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1.
Equilibria between different valence states of Fe and Mn have been studied in a microcline-plagioclase-quartz gneiss which locally contains ferromagnesian minerals unusually high in Mn+3 and Fe+3 and low in Fe+2. The compositions of coexistent minerals have been determined by chemical and microprobe analyses. The minerals in some layers were formed under highly-oxidizing conditions, as indicated by extremely low Fe+2/Fe+3 ratios in the silicates, by the presence of hematite, and by the occurrence of piemontite, which requires Mn+3 for its formation. The minerals in other layers were formed under less-oxidizing conditions, as indicated by the fact that epidote, rather than piemontite, crystallized with Mn-rich garnet and by the presence of biotite rather than phlogopite. In the less-oxidized layers Mn+3 appears to be absent. The differences in oxidation of Fe and Mn occur between adjacent layers and probably reflect sedimentary differences preserved despite the metamorphism.Iron and manganese with different valences are sharply partitioned between the coexisting phases. In highly-oxidized layers, muscovite contains more iron (as Fe+3) than coexistent phlogopite; in piemontite most of the manganese is Mn+3, while in coexistent garnet most of the manganese is Mn+2. In less-oxidized layers, epidote contains no Mn+3 and contains less Mn+2 than coexistent garnet, biotite, or amphibole. Analytical data, crystal-chemical arguments, and characteristics of Fe and Mn L-spectra indicate that in coexistent garnet and piemontite, Fe+2, Fe+3, Mn+2, and Mn+3 are present, in spite of the fact that trivalent manganese strongly oxidizes divalent iron in aqueous solution under normal conditions.Contribution No. 1468.  相似文献   

2.
Summary The orange cathodoluminescence (CL) of calcite is known to be due to the presence of Mn2+ cations. It has been demonstrated here using CL and electron paramagnetic resonance (EPR) crossed analysis from synthetic calcite that neither Fe2+ nor Fe3+ ions influence this luminescence emission. More complex natural calcium carbonates have been investigated to check whether or not this conclusion can be applied to them. For this purpose, different white marbles from Greek quarries were analysed with CL. The data are completed with neutron activation analysis (NAA) for manganese and iron contents. Again it is shown that only manganese plays a role in the orange CL of these white marbles. This result provides an important clue in the wide field of provenance determination of calcium carbonate used in ancient art.Received February 19, 2002; revised version accepted October 22, 2002 Published online March 10, 2003  相似文献   

3.
The control of cathodoluminescence in dolomite by iron and manganese   总被引：10，自引：0，他引：10  
Variations in the cathodoluminescent properties of carbonates are usually attributed to differing proportions of manganese (Mn2+) as the most important activator, and iron (Fe2+) as the main inhibitor of luminescence. Interactions between manganese and iron concentrations and the luminescent properties of dolomite are demonstrated by petrographic and chemical analyses of 86 samples of dolomite representing a range of depositional environments and ages (Cambrian to Cretaceous) and a wide geographical distribution (North America and Europe). Iron and manganese are positively correlated in the dolomites, with the former showing a greater range of variation. Very small amounts of manganese are sufficient to activate the luminescence and as little as 100 ppm Mn2+ is present in highly luminescing samples. The intensity of luminescence is not proportional to the manganese concentration. Iron begins to quench luminescence as its concentration reaches 10,000 ppm. Above that level, luminescence is rapidly lost and total extinction occurs among samples containing more than 15,000 ppm Fe2+, regardless of the manganese concentration.  相似文献   

