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1.
A number of different impurities are located in the open channels of natural beryl crystals. The rare Maxixe beryl contains an unusual amount of NO2. The isoelectronic CO2 radical is found in the irradiated Maxixe-type beryl. The NO2 radicals are distributed in the Be–Al plane of the crystal, with the nitrogen atom close to the oxygens of the beryl cavity wall. These oxygens repel the negative CO2 radical, which is located at the center of the beryl cavity and rotates around its O–O axis, which is parallel to the crystal c-axis. When there is a nearby alkali ion at the center of the beryl channel, it reorients the CO2 radical so that its bisector is parallel to the c-axis and points toward the positive ion. Different signals are analyzed for Li+, Na+, and another counter-ion, which probably is Cs+. The related NO3 and CO3 radicals are the color centers in the investigated deep blue beryls. The slow decay of the color, which makes these beryls useless as gem stones, is related to the decay of the hydrogen atoms which are present in these crystals. Evidence is given that NO3 is created in Maxixe beryl by a natural process, while CO3 in Maxixe-type beryl has been created by irradiation. The temperature dependence of the EPR signals of these two radicals was investigated, but a definitive proof that they rotate at the center of the beryl cavity could not be given. EPR signals from some other radicals in beryl have been observed and described.  相似文献   

2.
In order to determine the mechanisms of formation and properties of natural hydrosilicate liquids (HSLs), which are formed during the transition from magmatic to hydrothermal mineral formation in granitic pegmatites and rare-metal granites, the formation of HSLs was experimentally studied in the Na2O-SiO2-H2O, Na2O-Al2O3-SiO2-H2O, and Na2O-K2O-Li2O-Al2O3-SiO2-H2O systems at 600°C and 1.5 kbar. It was shown that the sequential extension of composition does not suppress HSL formation in the systems and expands the stability field of this phase. However, HSLs formed in extended chemical systems have different structure and properties: the addition of alumina induces some compression of the structure of the silicate framework of HSLs, which results in a decrease in water content in this phase and probably hinders the reversibility of its dehydration. It was demonstrated that HSL can be formed by the coagulation of silica present in a silica-oversaturated alkaline aqueous fluid. It was supposed that the HSL formed during this process has a finely dispersed structure. It was argued that anomalous enrichment in some elements in natural HSLs can be due to their sorption by the extensively developed surface of HSL at the moment of its formation.  相似文献   

3.
Detailed phase relations have been determined within the systems Fe2O3-MgO-TiO2 and FeO-MgO-TiO2. Experiments were performed over the temperature interval 1173–1473 K by equilibrating pelletized, fine-grained oxide mixtures in either inert calcia-stabilized zirconia pots (Fe2O3-MgO-TiO2 system) or evacuated silica tubes (FeO-MgO-TiO2 system). Equilibrium phase assemblages were determined by combined optical microscope, X-ray diffraction and EMP examination. Phase relations in the Fe2O3-MgO-TiO2 ternary are dominated by the instability of the M2O3 solid solution relative to the phase assemblage M3O4 + M3O5. A miscibility gap along the M2O3 binary also gives rise to two, 3-phase fields (α-M2O3 + M3O5 + M3O4 and α′-M2O3 + M3O5 + M3O4) separated by the M3O4 + M3O5 phase field. Phase relations in the FeO-MgO-TiO2 ternary were divided into two sub-systems. For the FeTiO3-MgTiO3-TiO2 sub-ternary, there is complete solid solution along the M2O3 and M3O5 binary joins at high temperature. At low temperatures (T < 1373 K) the M3O5 pseudobrookite solid solution decomposes to M2O3 + TiO2. Increasing the concentration of MgO in M3O5 phase results in a decrease in the temperature at which M3O5 becomes unstable and compositional tie lines linking M2O3 and TiO2 fan out, before the appearance of a three-phase region where M2O3, M3O5, and TiO2 coexist. Within the expanded FeO-MgO-TiO2 system, at temperatures above ∼1273 K there is a continuous solid solution along the M3O4 binary. At low temperatures (T < 1273 K) the Mg2TiO4 end-member breaks down to MgO and MgTiO3. The M3O4 phase shows significant non-stoichiometry, down to at least 1173 K. Fe2+-Mg partitioning data were obtained for coexisting M2O3-M3O5 and M2O3-M3O4 pairs in the FeO-MgO-TiO2 ternary. Assuming a regular solution mixing model for all phases, the M2O3 and M3O4 solid solutions were both found to exhibit moderate positive deviations from ideality (∼2600 J/mol), whereas the data for the M3O5 binary suggest close to ideal behaviour. Received: 22 May 1998 / Accepted: 3 November 1998  相似文献   

