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1.
Zero-valent iron (Fe0), as an alternative iron source, was evaluated to activate persulfate (PS) to degrade acetaminophen (APAP), a representative pharmaceutically active compound in water. Effects of key factors in the so-called Fe0/PS process, including Fe0 dosage, initial pH, temperatures and chelating agents, were studied. Under all the conditions tested, the APAP degradation followed a pseudo-first-order kinetics pattern. The degradation efficiency of APAP was highest when the Fe0 to PS molar ratio increased to 1:1, and the degradation rate constant and removal were 23.19 × 10?3 min?1 and 93.19 %, respectively. Comparing with Fe2+, Fe0 served as an alternative iron source that can gradually release Fe2+ into water, thereby consistently activating PS to produce sulfate radicals. The Fe0/PS system was effective in a broader pH range from 3 to 8.5. Heat could facilitate production of sulfate radicals and enhance the APAP degradation in the Fe0/PS system. High reaction temperature also improved the Fe2+/PS oxidation of APAP. Finally, sodium citrate (a chelating agent) at an appropriate concentration could improve the APAP degradation rate in the Fe2+/PS and Fe0/PS system. The optimal molar ratio of Fe0 to citrate depended on solution pH. Our results demonstrated that Fe0 was an alternative iron source to activate PS to degrade APAP in water.  相似文献   

2.
Samples with eclogitic composition in the system CaO–FeO–Fe2O3–MgO–Al2O3–SiO2 were produced from various kinds of starting materials held in graphite-lined Pt capsules at a pressure of 2.5–3.0 GPa and temperatures of 800–1,300 °C using a piston-cylinder or Belt apparatus. Garnets and clinopyroxenes were characterized by analytical transmission electron microscopy and electron probe micro-analysis (EPMA). Fe3+/ΣFe ratios determined by electron energy-loss spectroscopy (EELS) decrease in clinopyroxene from 22.2 ± 3.4 % at 800 °C to 13.3 ± 5.4 % at 1,300 °C, while in garnet, they vary between 10.8 ± 1.5 and 15.4 ± 4.7 %, respectively. Temperature estimates according to Krogh (Contrib Mineral Petrol 99:44–48, 1988) reproduce the experimental temperature to ±60 °C without systematic deviations if total iron is used in the calculation. If only the Fe2+ content is used, which was obtained by combining EPMA and EELS results, the experimental temperature is underestimated by 33 °C on average at 800–1,200 °C and overestimated by 77 °C on average at 1,300 °C. These systematic deviations can be explained by the temperature-dependent ratio of Fe2+/ΣFe in garnet divided by that in clinopyroxene. Since the difference between the calculated and experimental temperature is relatively small, a Fe2+-based recalibration of the thermometer appears not to be necessary for the investigated system in the range of pressure, temperature and composition covered by the experiments of this study.  相似文献   

3.
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   

4.
We report application of the flank method using the electron microprobe to a suite of twelve (Mg,Fe)O samples with composition 2–47 wt% Fe and Fe3+/ΣFe = 1 to 11%, where Fe3+/ΣFe was determined independently using Mössbauer spectroscopy on the same grains used for the flank method measurements. A calibration curve of the form Fe2+ = A + B × (ΣFe)2 + C × (Lβ/Lα) was fit to the data and gave excellent agreement between Fe3+/ΣFe calculated from the flank method and Fe3+/ΣFe determined using Mössbauer spectroscopy. We found the method to be sufficiently sensitive to determine meaningful variations in Fe3+/ΣFe for geophysically relevant compositions of (Mg,Fe)O (<25 wt% Fe), and calibration parameters remained constant within experimental uncertainty over the course of the entire study (20 months). Flank method measurements on an inhomogeneous sample of synthetic (Mg,Fe)O showed evidence of diffusion processes resulting from rupture of the capsule during the high-pressure experiment and the possibility to measure Lβ/Lα variations with a spatial resolution of a few microns. We detected the presence of exsolved magnesioferrite in a suite of (Mg,Fe)O single crystals using transmission electron microscopy and Mössbauer spectroscopy. Flank method measurements on the same suite of single crystals showed enhanced Fe3+/ΣFe values, consistent with the presence of magnesioferrite even though the grains were too small to be resolved by conventional electron microprobe measurements.  相似文献   