4.
Estimates of early atmosphere compositions from metamorphosed banded iron formations(BIFs)including the well-studied ≥3.7 BIFs of the Isua supracrustal belt(Greenland)are dependent on knowledge of primary versus secondary Fe-mineralogical assemblages.Using new observations from locally well preserved domains,we interpret that a previously assumed primary redox indicator mineral,magnetite,is secondary after sedimentary Fe-clays(probably greenalite)±carbonates.Within ~3.7 Ga Isua BIF,pre-tectonic nodules of quartz+Fe-rich amphibole±calcite reside in a finegrained(≤100 μm)quartz+magnetite matrix.We interpret the Isua nodule amphibole as the metamorphosed equivalent of primary Fe-rich clays,armoured from diagenetic oxidative reactions by early silica concretion.Additionally,in another low strain lacunae,~3.76 Ga BIF layering is not solid magnetite but instead fine-grained magnetite+quartz aggregates.These magnetite+quartz aggregates are interpreted as the metamorphosed equivalent of Fe-clay-rich layers that were oxidised during diagenesis,because they were not armoured by early silicification.In almost all Isua BIF exposures,this evidence has been destroyed by strong ductile deformation.The Fe-clays likely formed by abiotic reactions between aqueous Fe~(2+)and silica.These clays along with silica±carbonate were deposited below an oceanic Fe-chemocline as the sedimentary precursors of BIF.Breakdown of the clays on the sea floor may have been by anaerobic oxidation of Fe~(2+),a mechanism compatible with iron isotopic data previously published on these rocks.The new determinations of the primary redoxsensitive Fe-mineralogy of BIF significantly revise estimates of early Earth atmospheric oxygen and CO_2 content,with formation of protolith Fe-rich clays and carbonates compatible with an anoxic Eoarchean atmosphere with much higher CO_2 levels than previously estimated for Isua and in the present-day atmosphere.  相似文献   

5.
Mössbauer spectroscopy has been used widely to characterize the ferric (Fe3+) and ferrous (Fe2+) proportions and coordination of solid materials. To obtain these accurately, the recoilless fraction is indispensible. The recoilless fractions (f) of iron-bearing minerals, including oxides, oxyhydroxides, silicates, carbonates, phosphates and dichalcogenides, and silicate glasses were evaluated from the temperature dependence of their center shifts or absorption area with the Debye model approximation. Generally, the resolved Debye temperature (θD) of ferric iron in minerals, except dichalcogenides, through their center shifts ranging from 400 to 550 K, is significantly larger than ferrous iron ranging from 300 to 400 K, which is consistent with the conclusion from previous work. The resolved f (Fe3+)RT with the center shift model (CSM) ranges from 0.825 to 0.925, which is larger than that obtained for f(Fe2+)RT, which ranges from 0.675 to 0.750. Meanwhile, the θD and f resolved from temperature-dependence of absorption are generally lower than from center shifts, especially for ferric iron. The significant difference between f(Fe3+) and f(Fe2+) indicates the necessity of recoilless fraction correction on the Fe3+/(Fe3++Fe2+) resolved from Mössbauer spectra.  相似文献   