4.
《Chemical Geology》2004,203(1-2):139-151
Aragonite is precipitated by a new CO2-diffusion technique from a Ca2+–Mg2+–Cl solution between 10 and 50 °C. Crystallisation of aragonite instead of calcite occurs by maintaining a [Mg2+]/[Ca2+] ratio of 2 in the fluid. The dissolved inorganic carbon (DIC) is received by diffusion of CO2 through a polyethylene membrane (diffusion coefficient: DCO2=10−6.4 cm2 s−1 at 19 °C). It is suggested that significant amounts of DIC may be transferred by diffusion of CO2 in natural systems if the CO2 gradient is high. The CO2-diffusion technique is used as a kind of simple mixed flow reactor for the co-precipitation of barium and strontium with aragonite. The distribution coefficients of Ba2+ and Sr2+ decrease from 10 to 50 °C according to DBa,a*=2.42−0.03595T (°C) and DSr,a*=1.32−0.005091T (°C). At 25 °C, the distribution coefficients are DBa,a*=1.5±0.1 and DSr,a*=1.19±0.03. The effect of temperature on DBa,a* is about one order of magnitude higher versus that on DSr,a*. Thus, Ba2+ may be a potential paleotemperature indicator if the composition of the solution is known.  相似文献   

5.
Epochs of changing atmospheric CO2 and seawater CO2–carbonic acid system chemistry and acidification have occurred during the Phanerozoic at various time scales. On the longer geologic time scale, as sea level rose and fell and continental free board decreased and increased, respectively, the riverine fluxes of Ca, Mg, DIC, and total alkalinity to the coastal ocean varied and helped regulate the C chemistry of seawater, but nevertheless there were major epochs of ocean acidification (OA). On the shorter glacial–interglacial time scale from the Last Glacial Maximum (LGM) to late preindustrial time, riverine fluxes of DIC, total alkalinity, and N and P nutrients increased and along with rising sea level, atmospheric PCO2 and temperature led, among other changes, to a slightly deceasing pH of coastal and open ocean waters, and to increasing net ecosystem calcification and decreasing net heterotrophy in coastal ocean waters. From late preindustrial time to the present and projected into the 21st century, human activities, such as fossil fuel and land-use emissions of CO2 to the atmosphere, increasing application of N and P nutrient subsidies and combustion N to the landscape, and sewage discharges of C, N, P have led, and will continue to lead, to significant modifications of coastal ocean waters. The changes include a rapid decline in pH and carbonate saturation state (modern problem of ocean acidification), a shift toward dissolution of carbonate substrates exceeding production, potentially leading to the “demise” of the coral reefs, reversal of the direction of the sea-to-air flux of CO2 and enhanced biological production and burial of organic C, a small sink of anthropogenic CO2, accompanied by a continuous trend toward increasing autotrophy in coastal waters.  相似文献   

6.
To understand the influence of fluid CO_2 on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth,we monitored the reaction between San Carlos olivine and a CO_2-rich NaCl fluid at 300 C and 500 bars.During the experiments,the total carbonic acid concentration(∑XO_2) in the fluid decreased from approximately 65 to 9 mmol/kg.Carbonate minerals,magnesite,and subordinate amount of dolomite were formed via the water-rock interaction.The H_2 concentration in the fluid reached approximately 39 mmol/kg within 2736 h,which is relatively lower than the concentration generated by the reaction between olivine and a CO2-free NaCl solution at the same temperature.As seen in previous hydrothermal experiments using komatiite,ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H_2 generation during the olivine alteration.Considering carbonate mineralogy over the temperature range of natural hydrothermal fields,H_2 generation is likely suppressed at temperatures below approximately 300℃ due to the formation of the Mg-bearing carbonates.Nevertheless,H_2 concentration in fluid at 300℃ could be still high due to the temperature dependency of magnetite stability in ultramafic systems.Moreover,the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth.Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO_2 species into the deep mantle.This process may have reduced the huge initial amount of CO_2 on the surface of the early Earth.Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO_2 carriers from the surface to the deep mantle,even in hot subduction zones.  相似文献   

