A Mössbauer and X-ray diffraction study of annites synthesized at different oxygen fugacities and crystal chemical implications     

G. J. Redhammer  A. Beran  E. Dachs  G. Amthauer 《Physics and Chemistry of Minerals》1993,20(6):382-394

A refined set of Mössbauer parameters (isomer shifts, quadrupole splittings, Fe²⁺/Fe³⁺ ratios) and lattice parameters were obtained from annites synthesized hydrothermally at pressures between 3 and 5 kbars, temperatures ranging from 250 to 780° C and oxygen fugacities controlled by solid state buffers (NNO, QMF, IM, IQF). Mössbauer spectra showed Fe²⁺ and Fe³⁺ on both the M1 and the M2 site. A linear relationship between Fe³⁺ content and oxygen fugacity was observed. Towards low Fe³⁺ values this linear relationship ends at ≈10% of total iron showing that the Fe³⁺ content cannot be reduced further even if more reducing conditions are used. This indicates that in annite at least 10% Fe²⁺ are substituted by Fe³⁺ in order to match the larger octahedral layer to the smaller tetrahedral layer. IR spectra indicate that formation of octahedral vacancies plays an important role for charge balance through the substitution 3 Fe²⁺ → 2 Fe³⁺ + ?_(oct).  相似文献   

Estimation of Fe³⁺ from electron microprobe analyses: observations on calcic amphibole and chlorite     

C. E. JACOBSON 《Journal of Metamorphic Geology》1989,7(5):507-513

ABSTRACT Metabasites and metagreywackes from the Pelona and Rand Schists of southern California were analysed using three different electron microprobes. For all three instruments, the estimated Fe³⁺ contents of calcic amphibole, chlorite and epidote are positively correlated. For some samples, there is an additional correlation between high estimated Fe³⁺ and the presence of magnetite. These results imply that microprobe analyses can be used to discern relative differences in Fe³⁺. However, microprobe data and calculations on the sensitivity of the correction procedures to systematic analytical errors indicate that estimated values of Fe³⁺ are not significant in an absolute sense. Thus, estimates of Fe³⁺ are meaningful when comparing samples analysed with a single microprobe, but must be used with caution when comparing analyses obtained on more than one probe.  相似文献   

应用元素分析-电子顺磁共振能谱研究不同颜色青海软玉致色元素   总被引：2，自引：1，他引：1  

于海燕  阮青锋  沙鑫  杨育富 《岩矿测试》2019,38(3):288-296

颜色是软玉价值的重要体现,青海软玉颜色丰富,而致色方面的研究较为滞后。近年来青海软玉致色研究多为翠青玉和烟青玉,认为Cr~(3+)和Mn~(2+)分别为翠青玉和烟青玉致色元素。青海软玉的颜色非单一色彩,如青白色、翠绿色、灰紫色等,因此青海软玉致色应包含多种致色元素。本文在前人研究的基础上,利用X射线荧光光谱法(XRF)、化学滴定法、电感耦合等离子体质谱法(ICP-MS)和电子顺磁共振能谱(EPR)测试数据,根据分析数据与色调变化之间的关系揭示了8种颜色青海软玉的致色元素。结果表明:白玉致色元素为Fe~(3+);青白玉和碧玉致色元素为Fe~(2+)和Fe~(3+);青玉致色元素为Fe~(2+)、Fe~(3+)和高价态的Mn;翠青玉致色元素为Fe~(2+)、Fe~(3+)、Cr~(3+);黄玉和糖玉致色元素为Fe~(3+)和高价态的Mn;烟青玉致色元素为Fe~(3+)和Ti~(4+)。研究认为青海软玉中绿色调与Fe~(2+)有关,黄色调与Fe~(3+)和高价态的Mn有关,而蓝紫色调与Fe~(3+)和Ti~(4+)有关。本研究基本确定了不同颜色青海软玉的致色元素,为青海软玉致色机制的研究提供了理论依据。  相似文献   