6.
The paper presents the results of study of ferromanganese carbonate rocks in the Sob area (Polar Urals), which is located between the Rai-Iz massif and the Seida–Labytnangi Railway branch. These rocks represent low-metamorphosed sedimentary rocks confined to the Devonian carbonaceous siliceous and clayey–siliceous shales. In terms of ratio of the major minerals, ferromanganese rocks can be divided into three varieties composed of the following minerals: (1) siderite, rhodochrosite, chamosite, quartz, ± kutnahorite, ± calcite, ± magnetite, ± pyrite, ± clinochlore, ± stilpnomelane; (2) spessartite, rhodochrosite, and quartz, ± hematite, ± chamosite; (3) rhodochrosite, spessartite, pyroxmanite, quartz ± tephroite, ± fridelite, ± clinochlore, ± pyrophanite, ± pyrite. In all varieties, the major concentrators of Mn and Fe are carbonates (rhodochrosite, siderite, kutnahorite, Mn-calcite) and chlorite group minerals (clinochlore, chamosite). The chemical composition of rocks is dominated by Si, Fe, Mn, carbon dioxide, and water (L.O.I.): total SiO2 + Fe2O 3 tot + MnO + L.O.I. = 85.6?98.4 wt %. The content of Fe and Mn varies from 9.3 to 55.6 wt % (Fe2O 3 tot + MnO). The Mn/Fe ratio varies from 0.2 to 55.3. In terms of the aluminum module AlM = Al/(Al + Mn + Fe), the major portion of studied samples corresponds to metalliferous sediments. The δ13Ccarb range (–30.4 to–11.9‰ PDB) corresponds to authigenic carbonates formed with carbon dioxide released during the microbial oxidation of organic matter in sediments at the dia- and/or catagenetic stage. Ferromanganese sediments were likely deposited in relatively closed seafloor zones (basin-traps) characterized by periodic stagnation. Fe and Mn could be delivered from various sources: input by diverse hydrothermal solutions, silt waters in the course of diagenesis, river discharges, and others. The diagenetic delivery of metals seems to be most plausible. Mn was concentrated during the stagnation of bottom water in basin-traps. Interruption of stagnation promoted the precipitation of Mn. The presence of organic matter fostered a reductive pattern of postsedimentary transformations of metalliferous sediments. Fe and Mn were accumulated initially in the oxide form. During the diagenesis, manganese and iron oxides reacted with organic matter to make up carbonates. Relative to manganese carbonates, iron carbonates were formed under more reductive settings and higher concentrations of carbon dioxide in the interstitial solution. Crystallization of manganese and iron silicates began already at early stages of lithogenesis and ended during the regional metamorphism of metalliferous sediments.  相似文献   

7.
Sapphirine I     
Microprobe analyses of 26 natural sapphirines from 17 localities indicate that the predominant chemical substitutions in this mineral occur along the solid solution joinVI(Mg,Fe)2++IVSi4+=VI(Al, Fe)3++IVAl3+. Chromium and manganese are minor substituents. Evidence for the substitution SiAl+1/2Mg+1/2 vacancy is absent within the limits of analytical error.A partitioning scheme based on electrostatic charge balance considerations has been devised permitting calculation of Fe2+ and Fe3+ from total iron content. Results are in good agreement with previous Mössbauer studies which indicate Fe3+ is sometimes in octahedral and/or tetrahedral coordination.Distribution coefficients for Fe2+-Mg exchange equilibria between sapphirine-spinel and sapphirine-orthopyroxene are similar for most mineral pairs and suggest that most of the assemblages equilibrated at about the same temperature or that the exchange reactions are insensitive to temperature.Compositions of synthetic sapphirines as a function of temperature and pressure are qualitatively predictable from crystal chemical considerations. Changes in sapphirine composition along the MgSi= AlAl solid solution join toward more aluminous compositions stabilize the sapphirine structure at high temperatures and low pressures. The limited extent of MgSi=AlAl solid solution observed in natural sapphirines appears to be related to the requirements of geometrical fit among octahedra and tetrahedra in the almost idealized cubic closest-packed anion framework.  相似文献   

8.
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   

9.
In iron-manganese nodules from the floor of Pacific ocean, Baltic, White Sea and Kara Sea, iron bydroxide '-FeOOH was analysed in the laboratory. In buried ooze, reduction processes generate Fe(HCO3)2 which migrates into the upper part of the bottom ooze and into near bottom sea water where Fe(OH)2 is formed. The oxidation process of Fe2+ to Fe3+, without participation of iron bacteria, leads to the topotactic transformation of Fe(OH)2 to '-FeOOH. Marine water does not contain Fe2+ and cannot be a direct source of iron deposited in the nodules. Discovery of '-FeOOH in marine nodules permits the consideration that both iron and manganese were derived from the buried bottom mud, which during diagenetic processes led to the transfer of these metals in solutions and their upward migration.  相似文献   