5.
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   

6.
Application of advanced oxidation process for wastewater treatment has gained more attention recently. In this study, the efficiency of coagulation–flocculation pretreatment coupled with sulfate radical-based advanced oxidation process (SR-AOP) in the removal and mineralization of organic matter of sugarcane vinasse was evaluated. For coagulation–flocculation, jar-test experiment was carried out with ferric chloride as coagulant and the removal of TOC, color and UV254 was determined. The results revealed that by using 15 g/L of coagulant, 70 % of TOC removal and nearly 100 % of UV254 and color removal were achieved. The pretreated vinasse was then subjected to SR-AOP. In this study, sulfate radical was generated using persulfate (PS) and peroxymonosulfate (PMS) activated by Fe(II). The effect of reaction time, oxidants to Fe(II) ratio and pH on the TOC removal efficiency were investigated. For the effect of reaction time, the TOC removal was found to increase significantly for the first 5 min. TOC removal was found to increase with increasing concentration of Fe(II) for PMS. However, for Fe(II)/PS, the TOC removal efficiency was decreased with increasing Fe(II) concentration. Both Fe(II)/PMS and Fe(II)/PS showed the highest TOC removal efficiency when the oxidation was carried out at pH 7. By using the selected optimum condition, nearly 70 and 49 % of TOC removal were achieved for PMS/Fe(II) and PS/Fe(II), respectively. Therefore, it can be concluded that SR-AOP can be a promising alternative method for TOC removal from sugarcane vinasse.  相似文献   

7.
Experimental studies of the Fe0–(Mg, Ca)CO3–S system were carried out during 18–20 h at 6.3 GPa, 900–1400°C. It is shown that the major processes resulting in the formation of free carbon include reduction of carbonates upon redox interaction with Fe0 (or Fe3C), extraction of carbon from iron carbide upon interaction with a sulfur melt/fluid, and reduction of the carbonate melt by Fe–S and Fe?S–C melts. Reconstruction of the processes of graphite formation indicates that carbonates and iron carbide may be potential sources of carbon under the conditions of subduction, and participation of the sulfur melt/fluid may result in the formation of mantle sulfides.  相似文献   

8.
A phenanthrene-degrading strain PHE3, identified as the genus of Sphingobium, was isolated using a two-liquid-phase partitioning bioreactor. More than 96 % of the initial amount (up to 100 mg l?1 silicone oil) of phenanthrene was removed within 77 h by PHE3. Degradation of phenanthrene by PHE3 at pH 7 was also observed in the presence of Cu (II), Zn (II) and Cd (II) ions. Cu (II) showed the highest toxicity to PHE3, followed by Cd (II) and Zn (II). Tolerance to Cu (II) by PHE3 was up to 20 mg l?1 in terms of total aqueous concentration, and up to 40 mg l?1 for both Zn and Cd. Interestingly, 20 mg l?1 of Zn (II) stimulated phenanthrene degradation after 20 h incubation. Its high tolerance to toxic metals and phenanthrene degradation ability of PHE3 highlights its significance in the study of microbial remediation in soils co-polluted by PAHs and metals.  相似文献   

9.
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   

10.
A batch nitrification process was studied using synthetic wastewater as substrate and Chilean natural zeolite as biomass carrier at ambient temperatures (20 °C). Three groups of experiments were carried out: a first experimental set (I) with and without added zeolite using initial biomass concentrations of 1,000 and 2,000 mg VSS/L; a second set of experiments (II) with added zeolite and at the same initial biomass concentrations. In these two experimental sets, biomass from an activated sludge process located in an urban wastewater treatment plant at La Farfana, Santiago de Chile, was used as inoculum (1). Finally, a third set of experiments (III) was carried out with zeolite at an initial biomass concentration of 1,000 mg VSS/L using an inoculum derived from an activated sludge process treating wastewater from a paper mill (inoculum 2). Nitrifying biomass concentration values in the range of 13,000–18,800 mg VSS/L were achieved when initial biomass concentrations varied between 1,000 and 2,000 mg VSS/L. Inoculum (1) generated higher biomass concentrations than inoculum (2). Ammonium N removals higher than 70 % were obtained in experimental sets II and III when zeolite was used. For both initial biomass concentrations tested, an exponential biomass growth was observed up to the second day of operation, and a slight decrease was evident afterwards, achieving stationary values after 10–12 days of operation. The third experimental set (III) revealed that the highest N consumption took place between days 11 and 16 of digestion.  相似文献   