多硅白云母中Fe²⁺的高压有序效应          下载免费PDF全文

应育浦  宋仁奎 《地质科学》1995,30(4):355-362

21个多硅白云母来自4个低温高压变质带。用电子探针、X射线粉末衍射及穆斯堡尔谱测定其化学成分、b0值及Fe²⁺占位。建立Fe²⁺(M1)/Fe²⁺(M2)对b0值相关图,发现Fe²⁺在八面体晶位有序化并解释其有序机理。  相似文献   

Mössbauer spectra of kyanite,aquamarine, and cordierite showing intervalence charge transfer     

Kathleen M. Parkin  Bruce M. Loeffler  Roger G. Burns 《Physics and Chemistry of Minerals》1977,1(3):301-311

The blue colors of several minerals and gems, including aquamarine (beryl, Be₃Al₂Si₆O₁₈) and cordierite (Al₃(Mg, Fe)₂Si₅AlO₁₈), have been attributed to charge transfer (CT) between adjacent Fe²⁺ and Fe³⁺ cations, while Fe²⁺→Ti⁴⁺ CT has been proposed for blue kyanites (Al₂SiO₅). Such assignments were based on chemical analyses and on polarization-dependent absorption bands measured in visible-region spectra. We have attempted to characterize the Fe cations in each of these minerals by Mössbauer spectroscopy (MS). In blue kyanites, significant amounts of both Fe²⁺ and Fe³⁺ were detected with MS, indicating that Fe²⁺→Fe³⁺ CT, Fe²⁺→Ti⁴⁺ CT, and Fe²⁺ and Fe³⁺ crystal field transitions each could contribute to the electronic spectra. In aquamarines, coexisting Fe²⁺ and Fe³⁺ ions were resolved by MS, supporting our assignment of the broad, relatively weak band at 16,100 cm^?1 in E∥c spectra to Fe²⁺→Fe³⁺ CT between Fe cations replacing Al³⁺ ions 4.6Å apart along c. A band at 17,500 cm^?1 in E⊥c spectra of cordierite is generally assigned to Fe²⁺ (oct)→Fe³⁺ (tet) CT between cations only 2.74 Å apart. However, no Fe³⁺ ions were detected in the MS at 293K of several blue cordierites showing the 17,500 cm^?1 band and reported to contain Fe³⁺. A quadrupole doublet with parameters consistent with tetrahedral Fe³⁺ appears in 77K MS, but the Fe³⁺/Fe²⁺ ratios from MS are much smaller than values from chemical analysis. These results sound a cautionary note when correlating Mössbauer and chemically determined Fe³⁺/Fe²⁺ ratios for minerals exhibiting Fe²⁺→Fe³⁺ CT.  相似文献   

Metasomatic oxidation of upper mantle periodotite   总被引：1，自引：0，他引：1  

Anne V. McGuire  M. Darby Dyar  Jane E. Nielson 《Contributions to Mineralogy and Petrology》1991,109(2):252-264

