We have performed a series of interdiffusion experiments on magnesiowüstite samples at room pressure, temperatures from 1,320° to 1,400°C, and oxygen fugacities from 10?1.0 Pa to 10?4.3 Pa, using mixed CO/CO2 or H2/CO2 gases. The interdiffusion couples were composed of a single-crystal of MgO lightly pressed against a single-crystal of (Mg1-xFex)1-δO with 0.07<x<0.27. The interdiffusion coefficient was calculated using the Boltzmann–Matano analysis as a function of iron content, oxygen fugacity, temperature, and water fugacity. For the entire range of conditions tested and for compositions with 0.01<x<0.27, the interdiffusion coefficient varies as $$\tilde D\, =\,2.9\times10^{ - 6}\,f_{{\text{O}}_2 }^{0.19}\,x^{0.73}\,{\text{e}}^{ - (209,000\, -\,96,000\,x)/RT}\,\,{\text{m}}^{\text{2}} {\text{s}}^{ -1} $$These dependencies on oxygen fugacity and composition are reasonably consistent with interdiffusion mediated by unassociated cation vacancies. For the limited range of water activity that could be investigated using mixed gases at room pressure, no effect of water on interdiffusion could be observed. The dependence of the interdiffusion coefficient on iron content decreased with increasing iron concentration at constant oxygen fugacity and temperature. There is a close agreement between our activation energy for interdiffusion extrapolated to zero iron content (x=0) and that of previous researchers who used electrical conductivity experiments to determine vacancy diffusivities in lightly doped MgO. 相似文献
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, ao?= 7.3294(16)?Å, bo?=?7.4921(17)?Å, co?=?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
Ferrovalleriite, ideally 2(Fe,Cu)S · 1.5Fe(OH)2, a layered hydroxide-sulfide of the valleriite group and an analog of valleriite with Fe instead of Mg in the hydroxide block, has been approved by the IMA Commission on New Minerals, Nomenclature and Classification as a valid mineral species. It was found in the Oktyabr’sky Mine, Noril’sk, Krasnoyarsk krai, Siberia, Russia. Ferrovalleriite occurs in cavities of massive sulfide ore mainly consisting of cubanite and mooihoekite. In different cases, it is associated with magnetite, Fe-rich chlorite-like phyllosilicate, ferrotochilinite, hibbingite, or rhodochrosite. Ferrovalleriite forms crystals flattened on [001] (from scaly to tabular; up to 5 mm across and up to 0.3 mm thick), typically split and curved. Occasionally, they are combined into aggregates up to 1.5 × 2 cm. Ferrovalleriite is dark bronze-colored, with a metallic luster and black streak. The Mohs’ hardness is ca. 1; VHN is 35 kg/mm2. Cleavage is perfect parallel to {001}, mica-like. Individuals are flexible and inelastic. D(calc) = 3.72 g/cm3. In reflected light, ferrovalleriite is pleochroic from yellowish to gray; bireflectance is moderate. Anisotropy is strong, with bluish gray to yellowish beige rotation colors. Reflectance values [R1–R2 %, (λ, nm)] are: 15.6–16.6 (470), 14.8–20.5 (546), 14.7–22.3 (589), 14.5–24.1 (650). The IR spectrum shows the presence of (OH) groups bonded with Fe cations and the absence of H2O molecules. The chemical composition of the holotype (wt %; electron microprobe, H content is calculated) is as follows: 0.10 Al, 0.03 Mn, 45.31 Fe, 0.07 Ni, 18.29 Cu, 20.37 S, 15.62 O, 0.98 H, total is 100.77. The empirical formula calculated on the basis of 2 S atoms is: Al0.01Fe2.55Cu0.91S2(OH)3.07 = (Fe1.09Cu0.91)Σ2S2 · (Fe1.342+Fe0.123+Al0.01)Σ1.47(OH)3.07. The structure of ferrovalleriite is incommensurate (misfit); two sublattices are present: (1) sulfide sublattice, space group $R\bar 3m$, R3m or R32; the unit-cell dimensions are: a = 3.792(2), c = 34.06(3) Å, V = 424(1) Å3 and (2) hydroxide sublattice, space group $P\bar 3m1$, P3m1 or P321; the unit-cell dimensions: a = 3.202(3), c = 11.35(2)Å, V = 100.8(3) Å3. Together with this main polytype modification with three-layer (R-cell, Z = 3) sulfide block, the holotype ferrovalleriite contains the modification with one-layer (P-cell, Z = 1) sulfide block (sulfide sublattice with $P\bar 3m1$, P3m1 or P321, unit cell dimensions: a = 3.789(4), c = 11.35(1) Å, V = 141(5) Å3). The strongest reflections in the X-ray powder pattern (d, Å-I) are: 5.69–100; 3.268–58; 3.163–36; 1.894–34; 1.871–45. 相似文献