11.
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   

12.
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   

13.
《Geochimica et cosmochimica acta》1999,63(19-20):3417-3427
In order to verify Fe control by solution - mineral equilibria, soil solutions were sampled in hydromorphic soils on granites and shales, where the occurrence of Green Rusts had been demonstrated by Mössbauer and Raman spectroscopies. Eh and pH were measured in situ, and Fe(II) analyzed by colorimetry. Ionic Activity Products were computed from aqueous Fe(II) rather than total Fe in an attempt to avoid overestimation by including colloidal particles. Solid phases considered are Fe(II) and Fe(III) hydroxides and oxides, and the Green Rusts whose general formula is [FeII1−xFeIIIx(OH)2]+x· [x/z A−z]−x, where compensating interlayer anions, A−, can be Cl−, SO42−, CO32− or OH−, and where x ranges a priori from 0 to 1. In large ranges of variation of pH, pe and Fe(II) concentration, soil solutions are (i) oversaturated with respect to Fe(III) oxides; (ii) undersaturated with respect to Fe(II) oxides, chloride-, sulphate- and carbonate-Green Rusts; (iii) in equilibrium with hydroxy-Green Rusts, i.e., Fe(II)-Fe(III) mixed hydroxides. The ratios, x = Fe(III)/Fet, derived from the best fits for equilibrium between minerals and soil solutions are 1/3, 1/2 and 2/3, depending on the sampling site, and are in every case identical to the same ratios directly measured by Mössbauer spectroscopy. This implies reversible equilibrium between Green Rust and solution. Solubility products are proposed for the various hydroxy-Green Rusts as follows: log Ksp = 28.2 ± 0.8 for the reaction Fe3(OH)7 + e− + 7 H+ = 3 Fe2+ + 7 H2O; log Ksp = 25.4 ± 0.7 for the reaction Fe2(OH)5 + e− + 5 H+ = 2 Fe2+ + 5 H2O; log Ksp = 45.8 ± 0.9 for the reaction Fe3(OH)8 + 2e− + 8 H+ = 3 Fe2+ + 8 H2O at an average temperature of 9 ± 1°C, and 1 atm. pressure. Tentative values for the Gibbs free energies of formation of hydroxy-Green Rusts obtained are: ΔfG° (Fe3(OH)7, cr, 282.15 K) = −1799.7 ± 6 kJ mol−1, ΔfG° (Fe2(OH)5, cr, 282.15 K) = −1244.1 ± 6 kJ mol−1 and ΔfG° (Fe3(OH)8, cr, 282.15 K) = −1944.3 ± 6 kJ mol−1.  相似文献   

14.
The thermally induced reductive decomposition of a natural near end-member almandine [VIII(Fe2.85Mg0.11Ca0.05Mn0.02)VI(Al1.99)IV(Si2.99)O12] and possible hydrogen diffusion into its structure have been carried out at temperatures up to 1,200°C, monitored by simultaneous thermogravimetric analysis and differential scanning calorimetry (DSC), infrared and 57Fe Mössbauer spectroscopy and X-ray powder diffraction. Below 1,000°C, evidence for hydrogen diffusion into almandine structure was not observed. At temperatures above 1,000°C, reductive decomposition sets in, as displayed by a sharp endothermic peak at 1,055°C on the DSC curve accompanied by a total mass loss of 3.51%. We observe the following decomposition mechanism: almandine + hydrogen → α-Fe + cristobalite + hercynite + water. At higher temperatures, fayalite and sekaninaite are formed by consecutive reaction of α-Fe with cristobalite and water, and cristobalite with hercynite, respectively. The metallic α-Fe phase forms spherical and isolated particles (~1 μm).  相似文献   