Examination of Fe³⁺ in metasomatized spinel peridotite xenoliths reveals new information about metasomatic redox processes. Composite xenoliths from Dish Hill, California possess remnants of magmatic dikes which were the sources of the silicate fluids responsible for metasomatism of the peridotite part of the same xenoliths. Mössbauer spectra of mineral separates taken at several distances from the dike remnants provide data on Fe³⁺ contents of minerals in the metasomatized peridotite. Clinopyroxenes contain 33% of total iron (Fe_T) as Fe³⁺ (Fe³⁺/Fe_T=0.33); orthopyroxenes contain 0.06–0.09 Fe³⁺/Fe_T; spinels contain 0.30–0.40 Fe³⁺/Fe_T; olivines contain 0.01–0.06 Fe³⁺/Fe_T; and metasomatic amphibole in the peridotite contains 0.85–0.90 Fe³⁺/Fe_T. In each mineral, Fe³⁺ and Fe²⁺ cations per formula unit (p.f.u.) decrease with distance from the dike, but the Fe³⁺/Fe_T ratios of each mineral do not vary. Clinopyroxene, spinel, and olivine Fe³⁺/Fe_T ratios are significantly higher than in unmetasomatized spinel peridotites. Metasomatic changes in Fe³⁺/Fe_T ratios in each mineral are controlled by the oxygen fugacity of the system, but the mechanism by which each phase accommodates this ratio is affected by crystal chemistry, kinetics, rock mode, fluid composition, fluid/rock ratio, and fluid-mineral partition coefficients. Ratio increases in pyroxene and spinel occur by exchange reactions involving diffusion of Fe³⁺ into existing mineral grains rather than by oxidation of existing Fe²⁺ in peridotite mineral grains. The very high Fe³⁺/Fe_T ratio in the metasomatic amphibole may be a function of the high Fe³⁺/Fe_T of the metasomatic fluid, crystal chemical limitations on the amount of Fe³⁺ that could be accommodated by the pyroxene, spinel, and olivine of the peridotite, and the ability of the amphibole structure to accommodate large amounts of 3 + valence cations. In the samples studied, metasomatic amphibole accounts for half of the bulk-rock Fe₂O₃. This suggests that patent metasomatism may produce a greater change in the redox state of mantle peridotite than cryptic metasomatism. Comparison of the metasomatized samples with unmetasomatized peridotites reveals that both Fe²⁺ and Fe³⁺ cations p.f.u. were increased during metasomatism and 50% or more of iron added was Fe³⁺. With increasing distance from the dike, the ratio of added Fe³⁺ to added Fe²⁺ increases. The high Fe³⁺/Fe_T of amphibole and phlogopite in the dikes and in the peridotite, and the high ratios of added Fe³⁺/added Fe²⁺ in pyroxenes and spinel suggest that the Fe³⁺/Fe_T ratio of the metasomatic silicate fluid was high. As the fluid perolated through and reacted with the peridotite, Fe³⁺ and C–O–H volatile species were concentrated in the fluid, increasing the fluid Fe³⁺/Fe_T.  相似文献   

Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals     

David M. Sherman 《Physics and Chemistry of Minerals》1987,14(4):355-363

A number of mixed valence iron oxides and silicates (e.g., magnetite, ilvaite) exhibit thermally induced electron delocalization between adjacent Fe²⁺ and Fe³⁺ ions and optically induced electronic transitions which are assigned to Fe²⁺→Fe³⁺ intervalence charge transfer. In this paper, the mechanism of electron delocalization (i.e., polarons versus itinerant electrons) and the nature of optically induced intervalence charge-transfer in minerals are investigated using molecular orbital theory. SCF-Xα-SW molecular orbital calculations were done for several mixed-valence (Fe₂O₁₀)^15? clusters corresponding to edgesharing Fe²⁺ and Fe³⁺ coordination polyhedra. A spinunrestricted formalism was used so that the effect of ferromagnetic versus antiferromagnetic coupling of adjacent Fe²⁺ and Fe³⁺ cations could be determined. The molecular orbital results can be related to the polaron theory of solid state physics and the perturbation theory formalism used by Robin and Day (1967) and others to describe electron transfer in mixed valence compounds. Intervalence charge-transfer results from the overlap of Fe(3d) orbitals across the shared edges of adjacent FeO₆ polyhedra to give weak Fe-Fe bonds. Electron delocalization, however, requires that adjacent Fe cations be ferromagnetically coupled. Antiferromagnetic coupling results in distinguishable Fe²⁺ and Fe³⁺ cations. Electronic transitions between the Fe-Fe bonding and Fe-Fe antibonding orbitals results in the optically-induced intervalence charge transfer bands observed in the electronic spectra of mixed valence minerals. Such transitions are predicted to be polarized along the metal-metal bond direction, in agreement with experimental observations.  相似文献   

On the origin of natural sapphire color     

L. V. Nikolskaya  V. M. Terekhova  M. I. Samoilovich 《Physics and Chemistry of Minerals》1978,3(3):213-224

An attempt has been made to interpret natural sapphire optical absorption spectra with regard to the exchange-coupled pairs of iron impurities in their ferric and ferrous states. Level schemes have been calculated for Fe³⁺-Fe³⁺ and Fe²⁺-Fe²⁺ pairs of all the orders, their symmetry being observed. The selection rules are discussed. EPR and infrared spectroscopy information has been used to assist the optical spectroscopy data. The sapphire color has been interpreted as a function of Fe²⁺/Fe³⁺ ratios and of the presence of their pairs in the stone. The various types of charge compensation in Fe²⁺→Al³⁺ isomorphism are discussed.  相似文献   