Despite a large number of studies of iron spin state in silicate perovskite at high pressure and high temperature, there is still disagreement regarding the type and P–T conditions of the transition, and whether Fe2+ or Fe3+ or both iron cations are involved. Recently, our group published results of a Mössbauer spectroscopy study of the iron behaviour in (Mg,Fe)(Si,Al)O3 perovskite at pressures up to 110 GPa (McCammon et al. 2008), where we suggested stabilization of the intermediate spin state for 8- to 12-fold coordinated ferrous iron ([8–12]Fe2+) in silicate perovskite above 30 GPa. In order to explore the behaviour in related systems, we performed a comparative Mössbauer spectroscopic study of silicate perovskite (Fe0.12Mg0.88SiO3) and majorite (with two compositions—Fe0.18Mg0.82SiO3 and Fe0.11Mg0.88SiO3) at pressures up to 81 GPa in the temperature range 296–800 K, which was mainly motivated by the fact that the oxygen environment of ferrous iron in majorite is quite similar to that in silicate perovskite. The [8–12]Fe2+ component, dominating the Mössbauer spectra of majorites, shows high quadrupole splitting (QS) values, about 3.6 mm s?1, in the entire studied P–T region (pressures to 58 GPa and 296–800 K). Decrease of the QS of this component with temperature at constant pressure can be described by the Huggins model with the energy splitting between low-energy eg levels of [8–12]Fe2+ equal to 1,500 (50) cm?1 for Fe0.18Mg0.82SiO3 and to 1,680 (70) cm?1 for Fe0.11Mg0.88SiO3. In contrast, for the silicate perovskite dominating Mössbauer component associated with [8–12]Fe2+ suggests the gradual change of the electronic properties. Namely, an additional spectral component with central shift close to that for high-spin [8–12]Fe2+ and QS about 3.7 mm s?1 appeared at ~35 (2) GPa, and the amount of the component increases with both pressure and temperature. The temperature dependence of QS of the component cannot be described in the framework of the Huggins model. Observed differences in the high-pressure high-temperature behaviour of [8–12]Fe2+ in the silicate perovskite and majorite phases provide additional arguments in favour of the gradual high-spin—intermediate-spin crossover in lower mantle perovskite, previously reported by McCammon et al. (2008) and Lin et al. (2008). 相似文献
The Fe M2,3-edge spectra of solid solutions of garnets (almandine-skiagite Fe3(Al1–xFex)2[SiO4]3 and andradite-skiagite (Fe1–xCax)3Fe2[SiO4]3), pyroxenes (acmite-hedenbergite (Ca1–xNax)(Fe2+1−xFe3+x)Si2O6), and spinels (magnetite-hercynite Fe(Al1–xFex)2O4) have been measured using the technique of parallel electron energy-loss spectroscopy (EELS) conducted in a transmission
electron microscope (TEM). The Fe M2,3 electron energy-loss near-edge structures (ELNES) of the minerals exhibit a characteristic peak located at 4.2 eV and 2.2 eV
for trivalent and divalent iron, respectively, prior to the main maximum at about 57 eV. The intensity and energy of the pre-edge
feature varies depending on Fe3+/ΣFe. We demonstrate a new quantitative method to extract the ferrous/ferric ratio in minerals. A systematic relationship
between Fe3+/ΣFe and the integral intensity ratio of the main maximum and the pre-edge peak of the Fe M2,3 edge is observed. Since the partial cross sections of the Fe M2,3 edges are some orders of magnitude higher than those of the Fe L2,3 edges, the Fe M2,3 edges are interesting for valence-specific imaging of Fe. The possibility of iron valence-specific imaging is illustrated
by Fe M2,3-ELNES investigations with high lateral resolution from a sample of ilmenite containing hematite exsolution lamellae that
shows different edge shapes consistent with variations in the Fe3+/ΣFe ratio over distances on the order of 100 nm.