7.
E.M.Levin,R,Kohlmuller et al.^[1]have reported the phase diagrams of the Bi2O3-TeO2 and Bi2O3-MoO3 binary oxide systems.This paper is intended to describe a new phase named chilunited-Bi6Te2Mo2O21 in the Chilu molybdenium ore deposit at Anxian County,Fujian Province.Because of small-sized mineral grans(-10μm),it is difficult to determine the crystal structure and physical properties of the mineral.According to its composition,we have successfully synthesized this new mineral using the fusion method.The synthesized single crystal,up to 700×300×300μm^3(0.063mm^3)in size,has been studied in great detail on its compositional and structural characteristics as well as physical properties.  相似文献   

8.
Natural barbosalite Fe2+Fe3+ 2 (PO4)2(OH)2 from Bull Moose Mine, South Dakota, U.S.A., having ideal composition, was investigated with single crystal X-ray diffraction techniques, Mössbauer spectroscopy and SQUID magnetometry to redetermine crystal structure, valence state of iron and evolution of 57Fe Mössbauer parameter and to propose the magnetic structure at low temperatures. At 298?K the title compound is monoclinic, space group P21/n, a o ?= 7.3294(16)?Å, b o ?=?7.4921(17)?Å, c o ?=?7.4148 (18)?Å, β?=?118.43(3)°, Z?=?2. No crystallographic phase transition was observed between 298?K and 110?K. Slight discontinuities in the temperature dependence of lattice parameters and bond angles in the range between 150?K and 180?K are ascribed to the magnetic phase transition of the title compound. At 298?K the Mössbauer spectrum of the barbosalite shows two paramagnetic components, typical for Fe2+ and Fe3+ in octahedral coordination; the area ratio Fe3+/Fe2+ is exactly two, corresponding to the ideal value. Both the Fe2+ and the Fe3+ sublattice order magnetically below 173?K and exhibit a fully developed magnetic pattern at 160?K. The electric field gradient at the Fe2+ site is distorted from axial symmetry with the direction of the magnetic field nearly perpendicular to Vzz, the main component of the electric field gradient. The temperature dependent magnetic susceptibility exhibits strong antiferromagnetic ordering within the corner-sharing Fe3+-chains parallel to [101], whereas ferromagnetic coupling is assumed within the face-sharing [1?1?0] and [?1?1?0] Fe3+-Fe2+-Fe3+ trimer, connecting the Fe3+-chains to each other.  相似文献   

9.
The configurational heat capacity, shear modulus and shear viscosity of a series of Na2O–Fe2O3–Al2O3–SiO2 melts have been determined as a function of composition. A change in composition dependence of each of the physical properties is observed as Na2O/(Na2O + Al2O3) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts. Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous, the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time. As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to the lack of charge-balancing cations for the Al-tetrahedra.  相似文献   

10.
To understand the influence of fluid CO2 on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth, we monitored the reaction between San Carlos olivine and a CO2-rich NaCl fluid at 300 °C and 500 bars. During the experiments, the total carbonic acid concentration (ΣCO2) in the fluid decreased from approximately 65 to 9 mmol/kg. Carbonate minerals, magnesite, and subordinate amount of dolomite were formed via the water-rock interaction. The H2 concentration in the fluid reached approximately 39 mmol/kg within 2736 h, which is relatively lower than the concentration generated by the reaction between olivine and a CO2-free NaCl solution at the same temperature. As seen in previous hydrothermal experiments using komatiite, ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H2 generation during the olivine alteration. Considering carbonate mineralogy over the temperature range of natural hydrothermal fields, H2 generation is likely suppressed at temperatures below approximately 300 °C due to the formation of the Mg-bearing carbonates. Nevertheless, H2 concentration in fluid at 300 °C could be still high due to the temperature dependency of magnetite stability in ultramafic systems. Moreover, the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth. Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO2 species into the deep mantle. This process may have reduced the huge initial amount of CO2 on the surface of the early Earth. Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO2 carriers from the surface to the deep mantle, even in hot subduction zones.  相似文献   