The structural behavior of ferric and ferrous iron in aluminosilicate glass near meta-aluminosilicate joins     

Bjorn O. Mysen 《Geochimica et cosmochimica acta》2006,70(9):2337-2353

Iron-57 resonant absorption Mössbauer spectroscopy was used to describe the redox relations and structural roles of Fe³⁺ and Fe²⁺ in meta-aluminosilicate glasses. Melts were formed at 1500 °C in equilibrium with air and quenched to glass in liquid H₂O with quenching rates exceeding 200 °C/s. The aluminosilicate compositions were NaAlSi₂O₆, Ca_0.5AlSi₂O₆, and Mg_0.5AlSi₂O₆. Iron oxide was added in the form of Fe₂O₃, NaFeO₂, CaFe₂O₄, and MgFe₂O₄ with total iron oxide content in the range ∼0.9 to ∼5.6 mol% as Fe₂O₃. The Mössbauer spectra, which were deconvoluted by assuming Gaussian distributions of the hyperfine field, are consistent with one absorption doublet of Fe²⁺ and one of Fe³⁺. From the area ratios of the Fe²⁺ and Fe³⁺ absorption doublets, with corrections for differences in recoil-fractions of Fe³⁺ and Fe²⁺, the Fe³⁺/ΣFe is positively correlated with increasing total iron content and with decreasing ionization potential of the alkali and alkaline earth cation. There is a distribution of hyperfine parameters from the Mössbauer spectra of these glasses. The maximum in the isomer shift distribution function of Fe³⁺, δ_Fe³⁺, ranges from about 0.25 to 0.49 mm/s (at 298 K relative to Fe metal) with the quadrupole splitting maximum, Δ_Fe³⁺, ranging from ∼1.2 to ∼1.6 mm/s. Both δ_Fe³⁺ and δ_Fe²⁺ are negatively correlated with total iron oxide content and Fe³⁺/ΣFe. The dominant oxygen coordination number Fe³⁺ changes from 4 to 6 with decreasing Fe³⁺/ΣFe. The distortion of the Fe³⁺-O polyhedra of the quenched melts (glasses) decreases as the Fe³⁺/ΣFe increases. These polyhedra do, however, coexist with lesser proportions of polyhedra with different oxygen coordination numbers. The δ_Fe²⁺ and Δ_Fe²⁺ distribution maxima at 298 K range from ∼0.95 to 1.15 mm/s and 1.9 to 2.0 mm/s, respectively, and decrease with increasing Fe³⁺/ΣFe. We suggest that these hyperfine parameter values for the most part are more consistent with Fe²⁺ in a range of coordination states from 4- to 6-fold. The lower δ_Fe²⁺-values for the most oxidized melts are consistent with a larger proportion of Fe²⁺ in 4-fold coordination compared with more reduced glasses and melts.  相似文献   

SCF-Xα-SW MO Study of Fe-O and Fe-OH chemical bonds; applications to the mössbauer spectra and magnetochemistry of hydroxyl-bearing Fe3+ oxides and silicates     

David M. Sherman 《Physics and Chemistry of Minerals》1985,12(5):311-314

Results of SCF-Xα-SW molecular orbital calculations on (FeO₄(OH)₂)^7? and (FeO₆)^9? clusters are used to investigate the differences between Fe-O and Fe-OH bonding in hydroxyl-bearing iron oxides and silicates. The Fe³⁺-OH^? bond is more ionic, and has a smaller spinpolarization, then the Fe³⁺-O^2? bond. The smaller spinpolarizability of OH^? ligands explains why superexchange interactions between hydroxo-bridged Fe³⁺ cations are much weaker than those between oxo-bridged Fe³⁺ cations. Replacement of oxygens in the Fe³⁺ coordination environment by OH^? ligands appears to promote the covalency between Fe³⁺ centers and O^2? oxygens. The increased covalency lowers the effective spin of the Fe atom. This, in turn, explains the decreased magnetic hyperfine fields at the Fe nucleus in FeOOH polymorphs relative to those found in Fe³⁺ oxides.  相似文献   