Received: 14 April 1998 / Revised, accepted: 8 March 1999 相似文献
Iron (Fe) and manganese (Mn) are the two most common redox-active elements in the Earth’s crust and are well known to influence mineral formation and dissolution, trace metal sequestration, and contaminant transformations in soils and sediments. Here, we characterized the reaction of aqueous Fe(II) with pyrolusite (β-MnO2) using electron microscopy, X-ray diffraction, aqueous Fe and Mn analyses, and 57Fe Mössbauer spectroscopy. We reacted pyrolusite solids repeatedly with 3 mM Fe(II) at pH 7.5 to evaluate whether electron transfer occurs and to track the evolving reactivity of the Mn/Fe solids. We used Fe isotopes (56 and 57) in conjunction with 57Fe Mössbauer spectroscopy to isolate oxidation of Fe(II) by Fe(III) precipitates or pyrolusite. Using these complementary techniques, we determined that Fe(II) is initially oxidized by pyrolusite and that lepidocrocite is the dominant Fe oxidation product. Additional Fe(II) exposures result in an increasing proportion of magnetite on the pyrolusite surface. Over a series of nine 3 mM Fe(II) additions, Fe(II) continued to be oxidized by the Mn/Fe particles suggesting that Mn/Fe phases are not fully passivated and remain redox active even after extensive surface coverage by Fe(III) oxides. Interestingly, the initial Fe(III) oxide precipitates became further reduced as Fe(II) was added and additional Mn was released into solution suggesting that both the Fe oxide coating and underlying Mn phase continue to participate in redox reactions when freshly exposed to Fe(II). Our findings indicate that Fe and Mn chemistry is influenced by sustained reactions of Fe(II) with Mn/Fe oxides.
Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of
MgO in contact with (Mg0.73Fe0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe
analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For
a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in FexMg1−xO with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol−1. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced
rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of
hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the
lower mantle.
The partitioning of Fe2+ and Mn2+ between (Fe, Mn)TiO3 and (Fe, Mn)2SiO4 solid solutions in the system FeO-MnO-TiO2-SiO2 has been experimentally investigated at 1100 ∘C and pressures of 1 bar and 25 kbar, over a wide range of Fe/Mn ratios, using electron microprobe analysis of quenched run
products. The ilmenite solid solution in this system is within analytical uncertainty a simple binary between FeTiO3 and MnTiO3, but the olivine solid solution appears to contain up to 2.5 wt% TiO2. The Fe-Mn partitioning results constrain precisely the difference in the thermodynamic mixing properties of the two solid
solutions. If the mixing properties of (Fe, Mn)2SiO4 solid solutions are assumed to be ideal, as experimentally determined by Schwerdtfeger and Muan (1966), then the ilmenite
is a regular, symmetric solution with W ilmFe-Mn=1.8±0.1 kJ mol−1. The quoted uncertainty does not include the contribution from the uncertainty in the mixing properties of the olivine solution,
which is estimated to be ±1.8 kJ mol−1, and which therefore dominates the uncertainty in the present results. Nevertheless, this result is in good agreement with
the previous experimental study of O'Neill et al. (1989), who obtained W ilmFe-Mn=2.2±0.3 kJ mol−1 from an independent method. The results provide another item of empirical evidence supporting the proposition that solid
solutions between isostructural end-members, in which order-disorder effects are not important, generally have simple thermodynamic
mixing properties, with little asymmetry, modest excess entropies, and excess enthalpies approximately proportional to the
difference in the molar volumes of the end-members.
Received: 11 February 1998 / Accepted: 29 June 1998 相似文献
Summary In the Nuggihalli schist belt (India), chromite bodies were affected by intense serpentinization followed by weathering. In spite of the strong oxidation of the chromite grains, some unaltered cores were preserved, and they were characterised using electron probe microanalysis, single-crystal X-ray diffraction and low temperature 57Fe Mössbauer spectroscopy. Results of such investigations revealed that chromite cores from the Nuggihalli schist belt are effectively not oxidised, and their study revealed that chromite was not affected by greenschist-facies metamorphism. The apparently highly ordered cation distribution of the chromites, which would suggest low equilibration temperature, is just caused by the very high Cr contents, which prevent Mg–Al exchange between T and M sites. Using Fabries (1979) geothermometer a temperature of about 1180°C was retrieved (Mitra and Bidyananda, 2003), which therefore corresponds to the quenched-in igneous equilibrium. 相似文献
考察不同因素对异化铁还原菌(Dissimilatory Iron Reducing Bacteria,DIRB)还原高岭土中Fe(Ⅲ)的影响,通过在底液中添加不同有机酸、草酸盐、络合剂和重金属离子来研究微生物还原铁的机制。结果发现,添加草酸对微生物还原铁有明显的促进作用,而乙酸和水杨酸则抑制了微生物的生长;添加草酸钠的实验表明草酸对微生物的促进作用是通过草酸根离子的作用而与草酸的酸性并无联系;络合剂(NTA)可以提高微生物异化铁还原量,而EDTA不影响铁还原的作用;Cu(Ⅱ)对微生物具有毒害作用从而抑制了微生物的还原活性,Mn(Ⅱ)对铁的还原则有明显的促进作用。此外,采用logistic方程对有促进作用的曲线进行拟合,发现添加草酸钠对微生物的还原铁促进作用最大。 相似文献
Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach??the pilot ion method??has not been documented in detail.
