and photometric variability of SS 433 are discussed based on the data for 2018–2021 and compared with earlier results. The...  相似文献   

20.
Newly obtained data from microscopic, geochemical, and thermomagnetic studies of the large Kolyma fulgurite are presented here: the fulgurite was formed in the Holocene as a result of lightning affected black shale alluvium. The composition is very close to that of glass formed from a melt. The glass has elevated concentrations of Y, Zr, Nb, and REEs. The newly formed mineral phases have been identified: those are Al–Si glass, α-cristobalite, moissanite, native iron with a phosphorus admixture, nickel-less shreibersite (?), troilite, and possibly cohenite. The formation of these minerals is related to the melt fractionation and the effects of element concentration and segregation of ore components under conditions of the rock melting caused by the effect of high-energy plasma (lightning strike).  相似文献   

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