10.
The redox cycle of iron and manganese is a major geochemica process at the boundary layers of lake sediments.Lake Aha,which lies in the suburbs of Guiyang City,Guizhou Province,China,is a medium-sized artificial reservoir with seasonally anoxic hypolimnion,Long-term sedimentary accumulation of iron and manganese resulted in their enrichment in the upper sediments,In the anoxic season,Fe^2 and Mn^2 ,formed by diological oxidation,would diffuse up to overlying waters from sediments.However,the concentration of oxidation,would diffuse up to overlying waters from sediments,However,the concentration of Fe^2 increased later and decreased earlier than that of Mn^2 .Generally,sulfate reduction occurred at 6 cm below the sediment-water interface.Whereas,in the anoxic season.the reduction reached upper sediments,inhibiting the release of Fe^2 ,The Fe concentration of anoxic water is quickly decreased from high to low as a result of reduction of the suplhur system.  相似文献   

11.
The possibility of shock wave-induced interaction between meteoritic iron was estimated based on the results of experiments on the shock wave loading of mixtures of kamacite from the Sikhote Alin iron meteorite with quartz, albite, oligoclase, enstatite, olivine, and serpentine. The experimental samples were then examined with the application of optical microscopy, microprobe analysis, and M?ssbauer spectroscopy. As a result of shock wave load, the metal was proved to become enriched in Si, while the quartz, albite, and oligoclase melted glasses acquired bivalent Fe ions. The products of our experiments with quartz and feldspar mixtures with kamacite were determined to contain paramagnetic metallic iron, and the surroundings of iron atoms in the silicate constituent of the olivine and enstatite mixtures with kamacite become locally more heterogeneous. Our results indicate that shock waves induce redox reactions between Fe and silicates according to the scheme 2Fe+2 + Si+4 = 2Fe+2 + Si0, where Fe0 and Si0 are iron and silicon in metal and Fe+2 and Si+4 are iron and silicon in the sillimanite matrix.  相似文献   

12.
The Parnok deposit is made up of stratiform lodes of iron (magnetite) and manganese (oxide-carbonate, carbonate, and carbonate-silicate) ores localized among terrigenous-carbonate sediments (black shales) on the western slope of the Polar Urals. The lithological study showed that ore-bearing sediments were accumulated in a calm hydrodynamic setting within a relatively closed seafloor area (trap depressions). Periodic development of anaerobic conditions in the near-bottom seawater was favorable for the accumulation of dispersed organic matter in the terrigenous-carbonate sediments. Carbon required to form calcium carbonates in the ore-bearing sediments was derived from carbon dioxide dissolved in seawater. In the organic-rich sediments, carbonates were formed with the participation of carbon dioxide released by the destruction of organic matter. However, δ13C values (from 0.5 to ?4.4‰ PDB) suggest a relatively low fraction of the isotopically light biogenic carbon in the host calcite. The most probable sources of Fe and Mn were hydrothermal seepages at the seafloor. The Eh-pH conditions during stagnation were favorable for the precipitation of Fe and accumulation of Mn in a dissolved state. Transition from the stagnation regime to the concentration of oxygen in near-bottom waters was accompanied by oxidation of the dissolved Mn and its precipitation. Thus, fluctuations in Eh-pH parameters of water led to the differentiation of Fe and Mn. Initially, these elements were likely precipitated as oxides and hydroxides. During the subsequent lithification, Fe and Mn were reduced to form magnetite and rhodochrosite. The texture and structure of rhodochrosite aggregates indicate that manganese carbonates already began to form at the diagenetic stage and were recrystallized during the subsequent lithogenetic stages. Isotope data (δ13C from ?8.9 to ?17.1‰ PDB) definitely indicate that the oxidized organic matter of sediment served as the main source of carbon dioxide required to form manganese carbonates. Carbonates from host rocks and manganese ores have principally different carbon isotopic compositions. Unlike carbonates of host rocks, manganese carbonates were formed with an active participation of biogeochemical processes. Further processes of metagenesis (T ≈ 250–300°C, P ≈ 2 kbar) resulted in the transformation of textures, structures, and mineral composition of all rocks of the deposit. In particular, increase in temperature and pressure provided the formation of numerous silicates in manganese ores.  相似文献   