11.
The compound NaFeGe2O6 was grown synthetically as polycrystalline powder and as large single crystals suitable for X-ray and neutron-diffraction experiments to clarify the low temperature evolution of secondary structural parameters and to determine the low temperature magnetic spins structure. NaFeGe2O6 is isotypic to the clinopyroxene-type compound aegirine and adopts the typical HT-C2/c clinopyroxene structure down to 2.5?K. The Na-bearing M2 polyhedra were identified to show the largest volume expansion between 2.5?K and room temperature, while the GeO4 tetrahedra behave as stiff units. Magnetic susceptibility measurements show a broad maximum around 33?K, which marks the onset of low-dimensional magnetic ordering. Below 12?K NaFeGe2O6 transforms to an incommensurately modulated magnetic spin state, with k?=?[0.323, 1.0, 0.080] and a helical order of spins within the M1-chains of FeO6 octahedra. This is determined by neutron-diffraction experiments on a single crystal. Comparison of NaFeGe2O6 with NaFeSi2O6 is given and it is shown that the magnetic ordering in the latter compound, aegirine, also is complex and is best described by two different spin states, a commensurate one with C2??/c?? symmetry and an incommensurate one, best being described by a spin density wave, oriented within the (1 0 1) plane.  相似文献   

12.
The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H2O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al2O3 in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.  相似文献   

13.
The Chang'E-1 and Chang'E-2 missions have successfully obtained a huge amount of ltmar scientific data, through the seven onboard instruments including a CCD stereo camera, a laser altimeter, an interference imag- ing spectrometer, an X-ray spectrometer, a microwave radiometer, a high-energy particle detector and a solar-wind ion detector. Most of the Chang'E data are now publicly available to the science community, and this article serves as an official guide on how these data are classified and organized, and how they can be retrieved from http://159.226.88.59:7779/CE1OutENGWeb/. This article also presents the detailed specifications of various instru- ments and gives examples of research progress made based on these instruments.  相似文献   

14.
15.
Experimental uniaxial compression loading tests were conducted on molded gypsum and Carrara marble prismatic specimens to study the cracking and coalescence processes between pre-existing artificial flaws. The study showed that material had an influence on the cracking and coalescence processes (see the companion paper in this issue). As reported in the companion paper, one of the pronounced features as observed in the high-speed video recordings was the development of macroscopic white patches prior to the development of observable cracks in marble, but not in gypsum. This paper (part 2) deals with the microscopic aspects of the study. Specifically, the scanning electron microscope (SEM) and the environmental scanning electron microscope (ESEM) imaging techniques were used to study the microscopic development of white patches and their evolution into macroscopic tensile cracks and shear cracks in marble, and the microscopic initiation of hair-line tensile cracks and their evolution into macroscopic tensile cracks in gypsum. The microscopic imaging study in marble showed that the white patches were associated with extensive microcracking zones (process zones), while the extent of process zone development in gypsum was limited. The comparison of the macroscopic and microscopic results indicates that the different extent of microcracking zone development, related to the material textural properties, is a key factor leading to different macroscopic cracking behavior in gypsum and marble.
H. H. EinsteinEmail:
  相似文献   