Optical absorption spectra and Fe distribution in the structures of Li-Fe micas     

A. N. Platonov  V. M. Khomenko  T. N. Shuriga 《Geochemistry International》2009,47(2):174-185

The paper proposes pioneering data on the polarized optical absorption spectra of Li-Fe micas: intermediate members of the siderophyllite-zinnwaldite-polylithionite and annite-protolithionite-zinnwaldite-trilithionite series with variable Fe and Li proportions and Li- and Fe-bearing muscovite (phengite). Based on the analysis of structural data, the complicated structure of the Fe²⁺ → Fe³⁺ charge transfer band in the mica structures is explained, and arguments are presented to justify the ascribing of its shortwave component (CTB-1, ν = 17200-14900 cm^?1) to charge transfer in the pair Fe²⁺(M2) → Fe³⁺(M2) and the longwave component (CTB-2, ν = 14200-13600 cm^?1) to charge transfer in the pair Fe²⁺(M1) Fe³⁺(M2). It is demonstrated that the anomalous shift of the superposition of two-component CTB toward the shortwave region, to 17000 cm^?1, results from a decrease in the length of oxygen edges between adjacent M2M2 and M1M2 tetrahedrons when Li is accommodated in the mica structure. The first data are presented on the spectrum of Fe²⁺ ions in large distorted M3(M1) tetrahedrons (OAC Fe²⁺ II) in hetero-octahedral Li micas (zinnwaldite), and the behavior of the corresponding absorption bands at 11400 and 8000 cm^?1 is determined. It is proved that characteristics of the optical spectra of Fe²⁺ ions can be used as an indicator of the structure of the octahedral layer in the mica structures. Results of the comparative analyses of spectral parameters of the Fe²⁺ → Fe³⁺ charge transfer, crystal field spectra of Fe²⁺ ions, and the crystal-chemical characteristics controlling them in micas of the polylithionite-siderophyllite series are completely consistent with the character of cation ordering in the crystal structures of these micas determined by X-ray diffraction analysis.  相似文献   

Effect of the disproportionation reaction of ferrous iron in impact-evaporation processes     

O. I. Yakovlev  Yu. P. Dikov  M. V. Gerasimov 《Geochemistry International》2009,47(2):134-142

Evidence for the disproportionation of iron was found in model experiments imitating impact melting, evaporation, and condensation. The experiments were carried out using a laser system at a characteristic temperature of ～3000–4000 K and a pulse duration of ～10^?3 s in a He atmosphere (P = 1 atm). Augite and mixtures of peridotite with MnO₂ and WO₃ were used as starting target materials. Experimental products (condensed vapor phase) were analyzed by X-ray photoelectron spectroscopy. The results of condensate analysis provided compelling evidence for the presence of iron in three oxidation states (Fe⁰, Fe²⁺, and Fe³⁺). In an experiment with augite, the proportions of iron species of different valences were similar to the stoichiometry of the disproportionation reaction. Similar evidence for this reaction was first found in a condensate from the samples of the fine fraction of the Luna 16 regolith. In the layers of the lunar condensate, the proportions of the valence states of iron were on average Fe⁰:Fe²⁺:Fe³⁺ = 1.2: 1.9: 0.7.  相似文献   

Advances of ferrous and ferric Mössbauer recoilless fractions in minerals and glasses     

《地学前缘(英文版)》2022,13(2):101316

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 (θ_D) 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 θ_D 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   

The crystal chemistry of ferric iron in Fe0.05Mg0.95SiO3 perovskite as determined by Mössbauer spectroscopy in the temperature range 80–293 K     