13.
We report the first kinetic study of iron oxidation in a mica. Large singly-crystal biotite wafers were heated in air to various temperatures and for various times. Room temperature 57Fe Mössbauer spectroscopy was used to quantify the resulting Fe2+ and Fe3+ amounts. A simple activation model is consistent with the measurements and gives an activation energy of e b = 2.36 eV and an attempt frequency of f 0 = 2.9×107 Hz. We are lead to propose that, iron oxidation and ordinary dehydroxylation have the same rate limiting step: local dissociation of an OH group as OH?→O2-+H+. In oxidation this is followed by Fe2+ +H+→Fe3+H whereas in dehydroxylation it is followed by OH? +H+→H2O.  相似文献   

14.
Pumpellyite of the general formula W8X4Y8-Z12O56-n(OH)n contains Fe, Al and Mg in two crystallographically different octahedral sites. Three different pumpellyite samples covering the known compositional field from Al- to Fe-rich have been studied to determine the valence state and intracrystalline partitioning of the Fe cations between the two independent octahedral sites. Fe+2 and Fe+3 cation partitioning is interpreted on the basis of results obtained by 57Fe Mössbauer spectroscopy at 293 and 77 K and from Rietveld structure analysis performed on powder X-ray diffraction data. Pumpellyite from low-grade metamorphic rocks typically contains a majority of iron in the Fe+3 oxidation state, which is found in the smaller and less symmetrical octahedral Y-site. Fe+2 was also present in all pumpellyite samples studied and it is located in the larger and more symmetrical octahedral X-site.  相似文献   

15.
57Fe Mössbauer spectra of natural glasses (pumices and obsidians) and of synthetic glasses of granitic composition have been analyzed. — Ferric iron is found in tetrahedral coordination if enough M+-cations are available to balance the charge of both M+Fe3+O2 and M+AlO2 complexes. In other compositions the ratio of tetrahedrally to octahedrally coordinated Fe3+ depends on the ratio of mono-to divalent cations. — Ferrous iron occurs in two distinctly different octahedral sites. The existence of these sites can be attributed to different anionic units adjacent to Fe2+. The degree of polymerization of these units is reflected in the quadrupole splitting. The anionic units adjacent to Fe2+ are depolymerized for increasing mean Z/r 2 of the network modifiers, which do not stabilize M3+ in the tetrahedra by local charge balance. — Increasing pressure diminishes the geometric differences between these types of ferrous iron-oxygen-octahedra, which gives rise to a more even distribution of Fe2+ among these sites and thereby to an ordering in the network of melts.  相似文献   

16.
Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe2+ and Mn2+ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pHpzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe2+ (assuming surface detachment of Fe2+ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe2+ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe3+ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.  相似文献   

17.
The Southern Venn-Stavelot Massif is characterized by Ordovician and Devonian rocks very rich in manganese and aluminum, which are attacked by a low grade regional metamorphism. The assemblages 1 (phengite, paragonite, chlorite, chloritoid, garnet, quartz, hematite, rutile) and 2 (phengite, paragonite, chlorite, kaolinite (andalusite, pyrophyllite), garnet, quartz, hematite, rutile) are of basic interest for the formation of chloritoid. As the two rock types are isofaciell and quasi-identical in chemistry except for the iron oxides, there is clear evidence for the influence of on the chloritoid formation at its lower p-T stability limit. This can be shown by a discussion of the phase relations of chloritoid, garnet, kaolinite, chlorite and phengite in respect to the oxidation ratio mol 2 Fe2O3x 100/2 Fe2O3+ FeO of the host rocks. Especially chloritoid and chlorite change their chemistry in a characteristic way with rising oxidation ratio in getting richer and richer in manganese and magnesium (chloritoid) and magnesium (chlorite). A simultaneous increase in trivalent iron in these phases is supposed. At an oxidation ratio of 85–90 the stability limit of chloritoid is reached. The increasing substitution of manganese and magnesium up to this limit should have a stabilizing effect. In a rough estimate the oxygen partial pressure is supposed to be in the order of 10−10 atm at the stability limit of chloritoid assuming a temperature of metamorphism between 360–400° C. Rocks with oxidation ratios between 90 and 100 are characterized by the presence of kaolinite. If the oxidation ratio is still higher (all iron as Fe3+, parts of the manganese in the trivalent state), the rocks belong to assemblage 3 (phengite, paragonite, chlorite, viridine, (kaolinite), (garnet), quartz, hematite, braunite, rutile). Dedicated to Prof. Dr. K. Jasmund at his 60. birthday.  相似文献   