16.
In this paper, the behaviors of aqueous zinc sorption by hydroxyapatite in the co-existence of Pb^2+, Cd^2+ and Cu^2+ are investigated, the effects of Pb^2+, Cd^2+ and Cu^2+ on the sorption of Zn^2+ are discussed, and the hydroxyapatite sorption capabilities for Pb^2+, Cd^2+, Cu^2+ and Zn^2+ are compared. The experimental results show that the Zn^2+ removal efficiency decreases gradually with the increase of the Cd^2+ concentration of the solution, and there is no sorption preference between Cd^2+ and Zn^2+. On the other hand, the Zn^2+ removal efficiency rapidly decreases rapidly with the increase of the Cu^2+ concentration of the solution, and there is a clear sorption preference between Cu^2+ and Zn^2+. It is noticed that the Zn^2+ removal efficiency is hardly changed with the variance of Pb^2+ concentration because the removal mechanisms for these two ions are totally different. It is concluded that the adsorption affinities of the heavy metals for the hydroxyapatite follows this sequence: pb^2+〉 Cu^2+〉 Cd^2+〉 Zn^2+.  相似文献   

17.
18.
Two synthetic series of spinels, MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 have been studied by Raman spectroscopy to investigate the effects of Fe2+ and Fe3+ on their structure. In the first case, where Fe2+ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A1g and Eg toward lower wavenumbers with the increase of the chromite component into the spinel, while the F2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe3+ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe3+ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe3+ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm?1, when observed, show little or negligible Raman shift.  相似文献   

19.
Chemical interaction processes among injected CO2, saline fluids and potential reservoir materials are experimentally simulated to derive dissolution rates of natural materials (minerals) that can be used as input parameters for modeling of CO2 storage in deep saline formations and risk analyses. In order to study dissolution processes, mineral aliquots were exposed to CO2-bearing brines at elevated temperature (60, 100, 150 °C) and pressure (85 bar) and at various run durations. Several potential reservoir rocks include carbonates as cement. Calcite and dolomite grains were therefore mainly used as solid starting material. Experiments with the two feldspar varieties alkali feldspar and almost pure anorthite were performed in addition. Grain sizes of the mineral starting materials varied between <63 μm and 500 μm with most experiments performed at grain size fractions of 160 – 250 μm and 250 – 500 μm. All experiments run with a complex synthetic brine (total dissolved solids: ∼156 g/l) according to a natural upper cretaceous formation water. Dry ice was used as CO2-source. All experiments were done in closed batch reactors. These reactors allow mimicking reservoir conditions far from the injection site as well as reservoir conditions after finishing the CO2 injection. The concentration changes during the experiment were monitored by ICP-OES measurements of the initial and the post-run fluids. Dissolution rates were derived based on the concentration changes of the brine.Most of the studied experimental variables and parameters (temperature, run duration, grain size, brine composition – expressed as pH-value and ionic strength) impact alteration of the reacting agents, i.e. they change the chemical composition of the brine, change the surfaces of the mineral aliquots exposed to the CO2-bearing brine, and induce formation of secondary minerals. Hence, all influencing parameters on dissolution processes have to be considered and time-resolved changes of the dissolution behavior have to be implemented in numerical simulations of processes at CO2 injection sites and CO2 storage reservoirs.  相似文献   

20.
The Jianchaling nickel deposit in the Bikou Terrane (Shaanxi Province, China) occurs along the boundaries between granite porphyry and carbonated ultramafic rocks (carbonated serpentinite, talc–carbonate rocks, and listwaenite). Serpentine– magnetite, serpentine– magnesite– magnetite, and magnesite– talc– quartz– pyrite– violarite– millerite– chalcopyrite assemblage formed in carbonated ultramafic rocks during hydrothermal activities. Ni-bearing sulphides, coexisting with magnesite, postdated magnetite in carbonated ultramafic rocks. Compared with serpentinite, Ni, Co, Cu, Mn, and Pb concentrate in talc–carbonate rocks. The fact that the NiO contents of magnetite decrease with progressive carbonation of serpentinite suggests that Ni from magnetite concentrated in fluid and contributed to the formation of the Jianchaling nickel deposit. Sulphides precipitated from fluid with log fO2 value varying from −34.5 to −31.8 and log fS2 value varying from −10.3 to −9.2. High pH and HS activities triggered by transformation of serpentine into magnesite–talc–quartz assemblage promoted precipitation of Ni-bearing sulphides, and finally formed the Jianchaling hydrothermal nickel deposit.  相似文献   

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