C. A. McCammon 《Physics and Chemistry of Minerals》1998,25(4):292-300

Mössbauer spectra were recorded at multiple temperatures between 80 and 293 K to study the nature of Fe³⁺ in Fe_0.05Mg_0.95SiO₃ perovskite that had been synthesised in a multianvil press at 1650 °C and 25 GPa at its mimimum stability limit. The Mössbauer data were fitted to a model with quadrupole splitting distributions (Fe²⁺) and Lorentzian lineshapes (Fe³⁺ and Feⁿ⁺). The centre shift data were fitted to a Debye model with the following results: Θ_M (Fe²⁺)=365±52 K and Θ_M (Fe³⁺)=476±96 K. Hyperfine parameter data for Fe³⁺ suggest occupation of the octahedral site only. The average valence seen by the Mössbauer effect in rapid electron exchange that occurs between Fe²⁺ and Fe³⁺ is calculated from the hyperfine parameters to be 2.50±0.07. Correction of area fractions for site-dependent recoil-free fractions gives a value for Fe³⁺/∑Fe of 9.4±1.4%, which is independent of temperature. A perovskite phase of similar composition synthesised in the multianvil press at higher oxygen fugacity gives a value for Fe³⁺/∑Fe of 16±3%, where Fe³⁺ appears to occupy both sites in the perovskite structure.  相似文献   

Crystal chemistry of Fe-containing sphalerites   总被引：2，自引：0，他引：2  

P. Lepetit  K. Bente  T. Doering  S. Luckhaus 《Physics and Chemistry of Minerals》2003,30(4):185-191

 Cell dimensions and solvus properties of Fe-containing sphalerites, depending on temperature and sulfur fugacity, were investigated using equilibrated powdered materials synthesized from elements and binary sulfides under vacuum. The Fe solvus in sphalerite, determined by optical microscopy and microprobe analysis, are directly correlated with increasing temperature and decreasing sulfur fugacity controlled by solid-state buffers. The increase of lattice parameters with Fe correlates with an increase of FeS independent of sulfur fugacity up to 10 mol% FeS within ZnS. Above about 10 mol% the lattice parameters are strongly depending on the sulfur fugacity controlled Fe³⁺/Fe²⁺ ratios. The Fe³⁺/Fe²⁺ ratios determined by Moessbauer spectroscopy and involving metal vacancies depend on the sulfur fugacity. The critical Fe²⁺ content determined by experimental simulations as well as the minimal Fe³⁺/ Fe²⁺ ratios agree with the required minimal Fe content for CuFeS₂-DIS in sphalerite. The critical Fe²⁺ content also agrees with the change of Moessbauer signal from a singlet to a doublet for Fe²⁺ containing sphalerite. Pyrrhotite exsolutions in sphalerite caused by higher sulfur fugacity show orientationally intergrown with the sphalerite matrix. Density data calculated from lattice parameters and composition are compared with experimental density measurements. Received: 25 April 2001 / Accepted: 14 February 2003  相似文献   

57Fe Mössbauer study on compositions of the series Fe3+TaO4-Fe2+Ta2O6     

E. Schmidbauer  J. Lebküchner-Neugebauer 《Physics and Chemistry of Minerals》1987,15(2):196-200

Fe⁵⁷ Mössbauer spectra were measured on compositions of the series Fe_1?x/3Ta_1+x/3O₄, 0≤x≤1. The spectra are characterized by mixed valencies of Fe²⁺ and Fe³⁺ ions for 0<x<1. Starting from x=0 with rutile structure, a trirutile structure forms towards x=1. Quadrupole splitting QS of Fe³⁺ is QS(Fe³⁺)≈0.55 mm/s and isomer shift IS is IS(Fe³⁺)≈0.40 mm/s (referred to Fe); both quantities exhibit minor variations along the series. The Fe²⁺ subspectra for x>0.5 were fitted using one symmetrical doublet; however, for x<0.5 two symmetrical doublets were necessary to describe these patterns. QS(Fe²⁺)=2.0–3.2 mm/s and IS(Fe²⁺)=0.90–1.15 mm/s for all compositions. In the case x<0.5, marked temperature dependent QS values appear to exist. This feature may be related to short range order effects and possibly also in part to intervalence electron transfer betwee Fe²⁺ and Fe³⁺ ions.  相似文献   

Alteration patterns of chromian spinels from La Cabaña peridotite,south-central Chile     

Fernando Barra  Fernando Gervilla  Elkin Hernández  Martin Reich  José Alberto Padrón-Navarta  José Maria González-Jiménez 《Mineralogy and Petrology》2014,108(6):819-836