Results
A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II) and Mn(II), subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II) to Fe(II) varied by no more than 11% from one Hg/Au electrode to another and Fe(II) concentrations predicted by the Mn(II) pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15???M Fe(II) (46% different on average). The ratio of calibration slopes of Mn(II) to S(?II) varied by almost 20% from one Hg/Au electrode to another, and S(?II) predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II) and S(?II) concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At medium-to-high concentration for the ocean, naturally derived dissolved organic carbon did not significantly affect the baseline-corrected electrode response of Mn(II) and Fe(II), but did significantly affect the response of S(?II).
Conclusions
Despite their intrinsic variability, Hg/Au electrodes fabricated by hand can be used to quantify O2, S(?II), Fe(II), and Mn(II) without calibrating every electrode for every constituent of interest. The pilot ion method can achieve accuracies to within 20% or less, provided that the underlying principle??the independence of slope ratios??is demonstrated for all voltammetric techniques used, and effects of the physicochemical properties of the system on voltammetric signals are addressed through baseline subtraction. 相似文献
The Sin Quyen Cu–Fe–Au–REE deposit is localized in the Proterozoic deposits of the Phan Xi Pang zone, northern Vietnam. The mineralization is formed by lenticular and sheet-like bodies occurring concordantly with the host rocks. Seventeen orebodies have been recognized in the deposit, which form an ore horizon up to 140 m in total thickness, about 2 km in strike, and up to 350 m in dip. The ores are of simple mineral composition: Au-rich copper and iron sulfides (chalcopyrite, pyrite, pyrrhotite) and iron oxides (magnetite, hematite). Gold and silver are distributed unevenly in the ores: Their contents vary from hundredths and tenths of ppm to 1.8 ppm. Copper sulfide ores are the main concentrator of gold and silver. All ores are characterized by high REE contents, tens and hundreds of times exceeding the element clarkes. The highest contents have been revealed for Ce and La. Orthite is the main carrier of REE. No correlation between REE and ore elements of sulfide-oxide ores has been revealed, which points to the independent formation of the mineralization. Orebodies together with the host rocks underwent metamorphism at 500–600 to 630–685 °C and 3–7 kbar. The spatial association of the mineralization with amphibolites (metamorphosed basites) and the mineral composition of ores suggest that the Sin Quyen deposit is of Cyprian volcanogenic type. 相似文献
The mineralogical and chemical evolution of ochreous precipitates forming from acid mine drainage (AMD) from the abandoned Libiola Fe–Cu-sulfide mine (Eastern Liguria, Italy) was followed through a multianalytical approach (XRD, TEM, XRF, ICP) applied to surface precipitates and associated waters collected from several mine adits. The mineralogy of the precipitates changed significantly as a consequence of the variations of the chemical parameters of the circulating solutions (mainly pH, Eh, and sulfate concentrations) which, in turn, were mainly controlled by mixing with unpolluted stream and rill waters of the mining area. A progressive transition from jarosite-, to schwertmannite-, to goethite-, to ferrihydrite-, to amorphous-dominated precipitates was observed, mainly as a consequence of an increase in the pH of the associated solutions. This mineralogical evolution agrees well with the aqueous speciation and Eh–pH stability calculations performed on the waters associated with the different precipitate types. Furthermore, TEM analysis indicated that metastable pristine phases (schwertmannite) tend to transform progressively to well-crystallized more stable species, here represented by goethite. The comparison of the water chemistry and the crystal chemistry of the different precipitates showed a significant decrease in the Zn, Cu, Ni, Co contents in waters where the coexisting precipitates were almost exclusively composed of goethite. The distribution of V, Sr, As concentrations within the different precipitates showed that the most efficient scavenging phase for these elements was jarosite, whereas ferrihydrite efficiently took up Pb ions, and schwermannite acted as a natural sink for Cr. 相似文献
在Franckeit矿物中发现了一种新型硫化物(Zn0.5 Mn0.25 Fe0.25) S,用电子衍射、微区分析和高分辨结构像,证明它是一种ZnS型结构的多型体,其堆积序列为……AB AB AB AB CA……,其成分由X光能谱测定为:34.9±0.1％Zn,15.5±0.1％Fe,14.8±0.1％Mn,34.7±0.1％S。 相似文献