18.
Idiomorphic crystals of roedderite occur in melt-coated cavities of xenoliths of contact-altered quartz-sillimanite and quartz-feldspar gneisses which were ejected with the tephritic lava of the Bellerberg volcano. Physical and chemical properties of three different sets of crystals agree generally with those of roedderites from meteorites, in which so far the mineral had been found exclusively. In detail, however, there are characteristic chemical differences amongst the Eifel roedderites with one set of crystals matching closely the ideal formula (Na,K)2Mg5 Si12O30, a second set containing excess alkalies according to the substitution Na+0.5 Mg2+, and a third set richer in iron having an alkali deficiency following Fe3+Fe2++Na+.The terrestrial roedderites are considered to be precipitates from highly alkaline, MgSi-rich, but Aldeficient gas phases that evolved through contact heating of the gneisses by the tephrite magma.  相似文献   

19.
The present study deals with the direct determination of colloidal forms of iron in river-borne solids from main rivers of the Amazon Basin. The contribution of different forms of colloidal iron have been assessed using ultrafiltration associated with various techniques including electron paramagnetic resonance spectroscopy (EPR), high resolution transmission electron microscopy (HRTEM), and micro proton-induced X ray emission analysis (μPIXE). EPR shows the presence of Fe3+ bound to organic matter (Fe3+-OM) and colloidal iron oxides. Quantitative estimate of Fe3+-OM content in colloidal matter ranges from 0.1 to 1.6 weight % of dried solids and decreases as the pH of the river increases in the range 4 to 6.8. The modeling of the field data with the Equilibrium Calculation of Speciation and Transport (ECOSAT) code demonstrates that this trend is indicative of a geochemical control resulting from the solubility equilibrium of Fe oxyhydroxide phase and Fe binding to organic matter. Combining EPR and μPIXE data quantitatively confirms the presence of colloidal iron phase (min. 35 to 65% of iron content), assuming no divalent Fe is present. In the Rio Negro, HRTEM specifies the nature of colloidal iron phase mainly as ferrihydrite particles of circa 20 to 50 Å associated with organic matter. The geochemical forms of colloidal iron differentiate the pedoclimatic regions drained by the different rivers, corresponding to different major weathering/erosion processes. Modeling allows the calculation of the speciation of iron as mineral, organic and dissolved phases in the studied rivers.  相似文献   

20.
A series of powdered and oriented single crystals of riebeckite-arfvedsonite have been examined with the Mössbauer technique above and below the magnetic ordering temperatures. Using fitted spectra that result in essentially similar quadrupole pairs, site occupancies were determined for 5 samples. Fitted spectra of oriented single crystals are associated with inequal pairs. The quadrupole splitting and isomer shifts are indistinguishable from those of the powdered samples. For the purpose of determining site occupancy paramagnetic spectra at L.N. temperatures appear to have little advantage over those obtained at room temperatures. The use of cryogenics to obtain magnetic hyperfine splitting increases experimental times several fold; however we conclude that in most cases the additional information and greater accuracy of Fe+2/Fe+3 warrants the additional effort. Magnetic order detected at cryogenic temperatures has an overall antiferromagnetic character. The orientation of the magnetic moment for Fe+3 is not parallel to a principal crystallographic axis, and its orientation near 〈316〉 suggests that there is magnetic coupling between the cation ribbons containing the octahedrally coordinated iron. The magnetic behavior can be interpreted satisfactorily using the Ising model developed for two dimensional lattices and extended to loosely coupled chains.  相似文献   

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