La Cabaña peridotite is part of a dismembered ophiolite complex located within the metamorphic basement of the Coastal Cordillera of south-central Chile, and is the only location in Chile were Cr-spinels have been described so far. The La Cabaña peridotite is part of the Western Series unit, which comprises meta-sedimentary rocks, metabasites, and serpentinized ultramafic rocks. This unit has been affected by greenschist-facies metamorphism with reported peak PT conditions of 7.0–9.3 kbar and 380°–420 °C. Within La Cabaña peridotite Cr-spinels are present in two localities: Lavanderos and Centinela Bajo. In Lavanderos, Cr-spinel occurs in small chromitite pods and as accessory/disseminated grains with a porous or spongy texture in serpentinite, whereas in Centinela Bajo Cr-spinel is present as accessory zoned grains in partly serpentinized dunites, and in chromitite blocks. All Cr-spinels display variable degrees of alteration to Fe²⁺-rich chromite with a variation trend of major elements from chromite to Fe²⁺-rich chromite similar to those observed in other locations, i.e., an increase in Fe₂O₃ and FeO, a decrease in Al₂O₃ and MgO. Cr₂O₃ content increases from chromite to Fe²⁺-rich chromite in chromitite pods from Lavanderos and chromitite blocks from Centinela Bajo, but decreases in ferrian chromite zones in accessory grains from Centinela Bajo. The minor element (Ti, V, Zn, Ni) content is mostly low and does not exceed 0.4 wt.%, with the exception of MnO (<0.9 wt.%), which shows a correspondence with increasing degree of alteration. Cr# (Cr/Cr?+?Al) versus Mg# (Mg/Mg?+?Fe²⁺) and Fe³⁺/Fe³⁺+Fe²⁺ versus Mg# plots are used to illustrate the Cr-spinel alteration process. Overall, the Cr-spinels from Lavanderos (chromitite pods and disseminated grains) exhibit Cr# values ranging from 0.6 to 1.0, Mg# (Mg/Mg?+?Fe²⁺) below 0.5, and (Fe³⁺/Fe³⁺+Fe²⁺) <0.4. Cr-spinels from chromitites in Centinela Bajo have Cr# and Mg# values that range from 0.65 to 1.0, and 0.7-0.3, respectively, and (Fe³⁺/Fe³⁺+Fe²⁺)?3+/Fe³⁺+Fe²⁺) ratio is less than 0.4 in chromite cores and Fe²⁺-rich chromite, and >0.5 in ferrian chromite and Cr-magnetite. Interpretation of the data obtained and Cr-spinel textures indicate that the alteration of Cr-spinel is a progressive process that involves in its initial stages the reaction of chromite with olivine under water-saturated conditions to produce clinochlore and Fe²⁺-rich chromite. During this stage the chromite can also incorporate Ni, Mn, and/or Zn from the serpentinization fluids. As alteration progresses, Fe²⁺-rich chromite loses mass resulting in the development of a spongy texture. In a later stage and under more oxidizing conditions Fe³⁺ is incorporated in chromite/Fe²⁺-rich chromite shifting its composition to an Fe³⁺-rich chromite (i.e., ferrian chromite). Depending on the fluid/rock and Cr-spinel/silicate ratios, Cr-magnetite can also form over Fe²⁺-rich chromite and/or ferrian chromite as a secondary overgrowth. The compositional changes observed in Cr-spinels from La Cabaña reflect the initial stages of alteration under serpentinization conditions. Results from this study show that the alteration of Cr-spinels is dependent on temperature. The degree and extent of alteration (formation of Fe²⁺-rich and/or ferrian chromite) are controlled by the redox nature of the fluids, the Cr-spinel/silicate and the fluid/rock ratios.  相似文献   

Precise determination of ferrous iron in silicate rocks     

Tetsuya YokoyamaEizo Nakamura 《Geochimica et cosmochimica acta》2002,66(6):1085-1093