15.
Heat treatment was performed on selected Fe-dominant tourmalines to establish the nature of any change in optical properties. Two tourmaline samples from Dolní Bory, Czech Republic (TDB) and Vlachovo, Slovakia (TVL) were heated at 450, 700 and 900°C at 0.1 mPa and ambient oxidation conditions for 8 h. EMPA study shows that tourmaline from Vlachovo has schorlitic composition and tourmaline from Dolní Bory is alkali-depleted schorl to foitite. Although the black colour remained unchanged after heating at 450°C, it changed to brown at 700°C and reddish brown at 900°C. No significant changes of chemical composition were observed during heating. X-ray diffraction, infrared and Mössbauer study showed negligible oxidation of tourmaline heated at 450°C, but a significant change in iron valency state and deprotonization at 700°C. The oxidation of Fe is the main cause of tourmaline colour change, and the substitution vector for oxidation of Fe is Fe3+OFe ?1 2+ (OH)?1. The predicted deprotonization of OH was confirmed by infrared spectroscopy, which documented a decrease in OH groups in both samples, mainly at the V site. The oxidation of Fe is mostly significant in the Y site as documented on the compression of the Y-site octahedra and subsequent decrease in the a lattice parameter. This feature is consistent with lattice dimensions in the transition from schorl and foitite dimensions to those consistent with fluor-buergerite. The Z-site octahedra did not compressed and were not affected by heating-induced Fe oxidation, which indicates only negligible content of Z Fe2+ in original samples. After heating at 900°C, the tourmaline structure collapsed likely due to the thermally induced weakening of bonds in Y and Z octahedra, which results in amorphization of tourmaline. Subsequently, breakdown products including Fe-oxides and mullite replaced alkali-depleted amorphized tourmaline.  相似文献   

16.
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   

17.
A sulfide chimney ore sampled from the flank of the active Tiger vent area in the Yonaguni Knoll IV hydrothermal field, south Okinawa trough, consists of anhydrite, pyrite, sphalerite, galena, chalcopyrite and bismuthinite. Electron microprobe analysis indicates that the chalcopyrite contains up to 2.4 wt% Sn, whereas bismuthinite contains up to 1.7 wt% Pt, 0.8 wt% Cu and 0.5 wt% Fe. The Sn‐rich chalcopyrite and Pt–Cu–Fe‐bearing bismuthinite are the first reported occurrence of such minerals in an active submarine hydrothermal system. The results confirm that Sn enters the chalcopyrite as a solid solution towards stannite by the coupled substitution of Sn4+Fe2+ for Fe3+Fe3+, whereas Pt, Cu and Fe enter the bismuthinite structure as a solid solution during rapid nucleation. The fluid inclusions homogenization temperatures in anhydrite (220–310°C) and measured end‐member temperature of the vent fluids on‐site (325°C) indicate that Sn‐bearing chalcopyrite and Pt–Cu–Fe‐bearing bismuthinite express the original composition of the minerals that precipitated as metastable phases at a temperature above 300°C. The result observed in this study implies that sulfides in ancient volcanogenic massive sulfide deposits have similar trace element distribution during nucleation but it is remobilised during diagenesis, metamorphism or supergene enrichment processes.  相似文献   

18.
Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO3 perovskite more accurately, we synthesized single crystals of Mg0.946(17)Fe0.056(12)Si0.997(16)O3 perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe2+ and Fe3+) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O3 perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations.  相似文献   

19.
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   

20.
Mechanism and kinetics of hydrothermal replacement of magnetite by hematite   总被引：1，自引：1，他引：0  
The replacement of magnetite by hematite was studied through a series of experiments under mild hydrothermal conditions(140 -220℃, vapour saturated pressures) to quantify the kinetics of the transformation and the relative effects of redox and non-redox processes on the transformation. The results indicate that oxygen is not an essential factor in the replacement reaction of magnetite by hematite, but the addition of excess oxidant does trigger the oxidation reaction, and increases the kinetics of the transformation. However, even under high O_2(aq) environments, some of the replacement still occurred via Fe2+ leaching from magnetite. The kinetics of the replacement reaction depends upon temperature and solution parameters such as pH and the concentrations of ligands, all of which are factors that control the solubility of magnetite and affect the transport of Fe2+ (and the oxidant) to and from the reaction front. Reaction rates are fast at ~200℃, and in nature transport properties of Fe and,in the case of the redox-controlled replacement, the oxidant will be the rate-limiting control on the reaction progress. Using an Avrami treatment of the kinetic data and the Arrhenius equation, the activation energy for the transformation under non-redox conditions was calculated to be 26 ± 6 kJ mol-1.This value is in agreement with the reported activation energy for the dissolution of magnetite, which is the rate-limiting process for the transformation under non-redox conditions.  相似文献   

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