We have developed a highly precise method for the determination of ferrous iron (Fe²⁺) in silicate rocks. Our new method is based on Wilson’s procedure (1955) in which surplus V⁵⁺ is used to oxidize Fe²⁺ into Fe³⁺ while equivalently reducing V⁵⁺ into V⁴⁺. Because V⁴⁺ is more resistant to atmospheric oxidation than Fe²⁺, Fe²⁺ in the sample can be determined by measuring unreacted V⁵⁺ by adding excess Fe²⁺ after sample decomposition and then titrating the unreacted Fe²⁺ with Cr⁶⁺. With our method, which involves conditioning the sample solution with 5 M H₂SO₄ in a relatively small beaker (7 mL), the oxidation of Fe²⁺ or V⁴⁺ that leads to erroneous results can be completely avoided, even in 100-h sample decompositions at 100°C. We have measured the concentration of FeO in 15 standard silicate rock powders provided by the Geological Survey of Japan (GSJ). Analytical reproducibility was better than 0.5% (1σ) for all but those samples that had small amounts of Fe²⁺ (<1.5 wt.% of FeO). Fourteen of these samples gave FeO contents significantly higher than the GSJ reference values. This likely indicates that the GSJ reference values, obtained by compiling previously published data, contain a large number of poor-quality data obtained by methods with lower recovery of Fe²⁺ caused by oxidation or insufficient sample decomposition during analyses. To achieve accurate determinations of Fe²⁺ in our method, several factors besides the oxidation must be considered, including: (1) long-term variations in the concentration of Fe²⁺ solution must be corrected; (2) excess use of the indicator must be avoided; and (3) the formation of inert FeF⁺ complex must be avoided during titration when using boric acid as a masking agent.  相似文献   

Structure and physical property relations of Mn ilvaite     

E. Schmidbauer  Th. Fehr  R. Hochleitner  J. Schneider 《Physics and Chemistry of Minerals》2005,32(5-6):388-399

Structural and compositional data as well as ⁵⁷Fe Mössbauer parameters were determined on a natural Mn-rich monoclinic ilvaite crystal (ideal composition CaFe ₂ ²⁺ Fe³⁺Si₂O₈(OH)) which was used for electrical conductivity and thermopower measurements (part 2 of this paper). A zonar structure was found by electron microprobe analysis with a strong decrease in Mn concentration from the rim to the centre of the crystal in a plane perpendicular to the [001] direction. X-ray powder diffraction analysis of the most Mn-rich composition was performed. Mn²⁺ cations populate preferentially M2 sites of the ilvaite unit cell (space group P21/a), to a lower extent they reside on M1 and a reduced part is on Ca sites. The monoclinic angle was determined to β=90.178(4)°. The structural results are compared to literature data for other natural Mn-rich as well as low-impurity ilvaites; this concerns in particular the lattice b parameter and the undecided issue of the varying β angle. In the literature, the order parameter σ, which describes the varying degree of ordering of Fe²⁺–Fe³⁺ pairs on M11 and M12 sites in chains running parallel to the [001] direction, and structural defects are thought to be related to β. The interrelationship between β and σ with respect to a possible twin domain structure is discussed. Various ⁵⁷Fe Mössbauer spectra were recorded between 151 K and 327 K. Mössbauer parameters and Fe²⁺/Fe³⁺ concentration ratios were determined from the fits to the spectra. Fitting of subspectra was accomplished with the idea to find assignments of Fe²⁺ and Fe³⁺ doublets in agreement with X-ray results. The fraction of Mn²⁺ substituting Fe²⁺ on M1 sites could be estimated.  相似文献   

Identifying characteristics of charge transfer transitions in minerals     

Stephanie M. Mattson  George R. Rossman 《Physics and Chemistry of Minerals》1987,14(1):94-99

Criteria used to identify Fe²⁺-Fe³⁺ and Fe²⁺-Ti⁴⁺ intervalence charge transfer absorption bands in electronic spectra are reviewed and compared to the characteristics of unperturbed Fe²⁺ crystal field bands and those that are intensified by interaction with Fe³⁺. Band energy is the least definitive diagnostic criterion. Changes in band intensity with temperature are also of limited value. Large widths are the most reliable characteristic of charge transfer bands. New optical absorption spectra are presented for euclase, as well as 80 K spectra of rockbridgeite, babingtonite and lazulite. Comparison of optical spectra to magnetic susceptibility measurements for rockbridgeite and babingtonite provides support for recent theories regarding the effect of magnetic coupling on the variation of charge transfer intensity with temperature.  相似文献